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WO2018222349A1 - Batterie métal alcalin-soufre de forme adaptable - Google Patents

Batterie métal alcalin-soufre de forme adaptable Download PDF

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Publication number
WO2018222349A1
WO2018222349A1 PCT/US2018/031524 US2018031524W WO2018222349A1 WO 2018222349 A1 WO2018222349 A1 WO 2018222349A1 US 2018031524 W US2018031524 W US 2018031524W WO 2018222349 A1 WO2018222349 A1 WO 2018222349A1
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Prior art keywords
sulfonated
sulfur
carbon
active material
graphene
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PCT/US2018/031524
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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 US15/612,537 external-priority patent/US11394058B2/en
Priority claimed from US15/612,497 external-priority patent/US11335946B2/en
Application filed by Nanotek Instruments, Inc. filed Critical Nanotek Instruments, Inc.
Priority to JP2019565844A priority Critical patent/JP2020523733A/ja
Priority to CN201880035240.1A priority patent/CN110679008B/zh
Priority to KR1020197036699A priority patent/KR20200014325A/ko
Publication of WO2018222349A1 publication Critical patent/WO2018222349A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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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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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • 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
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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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    • H01M4/02—Electrodes composed of, or comprising, active material
    • 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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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • 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
    • H—ELECTRICITY
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—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
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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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
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • 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
    • 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
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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-sulfur batteries, including rechargeable lithium metal-sulfur batteries, sodium metal-sulfur batteries, lithium-ion sulfur batteries, and sodium-ion sulfur batteries.
  • Li-ion Rechargeable lithium-ion
  • Li-ion Rechargeable lithium-ion
  • Li-ion Rechargeable lithium-ion
  • Li metal batteries including Li-sulfur and Li metal-air batteries
  • EV electric vehicle
  • HEV hybrid electric vehicle
  • portable electronic devices such as lap-top computers and mobile phones.
  • Lithium as a metal element has the highest capacity (3,861 mAh/g) compared to any other metal or metal-intercalated compound as an anode active material (except Li 4 4 Si, which has a specific capacity of 4,200 mAh/g).
  • Li metal batteries have a
  • rechargeable lithium metal batteries were produced using non-lithiated compounds having relatively high specific capacities, such as TiS 2 , MoS 2 , Mn0 2 , Co0 2 , and V 2 0 5 , as the cathode active materials, which were coupled with a lithium metal anode.
  • non-lithiated compounds having relatively high specific capacities such as TiS 2 , MoS 2 , Mn0 2 , Co0 2 , and V 2 0 5
  • the cathode active materials When the battery was discharged, lithium ions were transferred from the lithium metal anode through the electrolyte to the cathode, and the cathode became lithiated.
  • the lithium metal resulted in the formation of dendrites at the anode that ultimately grew to penetrate through the separator, causing internal shorting and explosion.
  • the production of these types of secondary batteries was stopped in the early 1990's, giving ways to lithium-ion batteries.
  • lithium-ion batteries pure lithium metal sheet or film was replaced by carbonaceous materials as the anode.
  • the carbonaceous material absorbs lithium (through intercalation of lithium ions or atoms between graphene planes, for instance) and desorbs lithium ions during the re-charge and discharge phases, respectively, of the lithium ion battery operation.
  • the carbonaceous material may comprise primarily graphite that can be intercalated with lithium and the resulting graphite intercalation compound may be expressed as Li x C 6 , where x is typically less than 1.
  • Li-ion cells typically use a lithium transition-metal oxide or phosphate as a positive electrode (cathode) that de/re-intercalates Li + at a high potential with respect to the carbon negative electrode (anode).
  • the specific capacity of lithium transition-metal oxide or phosphate based cathode active material is typically in the range from 140-170 mAh/g.
  • the specific energy of commercially available Li-ion cells is typically in the range from 120-250 Wh/kg, most typically 150-220 Wh/kg. These specific energy values are two to three times lower than what would be required for battery-powered electric vehicles to be widely accepted.
  • Li-S lithium-sulfur
  • a Li-S cell consists of elemental sulfur as the positive electrode and lithium as the negative electrode.
  • the lithium-sulfur cell operates with a redox couple, described by the reaction S 8 + 16Li 8Li 2 S that lies near 2.2 V with respect to Li + /Li°.
  • This electrochemical potential is approximately 2/3 of that exhibited by conventional positive electrodes (e.g. LiMn0 4 ) in a conventional lithium-ion battery.
  • Li-S cells have the opportunity to provide a significantly higher energy density (a product of capacity and voltage). Assuming complete reaction to Li 2 S, energy densities values can approach 2,500 Wh/kg and 2,800 Wh/J, respectively, based on the combined Li and S weight or volume.
  • the energy densities can reach approximately 1,000 Wh/kg and 1, 100 Wh/J, respectively.
  • the current Li-sulfur cells reported by industry leaders in sulfur cathode technology have a maximum cell specific energy of 250-400 Wh/kg and 500-650 Wh/L (based on the total cell weight or volume), which are far below what is possible.
  • Sulfur or sulfur-containing organic compounds are highly insulating, both electrically and ionically. To enable a reversible electrochemical reaction at high current densities or charge/discharge rates, the sulfur must maintain intimate contact with an electrically conductive additive.
  • Various carbon-sulfur composites have been utilized for this purpose, but only with limited success owing to the limited scale of the contact area. Typical reported capacities are between 300 and 550 mAh/g (based on the cathode carbon-sulfur composite weight) at moderate rates.
  • the cell tends to exhibit significant capacity decay during discharge-charge cycling. This is mainly due to the high solubility of the lithium polysulfide anions formed as reaction intermediates during both discharge and charge processes in the polar organic solvents used in electrolytes.
  • the lithium polysulfide anions can migrate through the separator to the Li negative electrode whereupon they are reduced to solid precipitates (Li 2 S 2 and/or Li 2 S), causing active mass loss.
  • the solid product that precipitates on the surface of the positive electrode during discharge becomes electrochemically irreversible, which also contributes to active mass loss.
  • a significant drawback with cells containing cathodes comprising elemental sulfur, organosulfur and carbon-sulfur materials relates to the dissolution and excessive out-diffusion of soluble sulfides, polysulfides, organo-sulfides, carbon-sulfides and/or carbon-polysulfides (hereinafter referred to as anionic reduction products) from the cathode into the rest of the cell.
  • anionic reduction products This phenomenon is commonly referred to as the Shuttle Effect.
  • Zhang, et al. (US Pub. No. 2014/0234702; 08/21/2014) makes use of a chemical reaction method of depositing S particles on surfaces of isolated graphene oxide (GO) sheets. But, this method is incapable of creating a large proportion of S particles on GO surfaces (i.e. typically ⁇ 66% of S in the GO-S nanocomposite composition).
  • the resulting Li-S cells also exhibit poor rate capability; e.g. the specific capacity of 1, 100 mAh/g (based on S weight) at 0.02 C rate is reduced to ⁇ 450 mAh/g at 1.0 C rate.
  • a solution precipitation method was disclosed by Liu, et al. (US Pub. No. 2012/0088154; 04/12/2012) to prepare graphene-sulfur nanocomposites (having sulfur particles adsorbed on GO surfaces) for use as the cathode material in a Li-S cell.
  • the method entails mixing GO sheets and S in a solvent (CS 2 ) to form a suspension.
  • the solvent is then evaporated to yield a solid nanocomposite, which is then ground to yield nanocomposite powder having primary sulfur particles with an average diameter less than approximately 50 nm.
  • this method does not appear to be capable of producing S particles less than 40 nm.
  • the resulting Li-S cell exhibits very poor cycle life (a 50% decay in capacity after only 50 cycles).
  • the Li-S cell retains less than 80% of its original capacity after 100 cycles.
  • the cell also exhibits a poor rate capability (specific capacity of 1,050 mAh/g(S wt.) at 0.1 C rate, dropped to ⁇ 580 mAh/g at 1.0 C rate). Again, this implies that a large proportion of S did not contribute to the lithium storage, resulting in a low S utilization efficiency.
  • S utilization efficiency electro-active cathode materials
  • lithium metal including pure lithium, lithium alloys of high lithium content with other metal elements, or lithium-containing compounds with a high lithium content; e.g. > 80%) or preferably > 90%> by weight Li
  • Lithium metal would be an ideal anode material in a lithium-sulfur secondary battery if dendrite related issues could be addressed.
  • Sodium metal (Na) and potassium metal (K) have similar chemical characteristics to Li and the sulfur cathode in room temperature sodium-sulfur cells (RT Na-S batteries) or potassium-sulfur cells (K-S) face the same issues observed in Li-S batteries, such as: (i) low active material utilization rate, (ii) poor cycle life, and (iii) low Coulombic efficiency. Again, these drawbacks arise mainly from insulating nature of S, dissolution of S and Na or K polysulfide intermediates in liquid electrolytes (and related Shuttle effect), and large volume change during charge/discharge.
  • the cathode active material amount is typically 1.5-2.5 times higher than the anode active material amount in a cell.
  • the weight proportion of the anode active material (e.g. carbon) in a Na ion-sulfur or Li ion-sulfur battery cell is typically from 15% to 20%, and that of the cathode active material from 20%) to 35% (mostly ⁇ 30%>).
  • the weight fraction of the cathode and anode active materials combined is typically from 35% to 50% of the cell weight.
  • the low active material mass loading is primarily due to the inability to obtain thicker electrodes (thicker than 100-200 ⁇ ) using the conventional slurry coating procedure. This is not a trivial task as one might think, and in reality the electrode thickness is not a design parameter that can be arbitrarily and freely varied for the purpose of optimizing the cell performance.
  • an object of the present invention is to provide a rechargeable alkali metal-sulfur cell based on rational materials and battery designs that overcome or significantly reduce the following issues commonly associated with conventional Li-S and Na-S cells: (a) dendrite formation (internal shorting); (b) extremely low electric and ionic conductivities of sulfur, requiring large proportion (typically 30-55%) of non-active conductive fillers and having significant proportion of non-accessible or non-reachable sulfur or alkali metal polysulfides); (c) dissolution of S and alkali metal polysulfide in electrolyte and migration of polysulfides from the cathode to the anode (which irreversibly react with Li or Na metal at the anode), resulting in active material loss and capacity decay (the shuttle effect); (d) short cycle life; and (e) low active mass loading in both the anode and the cathode.
  • a specific object of the present invention is to provide a rechargeable alkali metal-sulfur battery (e.g. mainly Li-S and room temperature Na-S battery) that exhibits an exceptionally high specific energy or high energy density.
  • a rechargeable alkali metal-sulfur battery e.g. mainly Li-S and room temperature Na-S battery
  • One particular technical goal of the present invention is to provide an alkali metal-sulfur or alkali ion-sulfur cell with a cell specific energy greater than 400 Wh/kg, preferably greater than 500 Wh/kg, more preferably greater than 600 Wh/kg, and most preferably greater than 700 Wh/kg (all based on the total cell weight).
  • the volumetric energy density is greater than 600 Wh/L, further preferably greater than 800 Wh/L, and most preferably greater than 1,000 Wh/L.
  • Another object of the present invention is to provide an alkali metal-sulfur cell that exhibits a high cathode specific capacity, higher than 1,200 mAh/g based on the sulfur weight, or higher than 1,000 mAh/g based on the cathode composite weight (including sulfur, conducting additive or substrate, and binder weights combined, but excluding the weight of cathode current collector).
  • the specific capacity is preferably higher than 1,400 mAh/g based on the sulfur weight alone or higher than 1,200 mAh/g based on the cathode composite weight. This must be accompanied by a high specific energy, good resistance to dendrite formation, and a long and stable cycle life.
  • 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.
  • the present invention provides a method of producing a lithium-sulfur battery or sodium- sulfur 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 Li-S or Na-S battery can be a primary battery (non- rechargeable) or a secondary battery (rechargeable), including a rechargeable lithium metal- sulfur or sodium metal-sulfur battery (having a lithium or sodium metal anode) and a lithium-ion sulfur or sodium-ion sulfur battery (e.g. having a first lithium intercalation compound as an anode active material).
  • the invention provides an alkali-sulfur cell comprising: (a) a quasi-solid cathode containing about 30% to about 95% by volume of a sulfur-containing cathode active material (preferably selected from sulfur, a metal-sulfur compound, a sulfur- carbon composite, a sulfur-graphene composite, a sulfur-graphite composite, an organic sulfur compound, a sulfur-polymer composite, or a combination thereof), 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 (a) a
  • 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 1.0% 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 invention provides an alkali-sulfur cell comprising: (A) a quasi-solid anode containing about 1.0% 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 containing a sulfur-containing cathode active material selected from sulfur, a metal-sulfur compound, a sulfur-carbon composite, a sulfur-graphene composite, a sulfur- graphite composite, an organic sulfur compound, a sulfur-polymer composite, or
  • the presently invented quasi-solid polymer electrodes are deformable, flexible, and shape-conformable, enabling a shape-conformable battery.
  • the present invention also provides a method of preparing an alkali-sulfur 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,
  • 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, preferably lower than 0.5 x 10 6 g/mole), polypropylene oxide (PPO), poly(acrylonitrile) (PAN),
  • PEO poly(ethylene oxide)
  • PPO polypropylene oxide
  • PAN poly(acrylonitrile)
  • poly(methyl methacrylate) PMMA
  • poly(vinylidene fluoride) PVDF
  • poly bis-methoxy ethoxyethoxide-phosphazene polyvinyl chloride
  • Polydimethylsiloxane poly(vinylidene fluoride)-hexafluoropropylene (PVDF-HFP)
  • a sulfonated derivative thereof 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 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 copoly
  • 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 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 resulting electrolyte is in a supersaturated state without precipitation or crystallization of the salt and/or polymer from the electrolyte.
  • 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 resulting electrolyte is in a supersaturated state without precipitation or crystallization of the salt and/or polymer from the electrolyte.
  • 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;
  • the alkali metal-sulfur cell is a sodium metal-sulfur cell or sodium -ion sulfur 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,
  • 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 , most preferably no less than 40 mg/cm 2 ) 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 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
  • the resulting lithium battery cell does not exhibit a satisfactory cycle life (i.e. capacity decays rapidly).
  • the cathode active material constitutes an electrode active material loading greater than 15 mg/cm 2 (preferably greater than 25 mg/cm 2 , more preferably greater than 35 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).
  • 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
  • resin binder resin binder
  • 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).
  • a quasi-solid anode consisting of anode active material particles and conductive filaments directly mixed or dispersed in an electrolyte
  • a porous separator a quasi-solid cathode
  • cathode consististing of cathode active material particles and conductive filaments directly mixed or dispersed in an electrolyte
  • 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 graphite flakes (thickness > 100 nm), and graphene sheets (thickness ⁇ 100 nm, more typically ⁇ 10 nm, and can be as thin as 0.34 nm).
  • FIG. 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(A) Ragone plots (gravimetric power density vs. energy density) of Li-S cells containing S/CB composite particles as the cathode active materials and carbon nanofibers as conductive filaments. 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(A) Ragone plots (gravimetric power density vs. energy density) of Li-S cells containing graphene-supported S particles (S electrochemically deposited on graphene surfaces) as the cathode active materials and RGO as conductive filaments.
  • 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).
  • This invention is directed at a lithium-sulfur battery or sodium-sulfur battery exhibiting an exceptionally high energy density that has never been previously achieved.
  • This battery can be a primary battery, but is preferably a secondary battery selected from a lithium-ion sulfur battery, a lithium metal-sulfur secondary battery (e.g. using lithium metal as an anode active material), a sodium-ion sulfur battery, or a sodium metal-sulfur battery (e.g. using sodium metal as an anode active material and carbon-supported sulfur as a cathode active material).
  • 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 combined) 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. and can be an odd shape or irregular shape.
  • the present invention is not limited to any battery shape or configuration.
  • a prior art lithium or sodium battery cell including Li-S or room temperature Na-S cell, is typically composed of an anode current collector (e.g. Cu foil), an anode electrode or anode active material layer (e.g. Li metal foil, sodium foil, or prelithiated Si coating deposited on one or two sides of a Cu foil), a porous separator and/or an electrolyte component, a cathode electrode or cathode active material layer (or two cathode active material layers coated on two sides of an Al foil), and a cathode current collector (e.g. Al foil).
  • anode current collector e.g. Cu foil
  • an anode electrode or anode active material layer e.g. Li metal foil, sodium foil, or prelithiated Si coating deposited on one or two sides of a Cu foil
  • a porous separator and/or an electrolyte component e.g. Li metal foil, sodium foil, or prelithiated Si coating deposited on one or two sides of
  • 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 in a Li-ion cell and lithium polysulfide/carbon composite particles in a Li-S cell), 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
  • either the anode active material (e.g. Si coating) or the cathode active material is deposited in a thin film form directly onto a current collector, such as a sheet of copper foil or Al foil.
  • a current collector such as a sheet of copper foil or Al foil.
  • an extremely small thickness-direction dimension typically much smaller than 500 nm, often necessarily thinner than 100 nm implies that only a small amount of active material can be incorporated in an electrode (given the same electrode or current collector surface area), providing a low total lithium storage capacity and low lithium storage capacity per unit electrode surface area.
  • Such a thin film must have a thickness less than 100 nm to be more resistant to cycling-induced cracking (for the anode) or to facilitate a full utilization of the cathode active material. Such a constraint further diminishes the total lithium storage capacity and the lithium storage capacity per unit electrode surface area.
  • Such a thin-film battery has very limited scope of application.
  • a Si layer thicker than 100 nm has been found to exhibit poor cracking resistance during battery charge/discharge cycles. It takes but a few cycles 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. NMP) to form a dried anode electrode coated on Cu foil.
  • an anode current collector e.g. Cu foil
  • the cathode slurry is coated and dried to form a dried cathode electrode coated on Al foil.
  • Slurry coating is normally done in a roll-to-roll manner in a real manufacturing situation;
  • the third step includes laminating an anode/Cu foil sheet, a porous separator layer, and a cathode/ Al foil sheet together to form a 3-layer or 5-layer assembly, which is cut and slit into desired sizes and stacked to form a rectangular structure (as an example of shape) or rolled into a cylindrical cell structure, (d) The rectangular or cylindrical laminated structure is then encased in an aluminum-plastic laminated envelope or steel casing, (e) A liquid electrolyte is then injected into the laminated structure to make a lithium battery cell.
  • an electrode layer (anode layer or cathode layer) that is thicker than 200 ⁇ .
  • An electrode of 100- 200 ⁇ thickness typically requires a heating zone of 30-50 meters long in a slurry coating facility, which is too time consuming, too energy intensive, and not cost- effective.
  • electrode active materials such as metal oxide particles
  • the resulting electrodes are very fragile and brittle. Thicker electrodes have a high tendency to delaminate and crack.
  • the actual mass loadings of the electrodes and the apparent densities for the active materials are too low to achieve a gravimetric energy density of > 200 Wh/kg.
  • the anode active material mass loading of the electrodes is significantly lower than 25 mg/cm 2 and the apparent volume density or tap density of the active material is typically less than 1.2 g/cm 3 even for relatively large particles of graphite.
  • the cathode active material mass loading of the electrodes is significantly lower than 45 mg/cm 2 for lithium metal oxide-type inorganic materials and lower than 15 mg/cm 2 for organic or polymer materials.
  • non-active materials e.g. conductive additive and resin binder
  • conductive additive and resin binder add additional weights and volumes to the electrode without contributing to the cell capacity.
  • These low areal densities and low volume densities result in relatively low gravimetric energy density and low volumetric energy density.
  • the conventional process requires dispersing electrode active materials (anode active material 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 conventional 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-sulfur battery or room temperature sodium- sulfur 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 (containing a sulfur- containing cathode active material selected from sulfur, a metal-sulfur compound, a sulfur- carbon composite, a sulfur-graphene composite, a sulfur-graphite composite, an organic sulfur compound, a sulfur-polymer composite, or a combination thereof) , 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
  • 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. However, preferably, the cathode is a quasi-solid polymer electrode.
  • the present invention also provides a method of producing an alkali metal battery. In certain embodiments, 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
  • one preferred embodiment of the present invention is an alkali ion sulfur cell having a conductive quasi-solid polymer anode 236, a conductive quasi-solid polymer cathode 238 (containing a sulfur-containing cathode active material), and a porous separator 240 (or ion-permeable membrane) that electronically separates the anode and the cathode.
  • a protective housing typically has an anode tab (terminal) connected to the anode and a cathode tab (terminal) connected to the cathode. These tabs are for connecting to the external load (e.g. an electronic device to be powered by the battery).
  • the quasi-solid polymer anode 236 contains an anode active material (e.g. particles of Li, Si or hard carbon, not shown in FIG. 1(C)), 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)), and a conductive additive (containing conductive filaments) that forms a 3D network of electron-conducting pathways 244.
  • the quasi- solid polymer cathode contains a sulfur-containing 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-sulfur 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 polymer cathode 284, and a separator or ion-conducting membrane 282.
  • the quasi-solid polymer cathode 284 contains a cathode active material 272 (e.g.
  • porous carbon particles impregnated with S or lithium polysulfide, or composite particles containing S supported on graphene sheets an electrolyte phase 274 (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), and a conductive additive phase (containing conductive filaments) that forms a 3D network 270 of electron- conducting pathways.
  • 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.
  • 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 10 mg/cm 2 (more typically and preferably no less than 20 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).
  • conductive filaments such as carbon nanotubes and graphene sheets
  • These conductive filaments are originally a mass of randomly aggregated filaments prior to being mixed with particles of an active material and an electrolyte.
  • the mixing procedure could involve 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.
  • a highly flowable (non-viscous) liquid has been known to be notoriously difficult, let alone in a highly viscous quasisolid, 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 formation of electrode layers may be accomplished by using the following sequences of steps:
  • Sequence 1 A lithium salt or sodium salt (e.g. LiBF 4 ) and an ion-conducting polymer (e.g. PEO) may be dissolved in a mixture of PC and DOL first to form an electrolyte having a desired combined salt/polymer concentration. Then, conductive filaments (e.g. carbon nanofibers, reduced graphene oxide sheets, or CNTs) are dispersed in the electrolyte to form a filament-electrolyte suspension. Mechanical shearing may be used to help forming uniform dispersion. (This filament-electrolyte suspension, even with a low salt concentration of 1.0 M, is quite viscous). Particles of cathode active materials (e.g. S/carbon composite particles) are then dispersed in the filament-electrolyte suspension to form a quasi-solid polymer electrode material.
  • conductive filaments e.g. carbon nanofibers, reduced graphene oxide sheets, or CNTs
  • Mechanical shearing may be
  • Sequence 2 A lithium salt or sodium salt and an ion-conducting polymer are dissolved in a mixture of PC and DOL first to form an electrolyte having a desired combined salt/polymer concentration. Then, particles of the cathode active material are dispersed in the electrolyte to form an active particle-electrolyte suspension. Mechanical shearing may be used to help forming uniform dispersion. Conductive filaments are then dispersed in the active particle- electrolyte suspension to form a quasi-solid polymer electrode material.
  • Sequence 3 This is a preferred sequence.
  • a desired amount of conductive filaments is dispersed in the liquid solvent mixture (e.g. PC + DOL) containing no lithium salt or polymer dissolved therein. Mechanical shearing may be used to help forming uniform
  • 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. Furthermore, 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.
  • 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-sulfur 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-sulfur cells that we have investigated thus far.
  • 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).
  • the internal structure of liquid electrolyte is totally amorphous, having large fractions of free volume through which cations (e.g.
  • FIG. 2(C) 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 typically contains Li or Na metal in the form of a metal foil, thin film or thin coating ( ⁇ 50 ⁇ in thickness) deposited on a current collector (e.g. Cu foil or 3D graphene nano structure).
  • a current collector e.g. Cu foil or 3D graphene nano structure
  • 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.
  • 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 multilayer 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 isolated graphene sheets
  • 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.
  • 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 (d 02 , as determined by X-ray diffraction), thereby significantly reducing the van der Waals forces that otherwise hold graphene planes together along the c-axis direction.
  • the GIC or GO is most often produced by immersing natural graphite powder in a mixture of sulfuric acid, nitric acid (an oxidizing agent), and another oxidizing agent (e.g. potassium permanganate or sodium perchlorate).
  • an 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.
  • 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. Upon exposure of expandable graphite to a temperature in the range from typically 800 - 1,050°C for
  • graphite worms 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 from 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 application US20050271574 (Dec 8, 2005).
  • 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 graphite oxide suspension e.g. graphite oxide particles dispersed in water
  • This is based on the notion that the inter-graphene plane separation has 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 material group There are two different approaches that have been followed to produce fluorinated graphene: (1) 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; (2) 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
  • a sodium intercalation compound selected from petroleum coke, carbon black, amorphous carbon, activated carbon, hard carbon (carbon that is difficult to graphitize), soft carbon (carbon that can be readily graphitized), templated carbon, hollow carbon nanowires, hollow carbon sphere, titanates, NaTi 2 (P04)3, Na 2 Ti 3 07, Na 2 C 8 H 4
  • the alkali metal-sulfur cell is a sodium metal-sulfur cell or sodium -ion sulfur 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,
  • sulfur-based cathode active materials can be used to practice the presently invented lithium-sulfur or sodium-sulfur cell.
  • a sulfur-containing cathode active material may be selected from sulfur, a metal-sulfur compound (e.g. lithium polysulfide), a sulfur-carbon composite (e.g. carbon black-S composite prepared by ball-milling, or porous carbon particles impregnated with S), a sulfur-graphene composite, a sulfur-graphite composite, an organic sulfur compound, a sulfur-polymer composite, or a combination thereof.
  • the cathode active material may be selected from sulfur or sulfur compound supported by or bonded to a functional material or nanostructured material.
  • 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.
  • 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
  • MBE molecular beam epitaxy
  • ALE atomic layer epitaxy
  • electrolytes can be used for practicing the instant invention. Most preferred are non-aqueous organic and/or ionic liquid electrolytes.
  • the non-aqueous electrolyte to be employed herein may be produced by dissolving an electrolytic salt in a non-aqueous solvent.
  • Any known non-aqueous solvent which has been employed as a solvent for a lithium secondary battery can be employed.
  • a non-aqueous solvent mainly consisting of a mixed solvent comprising ethylene carbonate (EC) and at least one kind of non-aqueous solvent whose melting point is lower than that of aforementioned ethylene carbonate and whose donor number is 18 or less (hereinafter referred to as a second solvent) may be preferably employed.
  • This non-aqueous solvent is advantageous in that it is (a) stable against a negative electrode containing a carbonaceous material well developed in graphite structure; (b) effective in suppressing the reductive or oxidative decomposition of electrolyte; and (c) high in conductivity.
  • a non-aqueous electrolyte solely composed of ethylene carbonate (EC) is advantageous in that it is relatively stable against decomposition through a reduction by a graphitized carbonaceous material.
  • the melting point of EC is relatively high, 39 to 40°C, and the viscosity thereof is relatively high, so that the conductivity thereof is low, thus making EC alone unsuited for use as a secondary battery electrolyte to be operated at room temperature or lower.
  • the second solvent to be used in a mixture with EC functions to make the viscosity of the solvent mixture lower than that of EC alone, thereby promoting the ion conductivity of the mixed solvent.
  • the second solvent having a donor number of 18 or less (the donor number of ethylene carbonate is 16.4)
  • the aforementioned ethylene carbonate can be easily and selectively solvated with lithium ion, so that the reduction reaction of the second solvent with the carbonaceous material well developed in graphitization is assumed to be suppressed.
  • the donor number of the second solvent is controlled to not more than 18, the oxidative decomposition potential to the lithium electrode can be easily increased to 4 V or more, so that it is possible to manufacture a lithium secondary battery of high voltage.
  • Preferable second solvents are dimethyl carbonate (DMC), methylethyl carbonate (MEC), diethyl carbonate (DEC), ethyl propionate, methyl propionate, propylene carbonate (PC), .gamma. -butyrolactone (.gamma.-BL), acetonitrile (AN), ethyl acetate (EA), propyl formate (PF), methyl formate (MF), toluene, xylene and methyl acetate (MA).
  • DMC dimethyl carbonate
  • MEC methylethyl carbonate
  • DEC diethyl carbonate
  • ethyl propionate methyl propionate
  • PC propylene carbonate
  • AN acetonitrile
  • EA ethyl acetate
  • PF propyl formate
  • MF methyl formate
  • MA toluene
  • MA methyl acetate
  • the mixing ratio of the aforementioned ethylene carbonate in the mixed solvent should preferably be 10 to 80% by volume. If the mixing ratio of the ethylene carbonate falls outside this range, the conductivity of the solvent may be lowered or the solvent tends to be more easily decomposed, thereby deteriorating the charge/discharge efficiency. More preferable mixing ratio of the ethylene carbonate is 20 to 75% by volume. When the mixing ratio of ethylene carbonate in a non-aqueous solvent is increased to 20% by volume or more, the solvating effect of ethylene carbonate to lithium ions will be facilitated and the solvent decomposition-inhibiting effect thereof can be improved.
  • Examples of preferred mixed solvent are a composition comprising EC and MEC;
  • volume ratio of MEC being controlled within the range from 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 perchl orate (LiC10 4 ), lithium hexafluorophosphate (LiPF 6 ), lithium borofluoride (LiBF 4 ), lithium hexafluoroarsenide (LiAsF 6 ), lithium trifluoro- metasulfonate (LiCF 3 S0 3 ) and bis-trifluorom ethyl sulfonylimide lithium [LiN(CF 3 S0 2 ) 2 ].
  • a lithium salt such as lithium perchl orate (LiC10 4 ), lithium hexafluorophosphate (LiPF 6 ), lithium borofluoride (LiBF 4 ), lithium hexafluoroarsenide (LiAsF 6 ), lithium trifluoro- metasulfonate (LiCF 3 S0 3 ) and bis-trifluorom
  • the electrolyte (including non-flammable quasi-solid electrolyte) may contain a sodium salt preferably selected from sodium perchlorate (NaC10 4 ), sodium
  • 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.
  • 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
  • compositions, ionic liquids come in different classes that basically include aprotic, protic and zwitterionic types, each one suitable for a specific application.
  • RTILs room temperature ionic liquids
  • RTILs include, but not limited to, tetraalkylammonium, di-, tri-, and tetra-alkylimidazolium, alkylpyridinium, dialkyl- pyrrolidinium, dialkylpiperidinium, tetraalkylphosphonium, and trialkylsulfonium.
  • RTILs include, but not limited to, BF 4 " , B(CN) 4 “ , 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 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.
  • anode active materials sulfur-based cathode active materials, and ion-conducting polymers to illustrate the best mode of practicing the instant invention.
  • Natural graphite from Huadong Graphite Co. (Qingdao, China) was used as the starting material.
  • GO was obtained by following the well-known modified Hummers method, which involved two oxidation stages.
  • the first oxidation was achieved in the following conditions: 1100 mg of graphite was placed in a 1000 mL boiling flask. Then, 20 g of K 2 S 2 O 8 , 20 g of P 2 O 5 , and 400 mL of a concentrated aqueous solution of H 2 SO 4 (96%) were added in the flask. The mixture was heated under reflux for 6 hours and then let without disturbing for 20 hours at room temperature. Oxidized graphite was filtered and rinsed with abundant distilled water until neutral pH. A wet cake-like material was recovered at the end of this first oxidation.
  • the previously collected wet cake was placed in a boiling flask that contains 69 mL of a concentrated aqueous solution of H 2 S0 4 (96%).
  • the flask was kept in an ice bath as 9 g of KMn0 4 was slowly added. Care was taken to avoid overheating.
  • the resulting mixture was stirred at 35°C for 2 hours (the sample color turning dark green), followed by the addition of 140 mL of water. After 15 min, the reaction was halted by adding 420 mL of water and 15 mL of an aqueous solution of 30 wt % H 2 0 2 . The color of the sample at this stage turned bright yellow.
  • RGO was used as a conductive additive in either or both of the anode and cathode active material in certain lithium-sulfur batteries presently invented.
  • Prelithiated RGO e.g. RGO + lithium particles or RGO predeposited 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 sulfur batteries and lithium metal- sulfur batteries were investigated.
  • HEG highly exfoliated graphite
  • FHEG fluorinated highly exfoliated graphite
  • Precooled Teflon reactor was filled with 20-30 mL of liquid precooled 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 perchlorate (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
  • sodium salt or potassium salt is preferably selected from
  • the salt concentrations used in the present study were from 0.3M to 3.0 M (most often 0.5M to 2.0M).
  • 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), ⁇ -methyl -N- propylpiperidinium bis(trifluoromethyl sulfonyl)imide (PP 13 TFSI), and N ⁇ -diethyl-N-methyl-A 7 - (2-m ethoxyethyl) ammonium bi s(tri fl uorom ethyl sul fony 1 )i niide.
  • BEPyTFSI N-n-buty ⁇ -N- ethylpyrrolidinium bis(trifluoromethane sulfonyl)imide
  • PP 13 TFSI ⁇ -methyl -N- 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-HFP
  • 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 4 ), 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. With a very low vapor pressure, the vapor phase of the electrolyte either cannot ignite or cannot sustain a flame for longer than 3 seconds once initiated.
  • 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.
  • EXAMPLE 7 Alkali Metal Ion Transference Numbers in Several Electrolytes
  • the Na + ion transference numbers of several types of electrolytes e.g. (PEO + NaTFSI salt) in (EMImTFSI+DME) solvents
  • EMImTFSI+DME lithium salt molecular ratio
  • 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 Preparation of sulfur/carbon black (S/CB) composite particles for the cathode of a lithium-sulfur battery
  • Sulfur powder and CB particles were mixed (70/30 ratio) and ball-milled for 2 hours to obtain S/CB particles.
  • graphene sheets (RGO) and carbon nanofiber (CNF) were separately included as conductive filaments in an electrode containing S/CB particles as a cathode active material and an electrolyte (containing lithium salt and a polymer dissolved in an organic solvent).
  • the lithium salt used in this example includes lithium borofluoride (LiBF 4 ), and the organic solvents are PC, DOL, DEC, and their mixtures.
  • a wide range of conducting filament volume fractions from 0.1% to 30% was included in this study.
  • the formation of electrode layers was accomplished by using the following sequences of steps:
  • 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). S/CB 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, S/CB 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
  • 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 S/CB 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.
  • PC + DOL liquid solvent mixture
  • S/CB 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.
  • S/CB 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).
  • 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.
  • the electrochemical deposition may be conducted before the cathode active material is incorporated into an alkali metal-sulfur battery cell (Li-S or Na-S cell).
  • Li-S or Na-S cell alkali metal-sulfur battery cell
  • the anode, the electrolyte, and a layer of graphene sheets aggregated together (serving as a cathode layer) are positioned in an electrochemical deposition chamber.
  • the needed apparatus is similar to an electro-plating system, which is well-known in the art.
  • a metal polysulfide (M x S y ) is dissolved in a solvent (e.g. mixture of DOL/DME in a volume ratio from 1 :3 to 3 : 1) to form an electrolyte solution.
  • a solvent e.g. mixture of DOL/DME in a volume ratio from 1 :3 to 3 : 1
  • An amount of a lithium salt may be optionally added, but this is not required for external electrochemical deposition.
  • solvents can be utilized for this purpose and there is no theoretical limit to what type of solvents can be used; any solvent can be used provided that there is some solubility of the metal polysulfide in this desired solvent. A greater solubility would mean a larger amount of sulfur can be derived from the electrolyte solution.
  • the electrolyte solution is then poured into a chamber or reactor under a dry and controlled atmosphere condition (e.g. He or Nitrogen gas).
  • a metal foil can be used as the anode and a layer of the porous graphene structure as the cathode; both being immersed in the electrolyte solution.
  • This configuration constitutes an electrochemical deposition system.
  • the step of electrochemically depositing nanoscaled sulfur particles or coating on surfaces of graphene sheets is conducted at a current density preferably in the range from 1 mA/g to 10 A/g, based on the layer weight of the porous graphene structure.
  • the precipitated S is preferentially nucleated and grown on massive graphene surfaces to form nanoscaled coating or nanoparticles.
  • the coating thickness or particle diameter and the amount of S coating/particles may be controlled by the specific surface area, electro-chemical reaction current density, temperature and time. In general, a lower current density and lower reaction temperature lead to a more uniform distribution of S and the reactions are easier to control. A longer reaction time leads to a larger amount of S deposited on graphene surfaces and the reaction is ceased when the sulfur source is consumed or when a desired amount of S is deposited.
  • EXAMPLE 10 Chemical reaction-induced deposition of sulfur particles on isolated graphene sheets prior to cathode layer preparation
  • a prior art chemical deposition method is herein utilized to prepare S-graphene composites from isolated graphene oxide sheets (i.e. these GO sheets were not packed into an integral structure of porous graphene prior to chemical deposition of S on surfaces of GO sheets).
  • a graphene oxide-sulfur (GO-S) composite was prepared by a chemical deposition method in an aqueous solution.
  • 180 mg of graphite oxide was suspended in 180 ml ultrapure water and then sonicated at 50°C for 5 hours to form a stable graphene oxide (GO) dispersion.
  • the Na 2 S x solution was added to the above-prepared GO dispersions in the presence of 5 wt % surfactant cetyl trimethyl -ammonium bromide (CTAB), the as-prepared GO/Na 2 S x blended solution was sonicated for another 2 hours and then titrated into 100 ml of 2 mol/L HCOOH solution at a rate of 30-40 drops/min and stirred for 2 hours. Finally, the precipitate was filtered and washed with acetone and distilled water several times to eliminate salts and impurities. After filtration, the precipitate was dried at 50°C in a drying oven for 48 hours.
  • the reaction may be represented by the following reaction: S x 2" + 2H + ⁇ (x-1) S + H 2 S.
  • EXAMPLE 11 Redox chemical reaction-induced deposition of sulfur particles on isolated graphene sheets and activated carbon (AC) particles prior to cathode layer preparation
  • sodium thiosulfate Na 2 S 2 0 3
  • HCl sodium thiosulfate
  • a GO-water or activated carbon-water suspension was prepared and then the two reactants (HCl and Na 2 S 2 0 3 ) were poured into this suspension.
  • the reaction was allowed to proceed at 25-75°C for 1-3 hours, leading to the precipitation of S particles deposited on surfaces of GO sheets or into pores of AC particles.
  • the reaction may be represented by the following reaction: 2HC1 + Na 2 S 2 0 3 ⁇ 2NaCl + S j + S0 2 ⁇ + H 2 0.
  • GO sheets and S were mixed and dispersed in a solvent (CS 2 ) to form a suspension. After thorough stirring, the solvent was evaporated to yield a solid nanocomposite, which was then ground to yield nanocomposite powder.
  • the primary sulfur particles in these nanocomposite particles have an average diameter of approximately 40-50 nm.
  • EXAMPLE 13 Conductive Web of Filaments from Electro-spun PAA Fibrils as a Supporting Layer for the Anode
  • PAA precursors for spinning were prepared by copolymerizing of pyromellitic dianhydride (Aldrich) and 4,4'-oxydianiline (Aldrich) in a mixed solvent of tetrahydrofurane/methanol (TFIF/MeOH, 8/2 by weight).
  • the PAA solution was spun into fiber web using an electrostatic spinning apparatus.
  • the apparatus consisted of a 15 kV d.c. power supply equipped with the positively charged capillary from which the polymer solution was extruded, and a negatively charged drum for collecting the fibers.
  • Solvent removal and imidization from PAA were performed concurrently by stepwise heat treatments under air flow at 40°C for 12 h, 100°C for 1 h, 250 °C for 2 h, and 350 °C for 1 h.
  • the thermally cured polyimide (PI) web samples were carbonized at 1,000 °C to obtain carbonized nanofibers with an average fibril diameter of 67 nm.
  • Such a web can be used as a conductive substrate for an anode active material.
  • HEG highly exfoliated graphite
  • FUEG fluorinated highly exfoliated graphite
  • Precooled Teflon reactor was filled with 20-30 mL of liquid precooled 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.
  • FFIEG FFIEG
  • an organic solvent methanol and ethanol, separately
  • an ultrasound treatment 280 W
  • the dispersion became a brownish powder.
  • the graphene fluoride powder was mixed with sodium chips in a liquid electrolyte, allowing for pre-sodiation to occur before or after injection into pores of an anode current collector.
  • EXAMPLE 15 Graphene-enhanced nano silicon as an anode active material of a lithium-ion sulfur 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 16 Graphene-enhanced Tin oxide particulates as an anode active material
  • 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
  • EXAMPLE 17 Preparation and electrochemical testing of various battery cells For most of the anode and cathode active materials investigated, we prepared lithium-ion cells or lithium metal cells using both the presently invented method and the conventional method.
  • a typical anode composition includes 85 wt. % active material (e.g., Si-coated graphene sheets), 7 wt. % acetylene black (Super-P), and 8 wt. % polyvinylidene fluoride binder (PVDF, 5 wt. % solid content) dissolved in N-methyl-2- pyrrolidinoe ( MP).
  • active material e.g., Si-coated graphene sheets
  • Super-P acetylene black
  • PVDF polyvinylidene fluoride binder
  • MP N-methyl-2- pyrrolidinoe
  • Cathode layers are made in a similar manner (using Al foil as the cathode current collector) using the conventional slurry coating and drying procedures.
  • An anode layer, separator layer (e.g. Celgard 2400 membrane), and a cathode layer are then laminated together and housed in a plastic- Al envelop.
  • the cell is then injected with 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 polymer anode, a porous separator, and a quasi-solid polymer cathode are assembled in a protective housing. The pouch was then sealed.
  • FIG. 6(A) Shown in FIG. 6(A) are Ragone plots (gravimetric power density vs. energy density) of lithium-sulfur cells containing Li foil as the anode active material and carbon black-sulfur composite particles as the cathode active materials.
  • Three of the 4 data curves are for the cells prepared according to an embodiment of instant invention (with Sequence SI, S2, and S3, respectively) and the remaining one by the conventional slurry coating of electrodes (roll- coating).
  • 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 counterparts prepared via the conventional roll-coating method (denoted as "conventional”).
  • a change from a cathode thickness of 150 ⁇ (coated on a flat solid Al foil) to a thickness of 530 ⁇ having a quasi-solid polymer electrolyte results in a gravimetric energy density increase from 325 Wh/kg to 413 Wh/kg (SI), 425 Wh/kg (S2), and 526 Wh/kg (S3), respectively.
  • the battery containing presently invented quasi-solid electrodes having a 3D network of electron-conducting pathways deliver a significantly higher energy density (FIG. 6(A)) and more stable cycling behavior (FIG. 6(B)).
  • the differences are likely due to the significantly higher active material mass loading (not just mass loading) and the higher conductivity associated with the presently invented cells, reduced proportion of overhead (non-active) components relative to the active material weight/volume, and surprisingly better utilization of the electrode active material (most, if not all, of S contributing to the lithium ion storage capacity due to higher conductivity and no dry pockets or ineffective spots in the electrode, particularly under high charge/discharge rate conditions).
  • FIG. 7(A) shows the Ragone plots (gravimetric power density vs. gravimetric energy density) of two cells, both containing graphene-supported S particles as the cathode active material.
  • the experimental data were obtained from the Li-S battery cells that were prepared by the presently invented method and those by the conventional slurry coating of electrodes.
  • 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

La présente invention concerne une cellule métal alcalin-soufre comprenant : (a) une cathode quasi-solide contenant entre environ 30 % et environ 95 % en volume d'un matériau actif de cathode (un matériau contenant du soufre), entre environ 5 % > et environ 40 % en volume d'un premier électrolyte contenant un sel alcalin dissous dans un solvant et un polymère conducteur d'ions dissous, dispersé dans un solvant ou imprégné de ce dernier, et environ 0,01 %) à environ 30 %) en volume d'un additif conducteur, l'additif conducteur, contenant des filaments conducteurs, formant un réseau 3D de voies conductrices d'électrons de telle sorte que l'électrode quasi-solide présente une conductivité électrique comprise entre environ 10-6 S/cm et environ 300 S/cm ; (b) une anode ; et (c) une membrane conductrice d'ions ou un séparateur poreux disposé entre l'anode et la cathode quasi-solide ; la cathode quasi-solide ayant une épaisseur comprise entre 200 µm et 100 cm et un matériau actif de cathode ayant une charge de masse de matériau actif supérieure à 10 mg/cm2.
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CN112018434A (zh) * 2019-05-29 2020-12-01 丰田自动车工程及制造北美公司 用于合成和优化基于硼化合物的新型软材料的方法
CN112018434B (zh) * 2019-05-29 2024-04-30 丰田自动车工程及制造北美公司 用于合成和优化基于硼化合物的新型软材料的方法
CN112397765A (zh) * 2019-08-16 2021-02-23 通用汽车环球科技运作有限责任公司 具有含电子导电聚合物的电极的固态电池
CN112397765B (zh) * 2019-08-16 2024-04-19 通用汽车环球科技运作有限责任公司 具有含电子导电聚合物的电极的固态电池
CN116072963A (zh) * 2022-05-06 2023-05-05 齐齐哈尔大学 一种生物质衍生碳/聚合物凝胶电解质的制备方法和在钠硫电池中的应用
CN116072963B (zh) * 2022-05-06 2023-10-10 齐齐哈尔大学 一种生物质衍生碳/聚合物凝胶电解质的制备方法和在钠硫电池中的应用

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