WO2000067339A1 - Soufre electroactif contenant des materiaux polymeres conducteurs tres ramifies s'utilisant dans des cellules electrochimiques - Google Patents

Soufre electroactif contenant des materiaux polymeres conducteurs tres ramifies s'utilisant dans des cellules electrochimiques Download PDF

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WO2000067339A1
WO2000067339A1 PCT/US2000/012076 US0012076W WO0067339A1 WO 2000067339 A1 WO2000067339 A1 WO 2000067339A1 US 0012076 W US0012076 W US 0012076W WO 0067339 A1 WO0067339 A1 WO 0067339A1
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polymer
repeating units
highly branched
electroactive
sulfur
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PCT/US2000/012076
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English (en)
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Tatyana I. Movchan
Terje A. Skotheim
Alexei B. Gavrilov
Boris A. Trofimov
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Moltech Corporation
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/137—Electrodes based on electro-active polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/14—Polysulfides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/124—Intrinsically conductive polymers
    • H01B1/127—Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/124—Intrinsically conductive polymers
    • H01B1/128—Intrinsically conductive polymers comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H01M4/602—Polymers
    • 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
    • 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 pertains generally to the field of electroactive cathode materials for electrochemical cells. More particularly, the present invention pertains to an electroactive, highly branched, conductive organic polymer, wherein the polymer comprises a plurality of repeating units, which repeating units are bonded to polysulfide chains, and each of the polysulfide chains comprises a moiety selected from the group consisting of -(S m )-, -(S m ) " , and (S m )" " ; where m is an integer from 3 to 200, and is the same or different at each occurrence.
  • the present invention also pertains to composite cathodes comprising such polymers, to electrochemical cells comprising such cathodes, and to methods of making such polymers, composite cathodes, and cells.
  • cathode-active materials for use in high energy primary and secondary batteries with alkali-metal anode materials.
  • cathode materials comprising sulfur-sulfur bonds, wherein high energy capacity and rechargeabihty are achieved by the electrochemical cleavage (via reduction) and reformation (via oxidation) of these bonds.
  • elemental sulfur in combination with a lithium anode, has a specific capacity of 1680 mAh/g, and sulfur- containing polymers with trisulfide and longer polysulfide groups in the polymers have shown specific capacities of more than 1200 mAh/g.
  • sulfur containing cathode materials disclosed for use in lithium and sodium batteries include, for example, elemental sulfur, organo-sulfur, and carbon-sulfur polymer compositions.
  • Elemental sulfur is an attractive cathode material in alkali-metal batteries owing to its low equivalent weight, low cost, and low toxicity.
  • Many alkali-metal/sulfur battery cells have been described, as for example, in U.S. Pat. Nos. 3,532,543, 3,953,231, and 4,469,761; Rauh et al, J. Electrochem. Soc, 1979, 126, 523-527; Yamin et al., J Electrochem. Soc, 1988, 135, 1045-1048; and Peled et al., J. Power Sources, 1989, 26, 269-271. Many problems with alkali metal/elemental sulfur battery cells have been reported.
  • alkali-metal sulfides formed at the positive electrode on discharge, reacting with elemental sulfur to produce polysulfides that are soluble in the electrolyte causing self-discharge and loss of cell capacity.
  • Another problem is that alkali-metal sulfides once reoxidized on cell charge may lead to the formation of an insulating layer on the positive electrode surface which electrochemically and ionically isolates it from the electroactive elements in the cell, resulting in poor cell reversibility and loss of capacity.
  • the electrically and ionically non-conductive properties of sulfur are an obstacle to overcome in cells comprising elemental sulfur.
  • U.S. Pat. Nos. 5,460,905 and 5,462,566, to Skotheim describe an electrochemical cell which contains a composite cathode comprising carbon-sulfur compounds in combination with a conjugated polymer.
  • U.S. Pat. Nos. 5,529,905, 5,601,947 and 5,690,702 to Skotheim et al. and copending U.S. Pat. Application Ser. No. 09/033,218 to Skotheim et al. of the common assignee describe sulfur-containing organic polymer materials which undergo oxidation and reduction with the formation and breaking, respectively, of many sulfur-sulfur bonds which are attached to conjugated structures.
  • the conjugated polymer structures provide good electron transport and fast electrochemical kinetics at ambient temperatures and below.
  • the present invention pertains to electroactive, highly branched, conductive organic polymers, wherein the polymers, in their oxidized state, comprise a plurality of repeating units, wherein one or more of the repeating units are bonded to polysulfide chains; and, further wherein the polysulfide chains comprise one or more moieties selected from the group consisting of -(S m )-, -(S m ) " , and (S m ) " ; where m is an integer from 3 to 200 and is the same or different at each occurrence.
  • the repeating units comprise one or more moieties selected from the group consisting of pyrrole, aniline, indole, phenylene diamines, thiophene, acetylene, phenylene, vinyl phenylene, vinyl thienylene; and their substituted derivatives.
  • the one or more repeating units comprise pyrrole.
  • the one or more repeating units comprise aniline.
  • the electroactive, highly branched, conductive organic polymer comprises a polymer backbone and the polysulfide chains comprise covalent moieties, -(S m )-, which covalent moieties are covalently bonded by one or both of their terminal sulfur atoms as a side group to the polymer backbone.
  • the polysulfide chains comprise polysulfide anion moieties, -(S m ) " , which anion moieties are covalently bonded by a terminal sulfur atom to the polymer.
  • the polysulfide chains comprise polysulfide dianion moieties, (S m ) " , and the polymer repeating units comprise positively charged atoms; wherein the dianion moieties are ionically bonded to one or more of the positively charged atoms.
  • m of the moieties, -(S m )-, -(S m ) , and (S m ) " is an integer from 9 to 200 and is the same or different at each occurrence.
  • m of the moieties, -(S m )-, -(S m ) " , and (S m ) " is an integer from 24 to 100 and is the same or different at each occurrence.
  • the electroactive, highly branched, conductive organic polymer, in its oxidized state is of the formula: 5
  • M is a repeating unit; n is an integer from 0 to 3 and is the same or different at each occurrence, with the proviso that the number of (S m ) x" moieties in the polymer is equal to or greater than 1 ; y is an integer from 8 to 1000; m is an integer from 3 to 200 and is the same or different at each occurrence; and, x is an integer from 0 to 2 and is the same or different at each occurrence.
  • M comprises one or more repeating units selected from the group consisting of pyrrole, aniline, indole, phenylene diamines, thiophene, acetylene, phenylene, vinyl phenylene, vinyl thienylene; and their substituted derivatives.
  • M is pyrrole.
  • M is aniline.
  • y is an integer from 20 to 400.
  • the polymer comprises greater than 50% by weight of sulfur. In a preferred embodiment, the polymer comprises greater than 75% by weight of sulfur.
  • Another aspect of the present invention pertains to a method of making an electroactive, highly branched, conductive organic polymer of this invention, the method comprising the steps of: (a) providing a dispersion of elemental sulfur in a liquid medium; (b) adding to the dispersion of step (a) one or more monomers and a polymerization initiator comprising an oxidant; (c) stirring the mixture of step (b) thereby forming an electroactive, highly branched, conductive organic polymer; and (d) separating the polymer from the reaction medium of step (c).
  • the one or more monomers is selected from the group consisting of pyrrole, aniline, indole, phenylene diamines, thiophene, acetylene, phenylene, vinyl phenylene, vinyl thienylene; and their substituted derivatives.
  • the particle size of the elemental sulfur is from 0.01 microns to 100 microns. In one embodiment, the weight ratio of the monomer to elemental sulfur is from 1 :1 to 1 :15.
  • the polymerization initiator comprises an oxidant selected from the group consisting of FeCl 3 , Fe(NO 3 ) 3 , CuCl 2 , H 2 O 2 , (NH 4 ) 2 S 2 O 8 , KIO 3 , 1 2 , KMnO 4 , and K 2 Cr 2 O 7 .
  • the liquid medium comprises water. 6
  • the method further comprises after step (d), one or more steps of: (e) purifying the polymer after separation; and (f) drying the polymer.
  • a further aspect of the present invention pertains to an electroactive, highly branched, organic polymer prepared by the method as described herein.
  • the polymer comprises greater than 50% by weight of sulfur. In a preferred embodiment, the polymer comprises greater than 75% by weight of sulfur.
  • the composite cathode comprises: (a) an electroactive, highly branched, conductive organic polymer of this invention, as described herein; and (b) one or more conductive fillers selected from the group consisting of conductive carbons, graphites, activated carbon fibers, non-activated carbon nanofibers, metal flakes, metal powders, metal fibers, carbon fabrics, metal mesh, electrically conductive polymers, and electrically conductive metal chalcogenides.
  • the composite cathode further comprises elemental sulfur.
  • Another aspect of the present invention pertains to a method of preparing a composite cathode comprising the electroactive, highly branched, conductive organic polymers of the present invention, as described herein, which method comprises the steps of: (a) dispersing or suspending in a liquid medium the electroactive polymer; (b) optionally adding to the mixture of step (a) a conductive filler; (c) mixing the composition resulting from step (b) to disperse the electroactive polymer; (d) casting the composition resulting from step (c) onto a suitable substrate; and (e) removing some or all of the liquid from the composition resulting from step (d) to provide a composite cathode.
  • the method further comprises, subsequent to step (e), step (f) of heating the composite cathode structure to a temperature of 120 °C or greater.
  • the method further comprises the addition to any or all of the steps (a), (b), or (c) of one or more materials selected from the group consisting of binders, electrolytes, non-electroactive metal oxides, and electroactive transition metal chalcogenides.
  • Another aspect of the present invention pertains to an electrochemical cell.
  • the cell of this invention comprises an anode, a composite cathode comprising an electroactive, highly branched, conductive organic polymer of the present invention, as described herein, and an electrolyte interposed between the anode and the cathode.
  • the anode comprises one or more materials selected from the group consisting of lithium metal, lithium-aluminum alloys, lithium-tin alloys, lithium- intercalated carbons, and lithium-intercalated graphites.
  • the electrolyte is an organic electrolyte comprising one or more materials selected from the group consisting of liquid electrolytes, gel polymer electrolytes, and solid polymer electrolytes.
  • Another aspect of the present invention pertains to methods of forming an electrochemical cell.
  • the methods comprise the steps of providing an anode, providing a cathode comprising an electroactive, highly branched, conductive organic polymer of the present invention, as described herein, and interposing an electrolyte between the anode and the cathode.
  • Figure 1 shows the conductivity of a physical mixture of polypyrrole and sulfur (+) and the conductivity of highly branched pyrrole/sulfur polymers (•), prepared as described herein, as a function of sulfur content.
  • Figure 2 shows cyclic voltametry of Example 22, using as electrolyte 0.5 M lithium bis(trifluoromethylsulfonyl) imide in a mixture of 1,2-dimethoxy ethane (DME) and 1,3- dioxolane (DOL) at a scan rate of 10 mV/sec.
  • Figure 3 shows cyclic voltametry of Example 23, using as electrolyte 0.5 M lithium bis(trifluoromethylsulfonyl) imide in a mixture of DME and DOL at a scan rate of 10 mV/sec.
  • Figure 4 shows cyclic voltametry of Example 24, using as electrolyte 0.5 M lithium bis(trifluoromethylsulfonyl) imide in a mixture of DME and DOL at a scan rate of 10 mV/sec.
  • Cathode Active Polymers which are electroactive, highly branched, conductive organic polymers and which comprise a plurality of conjugated repeating units bonded to polysulfide chains. 8
  • branched polymer is used herein in the conventional sense to refer to polymers which are characterized by the presence of branch points, i.e., atoms or small groups from which more than two long chains emanate or by the presence of more than two end groups.
  • branch points i.e., atoms or small groups from which more than two long chains emanate or by the presence of more than two end groups.
  • highly branched polymer as used herein, pertains to branched polymers characterized by multiple end groups, such as from 5 to 500 end groups.
  • conductive polymer and "conductive organic polymer”, as used herein, refer, respectively, to polymers and organic polymers having conjugated ⁇ -electron polymeric segments which can be oxidized and reduced reversibly and which have electrically conductive properties in at least one of their oxidation states.
  • polysulfide chain relates to a divalent chemical moiety, -(Sm)-, -(S m ) , or (S m ) 2" , in its oxidized state, which moiety is bonded covalently, covalently and ionically, or ionically to repeating units of a polymer, where m is equal to or greater than 3.
  • m of the polysulfide chain is an integer from 3 to 200 and is the same or different at each occurrence.
  • m is an integer from 9 to 200 and is the same or different at each occurrence.
  • m is an integer from 24 to 100 and is the same or different at each occurrence.
  • Electroactive, highly branched, conductive organic polymers of the present invention may be described by the following formula:
  • M is a repeating unit and is the same or different at each occurrence; n is an integer from 0 to 3 and is the same or different at each occurrence, with the proviso that the number of (S m ) x ⁇ moieties in the polymer is equal to or greater than 1 ; y is an integer from 8 to 1000; m is an integer from 3 to 200 and is the same or different at each occurrence; and x is an integer from 0 to 2 and is the same or different at each occurrence.
  • the repeating unit, M is derived from the oxidative polymerization of pyrrole, aniline, indole, phenylene diamines, thiophene, acetylene, phenylene, vinyl phenylene, vinyl thienylene; and their substituted derivatives.
  • Suitable derivatives include, but are not limited to, alkyl derivatives, amine derivatives, and benzo derivatives. Examples of alkyl derivatives include methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, octyl, and decyl, such as N-methyl pyrrole, 3 -methyl pyrrole, and 2-methyl aniline.
  • Suitable monomers include, but are not limited to:
  • repeating units include, but are not limited to, phenylene, acetylene, thienylene-vinylene, and phenylene-vinylene.
  • the repeating units, M may comprise more than one type of repeating unit as one of the options to obtain the highly branched conductive polymers of the present invention.
  • polymers derived from aniline will be more highly branched when also incorporating phenylene diamine repeating units.
  • the ratio of aniline to phenylene diamine is from about 5 to 1 to about
  • the number of polymer repeating units, y is from 20 to
  • the electroactive, highly branched, conductive organic polymers of the present invention comprise at least 50% by weight of sulfur. In a preferred embodiment, the electroactive, highly branched, conductive polymers of the present invention comprise at least 75% by weight of sulfur.
  • Repeating units of the electroactive, highly branched, conductive organic polymer of this invention are bonded to polysulfide chains, wherein the polysulfide chains comprise one or more moieties selected from the group consisting of -(S m )-, -(S m ) " , and (S m ) " ; where m is an integer from 3 to 200 and is the same or different at each occurrence. In one embodiment, m is an integer from 9 to 200 and is the same or different at each occurrence. In one embodiment, m is from 24 to 100 and is the same or different at each occurrence.
  • the electroactive, highly branched, conductive organic polymer comprises a polymer backbone and the polysulfide chains comprise covalent moieties, - (S m )-, which covalent moieties are covalently bonded by one or both of their terminal sulfur atoms as a side group to the polymer backbone.
  • the polysulfide chains comprise polysulfide anion moieties,-(S m ) " , which anion moieties are covalently bonded by a terminal sulfur atom to the polymer.
  • the polysulfide chains comprise polysulfide dianion moieties, (S m ) " , and the polymer repeating units comprise positively charged atoms; wherein the dianion moieties are ionically bonded to one or more of the positively charged atoms.
  • the bonding of the polysulfide chains to repeating units of the highly branched, conductive polymer may be ionic or covalent or both covalent and ionic.
  • Covalent bonding of polysulfide chains, - (S m )-, or -(S m ) " may be, for example, through C-S bonds or N-S bonds to the repeating units.
  • Ionic bonding of polysulfide chains, -(S m ) " , and (S m ) " may be, for example, to N, S, or C positively charged atoms in the repeating units.
  • the highly branched polymer is characterized by more than 4 end groups comprising the repeating units, preferably by more than 6 end groups comprising the repeating units, and more preferably by more than 25 end groups comprising the repeating units. In one embodiment, the highly branched polymer is characterized by 7 to 100 end groups comprising the repeating units, and preferably by 26 to 100 end groups comprising the repeating units.
  • Another aspect of the present invention pertains to processes for making the electroactive, highly branched, conductive organic polymers of this invention.
  • the method comprises the steps of (a) providing a dispersion of elemental sulfur in a liquid medium; (b) adding to the dispersion of step (a) one or more monomers and a polymerization initiator comprising an oxidant; (c) stirring the mixture of step (b) thereby forming an electroactive material comprising the electroactive, highly branched, conductive organic polymer; and (d) separating the electroactive material from the reaction medium.
  • Dispersion or suspension of elemental sulfur in the liquid medium can be carried out by methods known in the art for dispersing or suspending solids in liquids.
  • the elemental sulfur such as flowers of sulfur
  • the particle size of the elemental sulfur dispersed in the liquid medium is from about 0.01 microns to 100 microns.
  • the dispersion of elemental sulfur may be made in situ from reduced sulfur moieties such as, for example, sulfide anions, polysulfide anions, or polysulfanes by oxidation.
  • reduced sulfur moieties include, but are not limited to, M 2 (S r ), and H 2 (S r ), where M is Li, Na, K, or NH 4 , and r is an integer from 1 to 8.
  • the polymerization initiator comprising an oxidant may both initiate polymerization and oxidize reduced sulfur moieties.
  • An electroactive, highly branched, conductive organic polymer of the present invention may be formed from a mixture of one or more monomers, reduced sulfur moieties and a polymerization initiator comprising an oxidant in a liquid medium.
  • the liquid medium for providing the elemental sulfur dispersion must be compatible with the oxidant polymerization initiator and may be aqueous or non-aqueous and may be a single solvent or a multi-component solvent.
  • the liquid medium comprises water. Additional liquids may be used in the liquid medium to enhance the dispersion of the hydrophobic sulfur.
  • water miscible liquids such as alcohols may be used in volume ratios of alcohol to water of from about T.5 to about 1 :20.
  • surfactants can aid the dispersion or suspension of solids in liquid media, such as water. Surfactants may optionally be added to the liquid medium for dispersing or suspending the elemental sulfur in the methods of the present invention.
  • Suitable surfactants include anionic, cationic, and non-ionic surfactants.
  • suitable surfactants include, but are not limited to, alkylbenzene sulfonates, alkyl sulfonates, alkyl sulfates, alkyl phosphates, dialkyl sulfosuccinates, ethoxylated alcohols, ethoxylated alkylphenols, acetylenic alcohols, trimethylalkyl ammonium halides, benzyl trimethyl ammonium halides, alkyl pyridinium halides, and alkylamine N-oxides.
  • the conductivity of the polymers of the present invention is much higher compared with the conductivity of physical mixtures of polypyrrole and sulfur with the same sulfur content, from about 80% to 95%), as can be seen in Figure 1.
  • the composition of the conductive polymer is supported by additional experiments.
  • Example 21 was treated with carbon disulfide as described in Example 22 in a process which removes elemental sulfur.
  • the polymer product of Example 22 was treated with an aqueous solution of sodium chloride as described in Example 23.
  • the polymer product of Example 22 was also treated with sodium borohydride in a reduction process as described in Example 24.
  • Sodium borohydride reduction of polysulfide materials, R(S ⁇ )R', where R is an organic group and R 1 is an organic group or H and 1 is > 2 is a standard method which produces RSH compounds. This method is described by Cardone in The Analytical Chemistry of Sulfur and its Compounds, Part II, pp. 363-365, Wiley, New York (1972). Elemental analysis of the polymers of Examples 21, 22, 23, and 24 is compiled in
  • FIG. 1 Figures 2, 3, and 4 summarize cyclic voltametry measurements on the polymers of Examples 22, 23, and 24, respectively.
  • the experimental data summarized in Examples 21, 22, 23, and 24 and in Table 3 and Figures 2, 3, and 4 provide support for the composition of one example of the highly branched conductive polymers of this invention derived from pyrrole and sulfur.
  • the polymer of Example 22, obtained by carbon disulfide extraction of the polymer of Example 21 to remove elemental sulfur is essentially free of elemental sulfur as shown by infrared spectroscopy and Differential Scanning Calorimetry (DSC). Sodium borohydride reduction of the polymer of Example 22 yields a material containing sulfur and pyrrole units.
  • Example 24 From the elemental analysis of Example 24, as shown in Table 3, it is clear that there are approximately 8-9 pyrrole units for each sulfur. From the solubility properties and thermal analysis, the product of Example 24 must be polymeric. The reduction in sulfur content from 30.88 % to 4.62 % in the conversion of the polymer of Example 22 to the polymer of Example 24 comes from removal of all S-S bonds by the sodium borohydride treatment. The cyclic voltametry data shown in Figure 2 indicates the absence of S-S bonds in the polymer of Example 24. The average sulfide chain length in the polymer of Example 22 must be approximately 8-10 sulfur atoms.
  • the polymer of Example 23 formed by washing the polymer of Example 22 with sodium chloride to liberate ionically bound polysulfides, shows a reduction of sulfur content by elemental analysis.
  • the examples support a composition for the conductive polymers of the present invention which possesses both ionically and covalently bonded polysulfide moieties.
  • the polymerization of the monomers in the presence of finely dispersed sulfur particles in the present invention may be viewed as a simultaneous coating process and chemical bonding process. In other words, as the polymerization of the monomers proceeds, the sulfur particles are coated by the developing polymer and at the same time chemical bonding of the polymer takes place to the sulfur particles which react to form polysulfide chains.
  • oxidative polymerization of pyrrole or aniline in presence of sulfur particles may create highly branched conductive polymers with bonded polysulfide chains in a number of ways.
  • pyrrole or aniline may undergo polymerization by reaction with the initiating oxidant to form a growing polymer which is subsequently terminated by reaction at the surface of sulfur particles with the formation of the polysulfide chains bonded to a repeat unit of the polymer.
  • the oxidant or its reduced form may react with sulfur to create reactive sites from which the polymer chains are built, e.g., of pyrrole or of aniline, or the oxidant may be adsorbed on the sulfur surface and create initiation sites.
  • oxidants are known to induce polymerization of the monomer repeat units useful in the methods of this invention.
  • the choice of oxidant will depend upon the monomer which is to be polymerized, the degree of branching desired, the molecular weight desired, and other factors.
  • reaction conditions for the preparation of two-dimensional, branched polypyrroles and their electronic and magnetic properties have been described by Schmeisser et al, Synthetic Metals, 1998, 93, 43-58.
  • the polymerization of aniline by electrochemical methods, in the presence of additives, is described by Wei et al, J. Phys. Chem., 1990, 94, 7716-7721.
  • Suitable oxidants for use as the polymerization initiators in the methods of the present invention include, but are not limited to, FeCl 3 , Fe(NO 3 ) 3 , CuCl 2 , H 2 O 2 , (NH 4 ) 2 S 2 O 8 , KIO 3 , 1 2 , KMnO 4 , (NH 4 ) 2 Cr 2 O 7 , and K 2 Cr 2 O 7 .
  • the concentration of the oxidant for the polymerization in the methods of this invention is typically close to that required by the stoichiometry of the oxidative process. Concentrations higher or lower than that required by the stoichiometry, such as from 85% to 150%, may be used. It is generally preferred to use a concentration from 100%) to 120%) of the amount required by the stoichiometry to obtain an acceptable reaction rate. Furthermore, excess oxidant may add cost without a commensurate improvement in rate.
  • the oxidative polymerization of the monomers can be carried out at temperatures from -30 °C to about 80 °C. It is preferred to use a temperature at or above ambient temperature to enhance the degree of the branching in the conductive polymer formed. Preferred temperatures are from about 20 °C to about 50 °C.
  • the oxidant in addition to initiating the formation of branched polymer bonded polysulfide chains, may directly oxidize the elemental sulfur introducing S-O bonds. These S-O species, such as for example, -(S m )-SO 3 " or -(S m )-SO " , where m is an integer equal to or greater than 3, may be present in various concentrations in the polymers of the present invention.
  • the oxidative polymerization initiators are more powerful oxidants and may generate a higher concentration of these S-O species. Likewise, more vigorous reaction conditions, such as a higher temperature, may generate a higher concentration of S-O species. These S-O species are thiophiles which would also readily react with and open elemental sulfur S 8 rings to further promote the polymerization process to form the polymers of the present invention.
  • the highly branched polymer of this invention further comprises one or more moieties selected from the group consisting of -(S m )-SO 3 " and -(S m )-SO 2 ⁇
  • X-ray photoelectron spectroscopy is a technique which measures the binding energy of electrons in chemical species.
  • the binding energy is sensitive to the specific environment of the atom.
  • the binding energy of the 2 p electrons of sulfur atoms in elemental sulfur differs from that in species with S-O bonds or in polysulfides.
  • the measurements on the polymers of Examples 21, 22, 23, and 24 by XPS show the presence of different sulfur species, including the presence of S-O species in addition to polysulfides and elemental sulfur.
  • Separating the electroactive, highly branched, conductive organic polymer from the reaction medium can be performed by procedures known in the art for the separation of solids from liquids.
  • the polymers which are typically insoluble in the liquid medium, can, for example, be separated by filtration, by centrifugation, or by simply decantation. After separation, the polymer may be further purified by washing with liquids which will remove impurities but will not dissolve the polymer, such as with water or organic liquids. After separation and any purification, it is normally desirable to dry the polymer. Drying can be performed by any of the drying methods known in the art.
  • One embodiment of the present invention pertains to a composite cathode for use in an electrochemical cell, wherein said cathode comprises: (a) an electroactive, highly branched, conductive organic polymer; which polymer, in its oxidized state, comprises a plurality of repeating units, which repeating units are bonded to polysulfide chains; wherein said polysulfide chains comprise one or more moieties selected from the group consisting of -(S m )-, -(S m ) " , and (S m ) 2" ; where m is an integer from 3 to 200 and is the same or different at each occurrence; and (b) one or more conductive fillers selected from the group consisting of conductive carbons, graphites, activated carbon fibers, non-activated carbon nano fibers, metal flakes, metal powders, metal fibers, carbon fabrics, metal mesh, electrically conductive polymers, and electrically conductive transition metal chalcogenides.
  • the highly branched polymer may also function both as an electrically conductive filler and an electroactive, conductive polymer.
  • the excellent electrical conductivity of the highly branched polymer as, for example, described in Example 20, may be advantageous in significantly reducing the amount of additional conductive filler, such as conductive carbons, in the composite cathode.
  • additional conductive filler such as conductive carbons
  • the method comprises the steps of: (a) dispersing or suspending in a liquid medium the electroactive, highly branched, conductive organic polymer, as described herein; (b) optionally adding to the mixture of step (a) a conductive filler; (c) mixing the composition resulting from step (b) to disperse the electroactive polymer; (d) casting the composition resulting from step (c) onto a suitable substrate; and (e) removing some or all of the liquid from the composition resulting from step (d) to provide a composite cathode.
  • liquid media suitable for use in the methods of the present invention include aqueous liquids, non-aqueous liquids, and mixtures thereof.
  • aqueous liquids such as methanol, ethanol, isopropanol, propanol, butanol, tetrahydrofuran, dimethoxyethane, acetone, toluene, xylene, acetonitrile, and cyclohexane.
  • Mixing of the various components can be accomplished using any of a variety of methods so long as the desired dissolution or dispersion of the components is obtained. Suitable methods of mixing include, but are not limited to, mechanical agitation, grinding, ultrasonication, ball milling, sand milling, and impingement milling.
  • the formulated dispersions can be applied to substrates by any of a variety of well- known coating methods and dried using conventional techniques.
  • Suitable hand coating techniques include, but are not limited to, the use of a coating rod or gap coating bar.
  • Suitable machine coating methods include, but are not limited to, the use of roller coating, gravure coating, slot extrusion coating, curtain coating, and bead coating.
  • Removal of some or all of the liquid from the mixture can be accomplished by any of a variety of conventional means. Examples of suitable methods for the removal of liquid from the mixture include, but are not limited to, hot air convection, heat, infrared radiation, flowing gases, vacuum, reduced pressure, extraction, and by simply air drying if convenient.
  • One aspect of the present invention pertains to a rechargeable electrochemical cell which comprises: (a) an anode; (b) the composite cathode comprising an electroactive highly branched, conductive organic polymer of the present invention, as described herein; and (c) an electrolyte interposed between said anode and said cathode.
  • the cells comprising the polysulfide-containing, highly branched, conductive organic polymers of the present invention possess properties which are advantageous in several respects.
  • the highly branched, conductive polymer structures enhance the 19 electrochemical cycling capability, for example, in relation to non-branched one- dimensional conductive polymer materials.
  • the highly branched conductive structures typically exhibit advantageous thermal stability, oxidative stability, and mechanical properties of benefit in the fabrication of the cathode materials.
  • the highly branched conductive polymers also typically possess higher electrical conductivity which is, furthermore, maintained over a wide temperature range in comparison to one dimensional conductive polymers. This is particularly useful for good low temperature and ambient temperature performance when the electroactive, highly branched polymers of this invention are utilized in electrochemical cells.
  • the highly branched, conductive polymer structure has a potential disadvantage of reducing the number of possible bonding sites for polysulfide chains in the presence of multiple branching points, in comparison to a non-branched, one dimensional conductive polymer.
  • this can be readily compensated for in the highly branched, conductive polymers of this invention by increasing the length of the polysulfide chains, while retaining the positive features of the highly branched, conductive polymer structure.
  • suitable methods to increase the length of the polysulfide chains in the highly branched, conductive polymers of the present invention include, but are not limited to, increasing the weight ratio of elemental sulfur to the one or more monomers during preparation of the polymer, adjusting the polarity and amount of liquid medium during preparation of the polymer, and adjusting the type, polarity, and amount of electrolyte solvents present during electrochemical cycling of the polymers in an electrochemical cell.
  • Another aspect of the present invention pertains to methods of forming rechargeable electrochemical cells, said methods comprising the steps of: (a) providing an anode; (b) providing a composite cathode of the present invention, as described herein; and (c) interposing an electrolyte between the anode and the cathode.
  • Suitable anode materials for the electrochemical cells of the present invention include, but are not limited to, lithium metal, lithium-aluminum alloys, lithium-tin alloys, lithium-intercalated carbons, and lithium-intercalated graphites.
  • the electrolytes used in battery cells function as a medium for the storage and transport of ions, and in the special case of solid electrolytes and gel electrolytes, these materials may additionally function as separator materials between the anode and the cathode.
  • Any liquid, solid, or gel material capable of storing and transporting ions may be used, so long as the material is electrochemically and chemically unreactive with respect to the anode and the cathode, and the material facilitates the transport of ions between the anode and the cathode.
  • the electrolyte must also be electronically non-conductive to prevent short circuiting between the anode and the cathode.
  • suitable electrolytes for use in the present invention include, but are not limited to, organic electrolytes comprising one or more materials selected from the group consisting of liquid electrolytes, gel polymer electrolytes, and solid polymer electrolytes.
  • liquid electrolytes include, but are not limited to, liquid electrolyte solvents, such as, for example, N-methyl acetamide, acetonitrile, carbonates, sulfones, sulfolanes, aliphatic ethers, cyclic ethers, glymes, siloxanes, dioxolanes, N- alkylpyrrolidones, substituted forms of the foregoing, and blends thereof; to which is added an appropriate ionic electrolyte salt.
  • liquid electrolyte solvents such as, for example, N-methyl acetamide, acetonitrile, carbonates, sulfones, sulfolanes, aliphatic ethers, cyclic ethers, glymes, siloxanes, dioxolanes, N- alkylpyrrolidones, substituted forms of the foregoing, and blends thereof; to which is added an appropriate ionic electrolyte salt.
  • liquid electrolyte solvents are themselves useful as plasticizers for gel polymer electrolytes.
  • useful gel polymer electrolytes include, but are not limited to, those comprising polymers selected from the group consisting of polyethylene oxides, polypropylene oxides, polyacrylonitriles, polysiloxanes, polyimides, polyphosphazenes, polyethers, sulfonated polyimides, perfluorinated membranes, such as, for example, NAFIONTM resins, polydivinyl polyethylene glycols, polyethylene glycol diacrylates, polyethylene glycol dimethacrylates, derivatives of the foregoing, copolymers of the foregoing, crosslinked and network structures of the foregoing, and blends of the foregoing; to which is added an appropriate ionic electrolyte salt.
  • useful solid polymer electrolytes include, but are not limited to, those comprising polymers selected from the group consisting of polyethers, polyethylene oxides, polypropylene oxides, polyimides, polyphosphazenes, polyacrylonitriles, polysiloxanes, derivatives of the foregoing, copolymers of the foregoing, crosslinked and network structures of the foregoing, and blends of the foregoing; to which is added an appropriate ionic electrolyte salt.
  • the non-aqueous electrolyte further comprises one or more ionic electrolyte salts, also as known in the art, to increase the ionic conductivity.
  • ionic electrolyte salts for use in the present invention include, but are not limited to, MSCN, MBr, MI, MClO 4 , MAsF 6 , MSO 3 CF 3 , MSO 3 CH 3 , MBF 4 , MB(Ph) 4 ,
  • MPF 6 MC(SO 2 CF 3 ) 3 , MN(SO 2 CF 3 ) 2 , MN — S0 2 CF 2 CF 2 CF 2 CF 2 — SO- ⁇ , 5 and the like, where M is Li or Na.
  • electrolyte salts useful in the practice of this invention are lithium polysulfides, lithium salts of organic ionic polysulfides, and those disclosed in U.S. Pat. No. 5,538,812 to Lee et al
  • Preferred ionic electrolyte salts are Lil, LiSCN, LiSO 3 CF 3 (lithium triflate), LiN(SO 2 CF 3 ) 2 (lithium imide), and LiC(SO 2 CF 3 ) 3 (lithium methide).
  • the yield of solid, highly branched, polymer was 11.5 g, melting point 116-118 °C. Additional washing of the polymer with acetone and diethyl ether yielded a purified polymer of melting point 108-120 °C. Analysis of the purified polymer gave the following results: C, 4.74%; H, 0.22%; N, 1.12%; S, 89.22%.
  • Powdered sulfur (2 g, 62.5 mmol) was dispersed in a stirred solution of FeCl 3 »6H 2 O (4.6 g, 17 mmol) in a mixture of methanol (20 mL) and water (20 mL). After stirring the dispersion for 3 hours, a solution of pyrrole (0.47 g, 7 mmol) and m-phenylene diamine (0.2 g, 1.8 mmol) in methanol (10 mL) was added during 3 hours. After stirring the reaction mixture for an additional 3 hours, the mixture was held overnight before filtration of the bluish-black solid. The filtered solid was washed with water and dried under vacuum to yield a solid highly branched polymer, 2.43 g. Analysis of the solid gave the following results: C, 15.09%; H, 1.27%; N, 2.58%; S, 80.45%.
  • Powdered sulfur (6.4 g, 200 mmol) was added to a solution of K Cr 2 O 7 (0.82 g, 2.8 mmol) in 24.5 mL of 2N aqueous HCl and stirred vigorously for 3 hours.
  • a mixture of aniline (0.5 g, 5.4 mmol) and m-phenylene diamine ( 0.06 g, 0.5 mmol) was introduced portionwise. The mixture changed color from yellow to black, and the temperature increased to 45 °C. After continuing stirring for 3 hours, the mixture was allowed to stand overnight.
  • a solid composite cathode comprising the polymer of Example 14 and a particulate carbon material was fabricated and evaluated in AA cells in the following way.
  • the slurry was cast by hand coating using a gap coater bar onto a two side coated conductive carbon coated aluminum foil substrate (Product No.
  • the solid composite cathode was then wound into a AA cell with a 50 micron lithium foil anode and a 25 micron E 25 SETELA separator (a trademark for a polyolefin separator available from Tonen Chemical Corporation, Tokyo, Japan, and also available from Mobil Chemical Company, Films Division, Pittsford, NY) and filled with a liquid electrolyte (50% 1,3-dioxolane, 45% 1,2- dimethoxyethane, and 5% o-xylene by volume with 1.3 M lithium triflate salt).
  • a liquid electrolyte 50% 1,3-dioxolane, 45% 1,2- dimethoxyethane, and 5% o-xylene by volume with 1.3 M lithium triflate salt.
  • Example 18 Following the procedure of Example 17, composite cathodes were prepared from the polymer of Example 15 by substitution for the polymer of Example 14 in the cathode formulation and then fabricated into AA cells. Following the cell test procedure of Example 17, the average specific capacity of three cells at the 1 st cycle was 841 mAh/g (based on total sulfur content), and at the 10 th cycle, the average specific capacity was 707 mAh/g (based on total sulfur content).
  • Comparative Example 2 Following the procedures of Example 17, composite cathodes were prepared from a cathode slurry formulation of 10 wt. % polypyrrole of Comparative Example 1 (PPy), 78 wt. % elemental sulfur, 5.5 wt. %> carbon SAB-50, and 6.5 wt. % polyethylene oxide binder (5,000,000 molecular weight), using an ethanol/water mixture (14/1) as the solvent. The composite cathode was then fabricated into AA cells by the procedures of Example 17.
  • the specific capacity of three cells at the 1 st cycle was 741 mAh/g (based on total sulfur content), at the 10 th cycle the average specific capacity was 466 mAh/g (based on total sulfur content), and at the 50 th cycle the average specific capacity was 394 mAh/g (based on total sulfur content).
  • Table 1 summarizes performance of highly branched polymers in cathode formulations by cyclic voltammetry in button cells.
  • Cathodes were prepared by coating 50 wt. % of the highly branched conductive polymer, 35 wt. % of conductive carbon, (SAB- 50), and 15 wt. % polyethylene oxide (PEO) (5,000,000 molecular weight) in acetonitrile as the solvent onto a conductive carbon coated aluminum foil (Product No. 60303) to provide a dry cathode coating thickness of about 25 microns.
  • the anode was lithium foil of about 175 microns thickness.
  • the electrolyte was a 1 M solution of lithium triflate in 28 dimethoxyethane (glyme).
  • the porous separator used was CELGARD 2500 (a trademark for a polyolefin separator available from Hoechst Celanese Corp., Charlotte, NC).
  • Example 20 Electronic conductivity measurements were performed on highly branched conductive polymers of the present invention and for comparison on intimate mixtures of polypyrrole (PPy) of Comparative Example 1 and sulfur with the same overall sulfur content.
  • the measurements of electronic conductivity were made by the two-electrode galvanostatic method.
  • the pellet of material under investigation was placed between stainless steel electrodes and polarized by a constant current of 0.1 mA/cm 2 . Voltage response was monitored with time until a steady-state condition was reached. The steady- state voltage was used to calculate the resistance of the investigated pellet.
  • the electronic conductivity was derived after measuring the thickness and diameter of the pellet. The conductivities were calculated without making any iR correction. The conductivity results obtained, therefore, represent a lower limit for the electronic conductivity.
  • Example 21 The polymer of Example 21 (200 g) was extracted with carbon disulfide (6 successive extractions with IL each) to remove elemental sulfur. The resulting solid material was dried in vacuum. DSC of the solid shows the absence of peaks at 108.3 °C and 119.3 °C present in elemental sulfur. In the infrared spectrum, a peak at 468 cm "1 attributable to elemental sulfur, present in the polymer of Example 21, was also absent.
  • Cyclic voltametry using as electrolyte 0.5 M lithium bis(trifluoromethylsulfonyl) imide in a mixture of dimethoxyethane and dioxolane at a scan rate of 10 mV/sec, showed a broad reduction peak at approximately 1.8 volts as shown in Figure 2.
  • XPS measured as in Example 21 gave binding energies for sulfur 2p of 164.8 eV (polysulfide), and 167.5 eV and 168.6 eV (both for S-O species).
  • XPS also gave a doublet structure for the nitrogen Is level which is characteristic of two-dimensional or branched polypyrroles and is not observed for one-dimensional or linear polypyrroles, as, for example, described by Schmeisser et al. in Synthetic Metals, 1993, 59211-221.
  • Example 22 The polymer of Example 22 (5 g) was stirred at under mild heating for 2 hours with sodium chloride (15 g) dissolved in water (1 L). The solid was filtered, washed with deionized water, and dried in vacuum. Cyclic voltametry by the method of Example 22 showed the absence of the broad reduction peak at approximately 1.8 V and a new peak at 1.2 V as shown in Figure 3.
  • XPS measured as in Example 21 gave binding energies for sulfur 2p of 164.85 eV (polysulfide), and 167.36 eV and 168.56 eV (both for S-O species). XPS also gave a doublet structure for the nitrogen Is level which is characteristic of two- dimensional or branched polypyrroles and is not observed for one-dimensional or linear polypyrroles.
  • Example 22 To the polymer of Example 22 (1 g) dispersed in dimethoxyethane (100 mL) was added sodium borohydride (1 g) at room temperature. The mixture was heated to 60 °C and held at this temperature for 2 hours. After cooling the mixture was diluted with water and the solid filtered. After washing with water and acetone, the solid was dried in vacuum. Cyclic voltametry by the method of Example 22 showed the essential absence of oxidation or reduction peaks as depicted in Figure 4. XPS measured as in Example 21 gave binding energies for sulfur 2p of 164.64 eV (polysulfide), and 167.58 eV and 168.69 eV (both for S-O species). XPS also gave a doublet structure for the nitrogen 1 s level which is characteristic of two-dimensional or branched polypyrroles and is not observed for one-dimensional or linear polypyrroles.
  • Examples 21-24 show that the electroactive polymer is branched and that the structure includes ionic and covalent polysulfide moieties -(S m )-, -(S m ) " , and (S m ) 2" in which m is greater than 8. These same examples also show that elemental sulfur may be present in the polymer as formed and that there is approximately one covalent sulfur attachment for each 8 pyrrole units.

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Abstract

La présente invention concerne un polymère électroactif, conducteur, très ramifié s'utilisant dans des cellules électrochimiques, ce polymère contenant une série de motifs répétés liés à des chaînes de polysulfure. Ces chaînes de polysulfure contiennent une fraction sélectionnée dans le groupe constitué par -(Sm)-, -(Sm)-, et (S¿m)?2-; m étant un nombre entier compris entre 3 et 200, celui-ci étant le même ou différent à chaque occurrence. En outre, cette invention concerne des cathodes composites contenant ces polymères, des cellules électrochimiques comprenant ces cathodes, et des procédés de préparation de ces polymères, cathodes composites ou cellules.
PCT/US2000/012076 1999-05-04 2000-05-03 Soufre electroactif contenant des materiaux polymeres conducteurs tres ramifies s'utilisant dans des cellules electrochimiques WO2000067339A1 (fr)

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US6488721B1 (en) 2000-06-09 2002-12-03 Moltech Corporation Methods of preparing electrochemical cells
US6544688B1 (en) 2000-09-20 2003-04-08 Moltech Corporation Cathode current collector for electrochemical cells
WO2004099317A1 (fr) * 2003-04-30 2004-11-18 Prc-Desoto International, Inc. Compositions de protection emi/rfi preformees profilees
WO2006070945A2 (fr) * 2004-12-28 2006-07-06 Ebara Corporation Matiere polymere organique chimiquement modifiee, methode et appareil de fabrication de cette matiere
US7553908B1 (en) 2003-01-30 2009-06-30 Prc Desoto International, Inc. Preformed compositions in shaped form comprising polymer blends
WO2013008166A1 (fr) * 2011-07-11 2013-01-17 Basf Se Matériau d'électrode comprenant du sulfure de métal
CN105355876A (zh) * 2015-11-07 2016-02-24 合肥国轩高科动力能源有限公司 复合导电聚合物包覆单质硫的制备方法及其用途
US20170062809A1 (en) * 2015-09-02 2017-03-02 Sumitomo Rubber Industries, Ltd. Sulfur-based positive-electrode active material, positive electrode and lithium-ion secondary battery
KR20190060237A (ko) 2017-11-24 2019-06-03 주식회사 엘지화학 과방전을 통해 변형된 황화 고분자를 포함하는 리튬-황 전지 및 이의 제조방법
WO2021252906A3 (fr) * 2020-06-12 2022-01-20 Cytec Industries, Inc. Matériau contenant du soufre et son utilisation

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Cited By (14)

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US6482334B2 (en) 2000-03-09 2002-11-19 Moltech Corporation Methods for preparing non-corrosive, electroactive, conductive organic polymers
US6488721B1 (en) 2000-06-09 2002-12-03 Moltech Corporation Methods of preparing electrochemical cells
US6544688B1 (en) 2000-09-20 2003-04-08 Moltech Corporation Cathode current collector for electrochemical cells
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WO2004099317A1 (fr) * 2003-04-30 2004-11-18 Prc-Desoto International, Inc. Compositions de protection emi/rfi preformees profilees
WO2006070945A3 (fr) * 2004-12-28 2007-02-15 Ebara Corp Matiere polymere organique chimiquement modifiee, methode et appareil de fabrication de cette matiere
WO2006070945A2 (fr) * 2004-12-28 2006-07-06 Ebara Corporation Matiere polymere organique chimiquement modifiee, methode et appareil de fabrication de cette matiere
WO2013008166A1 (fr) * 2011-07-11 2013-01-17 Basf Se Matériau d'électrode comprenant du sulfure de métal
US20170062809A1 (en) * 2015-09-02 2017-03-02 Sumitomo Rubber Industries, Ltd. Sulfur-based positive-electrode active material, positive electrode and lithium-ion secondary battery
US10847279B2 (en) 2015-09-02 2020-11-24 Sumitomo Rubber Industries, Ltd. Method for making a sulfur-based positive-electrode active material
CN105355876A (zh) * 2015-11-07 2016-02-24 合肥国轩高科动力能源有限公司 复合导电聚合物包覆单质硫的制备方法及其用途
KR20190060237A (ko) 2017-11-24 2019-06-03 주식회사 엘지화학 과방전을 통해 변형된 황화 고분자를 포함하는 리튬-황 전지 및 이의 제조방법
WO2021252906A3 (fr) * 2020-06-12 2022-01-20 Cytec Industries, Inc. Matériau contenant du soufre et son utilisation

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