Nothing Special   »   [go: up one dir, main page]

WO2013182360A1 - Procédé de production d'un matériau composite polyacrylonitrile-soufre - Google Patents

Procédé de production d'un matériau composite polyacrylonitrile-soufre Download PDF

Info

Publication number
WO2013182360A1
WO2013182360A1 PCT/EP2013/059302 EP2013059302W WO2013182360A1 WO 2013182360 A1 WO2013182360 A1 WO 2013182360A1 EP 2013059302 W EP2013059302 W EP 2013059302W WO 2013182360 A1 WO2013182360 A1 WO 2013182360A1
Authority
WO
WIPO (PCT)
Prior art keywords
sulfur
polyacrylonitrile
equal
weight
composite material
Prior art date
Application number
PCT/EP2013/059302
Other languages
German (de)
English (en)
Inventor
Jean Fanous
Martin Tenzer
Original Assignee
Robert Bosch Gmbh
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Robert Bosch Gmbh filed Critical Robert Bosch Gmbh
Publication of WO2013182360A1 publication Critical patent/WO2013182360A1/fr

Links

Classifications

    • 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
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/34—Introducing sulfur atoms or sulfur-containing groups
    • 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
    • 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
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/139—Processes of manufacture
    • H01M4/1399—Processes of manufacture of electrodes based on electro-active polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • 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
    • 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
    • H01M4/38—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
    • 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 to a method for producing a
  • Polyacrylonitrile-sulfur composite material in particular as an active material for an alkali-sulfur battery, for example for a lithium-sulfur battery.
  • the present invention further relates to a method for producing an active material for an electrode, in particular for a cathode of a lithium-sulfur battery.
  • the invention further relates to an energy store.
  • lithium-sulfur battery technology Li / S for short.
  • the cathode of a lithium-sulfur cell would consist entirely of elemental sulfur, theoretically an energy content above 1,000 Wh / kg could be achieved.
  • elemental sulfur is neither ionic nor electrically conductive, so additives must be added to the cathode that significantly lower the theoretical value.
  • elemental sulfur is conventionally reduced in the discharge of a lithium-sulfur cell to soluble polysulfides S x 2 " , which can diffuse into regions, for example the anode region, in which they participate in the electrochemical reaction of the following
  • Electrolytes polysulfides be dissolved, which can not be further reduced. In practice, therefore, currently the sulfur utilization and thus the
  • the present invention is a process for producing a polyacrylonitrile-sulfur composite material, comprising the process step: a) reacting sulfur with polyacrylonitrile with an excess of sulfur at a temperature of greater than or equal to 300 ° C, in particular greater than or equal to 550 ° C;
  • a composite material in particular a composite material can be understood, which is prepared by a reaction of polyacrylonitrile (PAN) with sulfur (S).
  • PAN polyacrylonitrile
  • S sulfur
  • the sulfur atoms in the polyacrylonitrile-sulfur composite may be bonded to a particular cyclized polyacrylonitrile backbone both directly by covalent sulfur-carbon bonds and indirectly by one or more covalent sulfur-sulfur bonds and one or more sulfur-carbon bonds. At least part of the sulfur atoms of the polyacrylonitrile-sulfur composite material, for example in the form of polysulfide chains, may be covalently bonded to a cyclized polyacrylonitrile strand.
  • Sulfur content and a good electrochemical cycle stability are produced, which is particularly suitable for producing an active material for a long-term stable cathode of a lithium-sulfur battery, wherein the largest possible proportion of the active material over a long period
  • sulfur is reacted with polyacrylonitrile in the process of the invention.
  • an excess of sulfur is suitably used.
  • temperatures are used for the production of composite materials, which are in a range of greater than or equal to 300 ° C, in particular greater than or equal to 550 ° C. This allows a conversion of sulfur and polyacrylonitrile proceed with particularly good turnovers and also a composite material can be achieved with a particularly good rate capability.
  • a particularly good charging or discharging behavior can be realized.
  • the reaction can be carried out in less than 12 hours, in particular less than 8 hours, for example 5 hours to 7 hours, for example in about 6 hours.
  • a first temperature for example in a range of greater than or equal to 300 ° C to less than or equal to 600 ° C
  • a second temperature which is lower than the first Temperature is, for example, in a range of greater than or equal to 300 ° C to less than or equal to 400 ° C
  • the phase within which the second temperature is set in particular, be longer than the phase in which the first temperature is set.
  • the first temperature phase a cyclization of the polyacrylonitrile can be effected.
  • the second temperature phase essentially the formation of covalent sulfur-carbon bonds can take place.
  • longer polysulfide chains can, as already explained, be linked to the cyclized polyacrylonitrile skeleton.
  • the ratio of sulfur to polyacrylonitrile is selected depending on in
  • Process step a) chosen reaction temperature, in particular the set during the reaction of the maximum temperature can be further ensured that the largest possible amount of sulfur can be incorporated into the formed matrix of the composite material.
  • Active material about a lithium-ion battery can be provided a particularly high capacity. In this case, this can be realized in particular without adversely affecting further reaction parameters, that is, for example, to extend the reaction time.
  • the polyacrylonitrile particles are sufficiently separated from each other, whereby each individual
  • Sulfur may have in the immediate vicinity. This can for example improved crosslinking of the polyacrylonitrile particles with about
  • the ratio of sulfur to polyacrylonitrile is chosen, in particular in such a dependence of the reaction temperature chosen in process step a), that at an increasing temperature, a larger amount of sulfur based on the amount of polyacrylonitrile used is used.
  • a temperature of about 330 ° C for example, a
  • Polyacrylonitrile in wt .-% in a range of 15: 1 can be adjusted.
  • a reaction of sulfur with polyacrylonitrile can be improved such that an excess of sulfur with respect to polyacrylonitrile is always selected as a function of the temperature such that a sufficient amount of sulfur is incorporated into the polyacrylonitrile matrix to form the composite material
  • the sulfur can be covalently bonded to the polyacrylonitrile matrix, but can still be reduced or prevented that excess sulfur remains as an unbound or free radical in the composite material.
  • Such a sulfur radical can be disadvantageous, for example, because it can change the defined structure of the sulfur-polyacrylonitrile composite material.
  • a mixture of sulfur and polyacrylonitrile in process step a), can be reacted in a range of greater than or equal to 7.5: 1 (% by weight).
  • Sulfur content in the composite particles to be produced can further increase.
  • a particularly high capacity can be achieved for the exemplary case of using such a composite material as active material in an electrode for a lithium-ion battery.
  • the rate capability is particularly improved in a particularly advantageous manner, but at the same time increases the capacity even at high temperatures.
  • the weight ratio of sulfur to polyacrylonitrile may be greater than or equal to 7.5: 1 (wt .-%) and in particular less than or equal to 20: 1 wt .-%).
  • pure polyacrylonitrile or a polyacrylonitrile-sulfur mixture may be introduced into a sulfur melt initially introduced at 250.degree.
  • the mixture can be stirred for some time at this temperature purely by way of example and the reaction then be continued at a temperature in a range of greater than or equal to 300 ° C to less than or equal to 550 ° C.
  • the method may comprise the further method step:
  • a composite material can serve directly as an active material after a cleaning.
  • the composite material after the cleaning can be dried in particular. Purification can be performed, for example, by offsetting the composite material with an organic solvent such as toluene. This may conveniently be done after cooling the composite material produced at elevated temperature.
  • the purification according to process step b) can be carried out by a Soxhlet extraction, in particular wherein the Soxhlet extraction can be carried out using an organic solvent.
  • the Soxhiet extraction can be carried out with an apolar solvent or solvent mixture, for example toluene, and the excess sulfur removed.
  • Soxhiet extraction is a particularly simple and cost-effective method and is particularly gentle on the composite material produced, so that no structural change of the particles can take place during the purification. As a result, the rate capability can remain particularly stable.
  • the Soxhiet extraction can also take place, for example, immediately after cooling of the composite material, or also after prior treatment of the composite material with an organic solvent, for example second
  • At least the method step a) can be carried out under an inert gas atmosphere.
  • an inert gas atmosphere can help to obtain a particularly homogeneous and defined structure of the polyacrylonitrile-sulfur composite material.
  • an inert gas atmosphere can be understood as meaning in particular an atmosphere of an unreactive gas in the conditions prevailing in process step a).
  • an inert gas atmosphere may be formed by argon or nitrogen.
  • a cyclized polyacrylonitrile can be reacted with sulfur in the process step a), wherein the cyclized polyacrylonitrile can be obtained by reacting polyacrylonitrile to cyclized polyacrylonitrile.
  • an electrically conductive base in the form of the electrically conductive, cyclized first for example, can thus be used
  • cPAN Polyacrylonitrile
  • the reaction can then be carried out with the electrochemically active sulfur, in particular wherein this can be covalently bonded to the electrically conductive skeleton of cyclized polyacrylonitrile to form a polyacrylonitrile-sulfur composite (ScPAN).
  • ScPAN polyacrylonitrile-sulfur composite
  • the sulfur atoms may be cyclized in the polyacrylonitrile-sulfur composite both directly through covalent sulfur-carbon bonds and indirectly through one or more covalent sulfur-sulfur bonds and one or more sulfur-carbon bonds
  • Polyacrylonitrile-sulfur composite material for example in the form of
  • Polyacrylonitrile strand annel sacred S-heterocycle, and / or intermolecularly with two cyclized polyacrylonitrile strands, in particular to form a bridge, in particular Polysulfid Portugal, between the cyclized polyacrylonitrile strands, covalently connected.
  • Atmosphere for example, an air or oxygen atmosphere, take place.
  • the cyclization may, for example, at a temperature in a range of greater than or equal to 150 ° C to less than or equal to 500 ° C,
  • reaction time of the first process step may be less than 3 hours, in particular less than 2 hours, for example less than 1 hour.
  • Cyclization take place.
  • known catalysts can be used, for example, from the production of carbon fiber.
  • Zykltechnikskatalysators can be added to the production of carbon fiber.
  • reaction temperature and / or the reaction time of the reaction of the polyacrylonitrile with the sulfur are reduced.
  • Polyacrylonitrile can be reacted with sulfur in the presence of a catalyst.
  • a catalyst By adding a catalyst can advantageously the
  • Reaction temperature and the reaction time can be reduced.
  • the chain length of polysulfides covalently bonded to the cyclized polyacrylonitrile can be increased. This is because elemental sulfur is present at room temperature in the form of S8 rings.
  • sulfur is in the form of medium chain Sx chains, for example, from 6 to 26 sulfur atoms, or large chain length, for example, from 103 to 106
  • a thermal cracking process begins and the chain length decreases again. From 444, 6 ° C (boiling point) is gaseous sulfur with a chain length of 1-8 atoms.
  • the use of a vulcanization catalyst has the advantage that at a lower temperature, longer inter- and / or intramolecular, covalently bonded to, in particular cyclized, polyacrylonitrile bound sulfur bridges can be introduced into the polyacrylonitrile-sulfur composite material.
  • a higher sulfur content of the polyacrylonitrile-sulfur composite and thus a higher capacity and energy density ofêtstattenden with the cathode material alkali-sulfur cell, in particular
  • Lithium-sulfur cell can be achieved.
  • Rubber vulcanization known.
  • the reaction is therefore preferably carried out here at least temporarily in the presence of a vulcanization catalyst or vulcanization accelerator.
  • a vulcanization catalyst or vulcanization accelerator In particular, the vulcanization catalyst or
  • Vulkanisationsbelixer comprise or consist of at least one sulfidic radical initiator.
  • the sulfidic radical initiator In particular, the sulfidic
  • Radical starter may be selected from the group consisting of sulfidic
  • Metal complexes for example obtainable by reaction of zinc oxide (ZnO) and tetramethylthiuramidisulfide or ⁇ , ⁇ -dimethylthiocarbamate, sulfenamides, for example 2-mercaptobenzothiazoylamine derivatives, and combinations thereof.
  • the reaction mixture may be greater than or equal to 3 wt% to less than or equal to 5 wt% zinc oxide and optionally greater than or equal to 0.5
  • the reaction can be carried out at least temporarily in the presence of a vulcanization inhibitor. Suitable for this
  • Vulcanization inhibitors are also known in the rubber vulcanization art.
  • N- (cyclohexylthio) phthalamide can be used as a vulcanization inhibitor.
  • the properties of the polyacrylonitrile-sulfur composite material can be adjusted in a targeted manner.
  • the catalyst and optionally the inhibitor are partially or completely removed in a removal step.
  • the invention further relates to a method for producing a
  • An active material for an electrode, in particular for a cathode of a lithium-sulfur battery, comprising a method configured as described above for producing a polyacrylonitrile-sulfur composite material.
  • a polyacrylonitrile-sulfur composite material produced as described above can have advantageous properties, in particular a high rate capability, in particular as active material of an electrode, in particular a cathode, for a lithium-sulfur battery.
  • an energy store equipped with this can have a particularly preferred charging and / or discharging behavior.
  • the method can continue the
  • Process step include: c) admixing at least one electrically conductive additive to the
  • Polyacrylonitrile-sulfur composite material in particular selected from the group consisting of carbon black, graphite, carbon fibers, carbon nanotubes and mixtures thereof.
  • greater than or equal to 0.1% by weight to less than or equal to 30% by weight, for example greater than or equal to 5% by weight to less than or equal to 20% by weight can be admixed to electrically conductive additives.
  • electrically conductive additives By adding an electrically conductive additive, the conductivity and thus the rate capability of the resulting mixture can be further improved, which makes use as an active material in an electrode particularly advantageous.
  • the method may further comprise the method step:
  • binders greater than or equal to 0.1% by weight to less than or equal to 30% by weight, for example greater than or equal to 5% by weight to less than or equal to 20% by weight, can be admixed to binders.
  • the stability of the cathode material can be improved by adding binders, which can improve use in electrochemical energy stores.
  • the binder may be added together with N-methyl-2-pyrrolidone as a solvent.
  • process step c) and / or in process step d) greater than or equal to 60% by weight to less than or equal to 90% by weight, in particular greater than or equal to 65% by weight to less than or equal to 75% by weight, for example 7% by weight be used on polyacrylonitrile-sulfur composite material, and / or
  • process step c) greater than or equal to 0.1% by weight to less than or equal to 30% by weight, for example greater than or equal to 5% by weight to less than or equal to 20% by weight, are admixed to electrically conductive additives, and / or in process step d) greater than or equal to 0.1 wt% to less than or equal to 30 wt%, for example greater than or equal to 5 wt% to less than or equal to 20 wt%, are admixed to binders.
  • the invention further provides the use of a polyacrylonitrile-sulfur composite material, prepared according to a previously described
  • a composite material thus produced can provide advantageous properties such as good capacity and rate capability.
  • the invention furthermore relates to an energy store, in particular a lithium-sulfur battery, comprising an electrode with an active material which has a polyacrylonitrile-sulfur composite material produced as described above.
  • an active material produced as described above in particular in the form of a
  • Kathodenmatenalschlickers for producing a cathode continue at least a solvent, for example N-methyl-2-pyrrolidone.
  • a cathode metal slag can be applied, for example by doctoring, to a carrier material, for example an aluminum plate or foil.
  • the solvents are preferably removed again after the application of the cathode material and before the assembly of the lithium-sulfur cell, preferably completely, in particular by a drying process.
  • the cathode material-carrier material arrangement can then be divided into several cathode material-carrier material units, for example by punching or cutting.
  • the cathode material-carrier material arrangement or units can be installed with a lithium metal anode, for example in the form of a plate or foil of metallic lithium, to form a lithium-sulfur cell.
  • the anode may in particular be an alkali metal anode, in particular a lithium metal anode, for example in the form of a plate or foil, for example of metallic lithium.
  • the alkali-sulfur cell or battery may comprise an electrolyte, in particular of at least one electrolyte solvent and at least one conductive salt.
  • the electrolyte solvent may be selected from the group consisting of carbonic acid esters,
  • the electrolyte solvent may be diethyl carbonate (DEC),
  • the salt can for example be selected from the group consisting of lithium hexafluorophosphate (LiPF 6), lithium bis (trifluormethylsulphonyl) imide (LiTFSI), lithium tetrafluoroborate (LiBF 4), lithium trifluoromethanesulfonate (LiCF 3 S0 3), lithium chlorate (LiCI0 4) Lithium bis (oxalato) borate (LiBOB), lithium fluoride (LiF), lithium nitrate (LiN0 3 ), lithium hexafluoroarsenate (LiAsF 6 ), and combinations thereof.
  • the electrolyte solvent may be selected from the group consisting of cyclic ethers, acyclic ethers, and combinations thereof, and / or may include the conductive salt lithium bis (trifluoromethylsulphonyl) imide (LiTFSI).
  • LiTFSI lithium bis (trifluoromethylsulphonyl) imide
  • An energy store that can be produced in this way can be, in particular, a mobile or stationary energy store, which comprises an alkali-sulfur cell or battery according to the invention, in particular a lithium-sulfur cell or battery.
  • the energy storage device may be an energy storage device for a vehicle, for example an electric or electronic vehicle
  • Hybrid vehicle or a power tool or device, such as a screwdriver or gardening tool, or an electronic device, such as a portable computer and / or a
  • Telecommunication device such as a mobile phone, PDA, or a
  • the alkali-sulfur cells or batteries according to the invention have a very high energy density, they are particularly suitable for vehicles and stationary storage systems, such as high-energy storage systems for houses or installations.
  • Fig. 1 is a diagram showing the capacity curve of test cells in
  • the sulfur-containing, cyclized polyacrylonitrile, ie the finished composite, is processed to a cathode slurry for forming a cathode active material.
  • the active material (SPAN), carbon black (such as the carbon black available under the trade name Super P Li) as an electrically conductive additive and polyvinylidene fluoride (PVDF) as a binder or binder in a ratio of 70:15:15 (in wt .-%) in N-methyl-2-pyrrolidone (NMP) as
  • Solvent mixed and homogenized The slurry will be on one

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

L'invention concerne un procédé pour produire un matériau composite polyacrylonitrile-soufre, qui comprend les étapes suivantes : a) faire réagir du soufre avec du polyacrylonitrile avec un surplus de soufre à une température supérieure ou égale à 300°C, en particulier supérieure ou égale à 550°C, le rapport du soufre au polyacrylonitrile étant sélectionné en fonction de la température de réaction choisie à l'étape a) du procédé. L'invention concerne en outre un procédé de production d'un matériau actif pour une électrode ainsi qu'un accumulateur d'énergie.
PCT/EP2013/059302 2012-06-08 2013-05-03 Procédé de production d'un matériau composite polyacrylonitrile-soufre WO2013182360A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102012209642.6 2012-06-08
DE102012209642A DE102012209642A1 (de) 2012-06-08 2012-06-08 Verfahren zum Herstellen eines Polyacrylnitril-Schwefel-Kompositwerkstoffs

Publications (1)

Publication Number Publication Date
WO2013182360A1 true WO2013182360A1 (fr) 2013-12-12

Family

ID=48407494

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2013/059302 WO2013182360A1 (fr) 2012-06-08 2013-05-03 Procédé de production d'un matériau composite polyacrylonitrile-soufre

Country Status (2)

Country Link
DE (1) DE102012209642A1 (fr)
WO (1) WO2013182360A1 (fr)

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104201389A (zh) * 2014-08-20 2014-12-10 中南大学 一种锂硒电池正极的制备方法
WO2015185337A2 (fr) 2014-06-06 2015-12-10 Robert Bosch Gmbh Électrolyte polymère pour élément de batterie lithium-soufre
DE102014213679A1 (de) 2014-07-15 2016-01-21 Robert Bosch Gmbh Separator mit kraftschlüssig eingespannten Partikeln
WO2016019901A1 (fr) * 2014-08-07 2016-02-11 Robert Bosch Gmbh Composite soufre-pan, son procédé de préparation, et électrode et batterie au lithium-soufre le contenant
DE102014221737A1 (de) 2014-10-24 2016-04-28 Robert Bosch Gmbh Elektrolyt für Lithium-Schwefel-Zelle
DE102014221736A1 (de) 2014-10-24 2016-04-28 Robert Bosch Gmbh Polymerelektrolyt für Lithium-Schwefel-Zelle
DE102015210402A1 (de) 2015-06-05 2016-12-08 Robert Bosch Gmbh Kathodenmaterial für Lithium-Schwefel-Zelle
DE102015210404A1 (de) 2015-06-05 2016-12-08 Robert Bosch Gmbh Elektrospinnen von Kathodenaktivmaterialfasern
DE102015219473A1 (de) * 2015-10-08 2017-04-13 Robert Bosch Gmbh Elektrodenmaterial, Batteriezelle dieses enthaltend und Verfahren zu deren Herstellung
CN106663788A (zh) * 2014-06-06 2017-05-10 罗伯特·博世有限公司 用于锂‑硫‑电池的聚合物电解质
DE102015224335A1 (de) 2015-12-04 2017-06-08 Robert Bosch Gmbh Feststoffelektrode mit elektrolytgetränkten Aktivmaterialpartikeln
DE102015224345A1 (de) 2015-12-04 2017-06-08 Robert Bosch Gmbh SIC-Separator und SIC-Zelle
CN106953071A (zh) * 2015-12-03 2017-07-14 罗伯特·博世有限公司 在整个反应时间期间利用恒定的硫含量进行span合成的方法
DE102016225273A1 (de) 2016-12-16 2018-06-21 Robert Bosch Gmbh SIC-MOF-Elektrolyt
CN110911668A (zh) * 2019-12-02 2020-03-24 电子科技大学 一种锂硫电池pip@s正极材料及制备方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102015224194A1 (de) 2015-12-03 2017-06-08 Robert Bosch Gmbh Polyacrylnitril-Schwefel-Komposit mit erhöhter Kapazität

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
ADVANCED FUNCTIONAL MATERIALS, vol. 13, no. 6, 2003, pages 487 - 492
JOURNAL OF POWER SOURCES, vol. 146, 2005, pages 335 - 339
NAZAR ET AL., NATURE MATERIALS, vol. 8, June 2009 (2009-06-01), pages 500 - 506
WANG ET AL., ADVANCED MATERIALS, vol. 14, no. 13-14, 2002, pages 963 - 965
YU ET AL., JOURNAL OF ELECTROANALYTICAL CHEMISTRY, vol. 573, 2004, pages 121 - 128
YU X ET AL: "Stable-cycle and high-capacity conductive sulfur-containing cathode materials for rechargeable lithium batteries", JOURNAL OF POWER SOURCES, ELSEVIER SA, CH, vol. 146, no. 1-2, 26 August 2005 (2005-08-26), pages 335 - 339, XP027756442, ISSN: 0378-7753, [retrieved on 20050826] *

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106537658B (zh) * 2014-06-06 2021-12-07 罗伯特·博世有限公司 用于锂-硫-电池的聚合物电解质
WO2015185337A2 (fr) 2014-06-06 2015-12-10 Robert Bosch Gmbh Électrolyte polymère pour élément de batterie lithium-soufre
WO2015185337A3 (fr) * 2014-06-06 2016-01-21 Robert Bosch Gmbh Électrolyte polymère pour élément de batterie lithium-soufre
CN106663788A (zh) * 2014-06-06 2017-05-10 罗伯特·博世有限公司 用于锂‑硫‑电池的聚合物电解质
DE102014221731A1 (de) 2014-06-06 2016-01-21 Robert Bosch Gmbh Polymerelektrolyt für Lithium-Schwefel-Zelle
CN106537658A (zh) * 2014-06-06 2017-03-22 罗伯特·博世有限公司 用于锂‑硫‑电池的聚合物电解质
US10601031B2 (en) 2014-06-06 2020-03-24 Robert Bosch Gmbh Polymer electrolyte for a lithium sulfur cell
DE102014213679A1 (de) 2014-07-15 2016-01-21 Robert Bosch Gmbh Separator mit kraftschlüssig eingespannten Partikeln
WO2016019897A1 (fr) * 2014-08-07 2016-02-11 Robert Bosch Gmbh Composite soufre-pan, procédé de préparation dudit composite, et électrode et batterie au lithium-soufre comprenant ledit composite
WO2016019901A1 (fr) * 2014-08-07 2016-02-11 Robert Bosch Gmbh Composite soufre-pan, son procédé de préparation, et électrode et batterie au lithium-soufre le contenant
CN104201389A (zh) * 2014-08-20 2014-12-10 中南大学 一种锂硒电池正极的制备方法
DE102014221736A1 (de) 2014-10-24 2016-04-28 Robert Bosch Gmbh Polymerelektrolyt für Lithium-Schwefel-Zelle
DE102014221737A1 (de) 2014-10-24 2016-04-28 Robert Bosch Gmbh Elektrolyt für Lithium-Schwefel-Zelle
DE102015210404A1 (de) 2015-06-05 2016-12-08 Robert Bosch Gmbh Elektrospinnen von Kathodenaktivmaterialfasern
WO2016193216A1 (fr) 2015-06-05 2016-12-08 Robert Bosch Gmbh Filage électrostatique de fibres de matériau actif de cathode
DE102015210402A1 (de) 2015-06-05 2016-12-08 Robert Bosch Gmbh Kathodenmaterial für Lithium-Schwefel-Zelle
DE102015219473A1 (de) * 2015-10-08 2017-04-13 Robert Bosch Gmbh Elektrodenmaterial, Batteriezelle dieses enthaltend und Verfahren zu deren Herstellung
CN106953071A (zh) * 2015-12-03 2017-07-14 罗伯特·博世有限公司 在整个反应时间期间利用恒定的硫含量进行span合成的方法
DE102015224335A1 (de) 2015-12-04 2017-06-08 Robert Bosch Gmbh Feststoffelektrode mit elektrolytgetränkten Aktivmaterialpartikeln
DE102015224345A1 (de) 2015-12-04 2017-06-08 Robert Bosch Gmbh SIC-Separator und SIC-Zelle
US10461317B2 (en) 2015-12-04 2019-10-29 Robert Bosch Gmbh Solid electrode including electrolyte-impregnated active material particles
DE102016225273A1 (de) 2016-12-16 2018-06-21 Robert Bosch Gmbh SIC-MOF-Elektrolyt
CN110911668A (zh) * 2019-12-02 2020-03-24 电子科技大学 一种锂硫电池pip@s正极材料及制备方法

Also Published As

Publication number Publication date
DE102012209642A1 (de) 2013-12-12

Similar Documents

Publication Publication Date Title
EP2859033B1 (fr) Procédé pour la préparation d'un composite de polyacrylnitrile-soufre
WO2013182360A1 (fr) Procédé de production d'un matériau composite polyacrylonitrile-soufre
EP2705060B1 (fr) Matériau de cathode pour pile alcaline au soufre
EP2705059B1 (fr) Matériau composite de polyacrylonitrile-soufre
DE102019135173B4 (de) Verfahren zur Herstellung von Elektroden für elektrochemische Zellen durch kontinuierliche lokalisierte Pyrolyse
DE102011075053A1 (de) Polyacrylnitril-Schwefel-Kompositwerkstoff
DE69631900T2 (de) Elektrodenmaterial für elektrochemische lithiumeinlagerung
DE102016117690A1 (de) Ein poröser karbonisierter Verbundwerkstoff für Silicium-Hochleistungsanoden
WO2013182362A1 (fr) Procédé de production d'un matériau composite polyacrylonitrile-soufre
DE102014219421A1 (de) Kathode (positive Elektrode) und diese umfassende Lithiumionenbatterie im Zustand vor dem ersten Ladevorgang, Verfahren zur Formation einer Lithiumionenbatterie und Lithiumionenbatterie nach Formation
DE69518476T2 (de) Nichtwässrige Sekundärbatterie und Negativelektrode
EP3063811B1 (fr) Sulfure de lithium revêtu de carbon
DE102012109641A1 (de) Aktivmaterialien für Batterien
DE3855938T2 (de) Wasserfreie Sekundärbatterie
DE102013216814A1 (de) Positives, aktives Elektrodenmaterial, Herstellungsverfahren für dasselbige und wiederaufladbare Batterie aus nichtwässrigem Elektrolyt, welche dasselbige aufweist
DE102014202180A1 (de) Elektrolytzusammensetzungen für Lithium-Schwefel-Batterien
EP2668692B1 (fr) Additif redox pour cellules secondaires à changement de phase liquide-solide
DE102015224194A1 (de) Polyacrylnitril-Schwefel-Komposit mit erhöhter Kapazität
WO2011144605A1 (fr) Composés et leur utilisation pour produire des piles électrochimiques
DE102014207882A1 (de) Neue Beschichtung von Siliziumpartikeln für Lithium-Ionen-Batterien zur verbesserten Zyklenstabilität
EP3648201A1 (fr) Procédé d'élimination de composés formant potentiellement de l'hydrogène à partir de cellules électrochimiques
DE102014207881A1 (de) Herstellverfahren von nanoskaligen Siliziumpartikeln mit einer reduzierten Siliziumdioxid-Beschichtung
DE102022118607A1 (de) Mit Kohlenstoff beschichtete lithiierte elektroaktive Materialien auf Siliziumbasis und Verfahren zur Herstellung derselben
DE102020132661A1 (de) Kathodenaktivmaterial und Lithiumionen-Batterie mit dem Kathodenaktivmaterial
DE102022126495A1 (de) Verfahren zum herstellen von schwefel-polyacrylnitril (span)

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13721671

Country of ref document: EP

Kind code of ref document: A1

122 Ep: pct application non-entry in european phase

Ref document number: 13721671

Country of ref document: EP

Kind code of ref document: A1