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WO2012150062A1 - Matériau composite polyacrylonitrile-soufre - Google Patents

Matériau composite polyacrylonitrile-soufre Download PDF

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Publication number
WO2012150062A1
WO2012150062A1 PCT/EP2012/053857 EP2012053857W WO2012150062A1 WO 2012150062 A1 WO2012150062 A1 WO 2012150062A1 EP 2012053857 W EP2012053857 W EP 2012053857W WO 2012150062 A1 WO2012150062 A1 WO 2012150062A1
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WO
WIPO (PCT)
Prior art keywords
sulfur
polyacrylonitrile
lithium
composite material
alkali
Prior art date
Application number
PCT/EP2012/053857
Other languages
German (de)
English (en)
Inventor
Jens Grimminger
Jean Fanous
Martin Tenzer
Marcus Wegner
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 WO2012150062A1 publication Critical patent/WO2012150062A1/fr

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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H01M10/39—Accumulators not provided for in groups H01M10/05-H01M10/34 working at high temperature
    • H01M10/3909—Sodium-sulfur cells
    • 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
    • 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 process for the preparation of a polyacrylonitrile-sulfur composite material, a polyacrylonitrile-sulfur
  • Composite material a cathode material, an alkali-sulfur cell - or battery and an energy storage.
  • 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 to soluble polysulfides S x 2 " upon discharge of a lithium-sulfur cell, which may diffuse into regions, such as the anode region, where they can no longer participate in the electrochemical reaction of the subsequent charge / discharge cycles
  • polysulfides which can not be further reduced can be dissolved in the electrolyte, and in practice the sulfur utilization and thus the energy density of lithium-sulfur cells is currently significantly lower and is currently estimated to be between 400 Wh / kg and 600 Wh / kg ,
  • the present invention provides a process for producing a polyacrylonitrile-sulfur composite material, wherein polyacrylonitrile is reacted with sulfur at least temporarily in the presence of a catalyst to form a polyacrylonitrile-sulfur composite material.
  • 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 due to the fact that elemental sulfur is present at room temperature in the form of S 8 rings. At temperatures above room temperature, sulfur is present in the form of medium chain Sx chains, for example from 6 to 26 sulfur atoms, or long chain length, for example from 10 3 to 10 6 sulfur atoms. Above 187 ° C, a thermal cracking process begins and the chain length decreases again. From 444, 6 ° C (boiling point) is gaseous sulfur with a
  • a vulcanization catalyst has the advantage that at a lower temperature longer inter- and / or intramolecular, covalently bonded, in particular cyclized, polyacrylonitrile bound sulfur bridges can be introduced into the polyacrylonitrile-sulfur composite material.
  • inventive vulcanization catalyst has the advantage that at a lower temperature longer inter- and / or intramolecular, covalently bonded, in particular cyclized, polyacrylonitrile bound sulfur bridges can be introduced into the polyacrylonitrile-sulfur composite material.
  • Polysulfide chains with a chain length of> 3 sulfur atoms, in particular particular> 4 or> 5 or> 6 or> 7 or> 8 or> 9 or> 10 sulfur atoms, are covalently bonded to the polyacrylonitrile skeleton of the polyacrylonitrile-sulfur composite.
  • a higher sulfur content of the polyacrylonitrile-sulfur composite material can be achieved.
  • this can lead to a reduction in the cycle stability, but this can be compensated for example by the choice of a suitable electrolyte.
  • the polyacrylonitrile-sulfur composite material which can be produced by the process according to the invention can be used particularly advantageously as cathode material for alkali metal compounds.
  • Sulfur cells in particular lithium-sulfur cells
  • cathodes or alkali-sulfur cells, in particular lithium-sulfur cells, which comprise the polyacrylonitrile-sulfur composite material produced according to the invention can advantageously - with respect to known polyacrylonitrile-sulfur composite materials, have improved electrochemical properties.
  • alkali-sulfur cells may advantageously have a high capacity and energy density.
  • Suitable catalysts for the process according to the invention are known from the technical field of rubber vulcanization.
  • the reaction is carried out, at least temporarily, in the presence of a vulcanization catalyst or vulcanization accelerator.
  • the vulcanization catalyst or vulcanization accelerator comprises at least one sulfidic radical initiator. If appropriate, the vulcanization catalyst or vulcanization accelerator may consist of at least one sulfidic radical initiator. Sulfidic radical initiators are particularly suitable for the process according to the invention.
  • the sulfidic radical initiator is selected from the group consisting of sulfidic metal complexes, obtainable, for example, by reaction of zinc oxide (ZnO) and tetramethylthiurea. midisulfide or ⁇ , ⁇ -dimethylthiocarbamate, sulfenamides, for example, 2-mercaptobenzothiazoylamine derivatives, and combinations thereof.
  • the reaction mixture may comprise> 3 wt% to ⁇ 5 wt% zinc oxide and optionally> 0.5 wt% to ⁇ 1 wt% tetramethylthiuramidisulfide.
  • Such catalysts are particularly suitable for the process according to the invention.
  • At least one vulcanization inhibitor may be added.
  • the reaction is therefore carried out, at least temporarily, in the presence of a vulcanization inhibitor.
  • a vulcanization inhibitor suitable for this purpose are likewise known from the technical field of rubber vulcanization. For example, N- (cyclohexylthio) phthalamide may be used as
  • Vulkanisationsinhibitor be used.
  • elemental sulfur for example sublimed elemental sulfur
  • Elemental sulfur in particular sublimated elemental sulfur
  • sulfur compounds especially those which react with the cyclized polyacrylonitrile to form a covalent sulfur-carbon bond.
  • the sulfur can be used in excess.
  • the weight ratio of sulfur to cyclized polyacrylonitrile is> 1: 1, in particular> 1.5: 1, for example> 2: 1, for example> 3: 1, and / or ⁇ 20: 1, in particular ⁇ 15: 1 or ⁇ 10: 1, for example ⁇ 5: 1 or ⁇ 3: 1 or ⁇ 2.5: 1 or ⁇ 2: 1. These proportions They have proved to be suitable for carrying out the process according to the invention.
  • reaction is carried out temporarily or completely at a temperature in a range of> 120 ° C to
  • ⁇ 380 ° C in particular from> 150 ° C to ⁇ 350 ° C, for example from> 180 ° C to ⁇ 330 ° C.
  • a first temperature is first during the reaction, for example in a range of> 250 ° C to
  • ⁇ 600 ° C in particular from> 300 ° C to ⁇ 500 ° C, for example from> 330 ° C to ⁇ 450 ° C, and then a second temperature which is lower than the first temperature, for example in a range of> 120 ° C to ⁇ 250 ° C, in particular from> 150 ° C to ⁇ 250 ° C, for example from> 180 ° C to ⁇ 200 ° C, adjusted.
  • the phase within which the second temperature is adjusted 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 be linked to the cyclized polyacrylonitrile skeleton.
  • the reaction takes place at a temperature of ⁇ 300 ° C.
  • the reaction can be carried out temporarily or completely in an inert gas atmosphere, for example in an argon or nitrogen atmosphere.
  • the reaction is 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.
  • the method further comprises the method step:
  • Removing, for example, extracting, excess or unbound sulfur When using the polyacrylonitrile-sulfur composite material as the cathode material of an alkali-sulfur cell, unbound or elemental sulfur can react with the reduction with some electrolyte systems, which is why the choice of the electrolyte system is limited in the presence of unbound or elemental sulfur. By removing excess or unbound sulfur, further or different electrolyte systems can advantageously be used and / or properties of the alkali-sulfur cell, in particular the cycle stability, can be improved.
  • the catalyst and optionally the inhibitor are also partially or completely removed in the same removal step or in a further removal step.
  • elemental sulfur can be carried out by means of a Soxhlet extraction, in particular with an apolar solvent or solvent mixture, for example toluene.
  • reaction mixture when used as the cathode material for an alkali-sulfur cell, in particular a lithium-sulfur cell, an even higher voltage and capacity of the cell can advantageously be achieved.
  • the sulfur utilization can be improved by the excess or unreacted or unbound, in particular elemental, sulfur, in particular in combination with the polyacrylonitrile-sulfur composite material according to the invention.
  • the polyacrylonitrile-sulfur composite material offers a conductive surface that can be used to reduce elemental sulfur.
  • the polyacrylonitrile-sulfur composite material can inhibit a migration of polysulfides formed during a reduction of the elemental sulfur, for example into the anode region, by virtue of the covalently bonded sulfur of the polyacrylonitrile
  • the polysulfide anions can open sulfur bridges in the polyacrylonitrile-sulfur composite material, wherein, for example, in each case two polysulfide monoanions are formed which are covalently bound to the cyclized polyacrylonitrile skeleton at one chain end.
  • such polysulfide chains can be built up successively. Since these polysulfide chains are covalently bonded to the cyclized polyacrylonitrile skeleton, they can no longer be dissolved by the electrolyte.
  • the reaction can be a one-step synthesis, for example analogous to that described by Wang et al. and Yu et al. act.
  • the method may include the method steps:
  • an electrically conductive base in the form of the electrically conductive, cyclized polyacrylonitrile (cPAN) can be formed first of all.
  • the reaction with the electrochemically active sulfur can then take place, in particular wherein it is covalently bonded to the electrically conductive skeleton of cyclized polyacrylonitrile to form a polyacrylonitrile-sulfur composite material (ScPAN).
  • Process step a) here resembles a dehydrogenation reaction known from carbon fiber production, process step b) being similar to a reaction from another entirely different technical field, namely the vulcanization reaction of rubber. This has the advantage that it can be made possible the production of a polyacrylonitrile-sulfur composite material with a defined structure.
  • the sulfur already has an oxidation number of -2 and, when used in a cathode of an alkali-sulfur cell, in particular a lithium-sulfur cell, theoretically can not be further reduced.
  • the sulfur of thioamide units thus reduces the theoretical sulfur utilization of the cathode material.
  • Process step a) can be carried out in particular in an oxygen-containing atmosphere, for example an air or oxygen atmosphere.
  • process step a) for example, at a temperature in a range of> 150 ° C to ⁇ 500 ° C, in particular from> 150 ° C to ⁇ 330 ° C or ⁇ 300 ° C or ⁇ 280 ° C, for example of> 230 ° C to ⁇ 270 ° C, take place.
  • the reaction time of process step a) can be less than 3 h, in particular less than 2 h, for example less than 1 h.
  • process step a) can take place in the presence of a cyclization catalyst.
  • cyclization catalysts known catalysts can be used, for example, from the production of carbon fiber.
  • reaction temperature and / or the reaction time in process step a) can be reduced.
  • the reaction mixture is mixed occasionally or continuously in process step a).
  • process step b) it is possible in particular to use a previously explained vulcanization catalyst or vulcanization accelerator.
  • Process step b) can be carried out in particular in an inert gas atmosphere, for example in an argon or nitrogen atmosphere.
  • the reaction time of process step b) may be less than 8 hours, for example 1 hour to 7 hours, for example less than 3 hours.
  • Another object of the present invention is a polyacrylonitrile-sulfur composite material, for example, for use as a cathode material for an alkali-sulfur cell, in particular for a lithium-sulfur cell.
  • the inventive polyacrylonitrile-sulfur composite material can be produced by a method according to the invention.
  • polysulfide chains having a chain length of> 3 sulfur atoms, in particular> 4 or> 5 or> 6 or> 7 or> 8 or> 9 or> 10 sulfur atoms may be covalently bonded to the polyacrylonitrile skeleton of the polyacrylonitrile skeleton by the process according to the invention.
  • Sulfur composite material are bound.
  • polysulfide chains having a chain length of> 3 sulfur atoms are therefore covalent in the polyacrylonitrile-sulfur composite material according to the invention bonded to one or the polyacrylonitrile skeleton of the polyacrylonitrile-sulfur composite material.
  • a particularly high covalently bound sulfur content and thus a high capacity and energy density of the alkali-sulfur cell can be achieved.
  • at least a part of the sulfur atoms for example in the form of
  • Polysulfide chains intramolecularly on one or both sides with a cyclized polyacrylonitrile strand, in particular with formation of an annelated at the cyclized polyacrylonitrile strand S-heterocycle, and / or on both sides intermolecularly covalently bonded with two cyclized polyacrylonitrile strands, in particular forming a bridge, especially Polysulfid Portugal, between the cyclized polyacrylonitrile strands be.
  • the sulfur atoms can thereby probably directly by covalent sulfur-carbon bonds, as well as indirectly by one or more covalent sulfur-sulfur bonds, in particular polysulfide chains, and one or more sulfur-carbon bonds to the cyclized polyacrylonitrile skeleton.
  • a further subject of the present invention is a cathode material for an alkali-sulfur cell, in particular for a lithium-sulfur cell, which surrounds a polyacrylonitrile-sulfur composite material according to the invention.
  • the cathode material may comprise at least one electrically conductive additive, in particular selected from the group consisting of carbon black, graphite, carbon fibers, carbon nanotubes and mixtures thereof.
  • the cathode material may further comprise at least one binder, for example polyvinylidene fluoride (PVDF) and / or polytetrafluoroethylene (PTFE).
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • the cathode material is the cathode material
  • the cathode material may further comprise additional elemental sulfur. As already related to the
  • the cathode material can thereby
  • the sum of the percentages by weight of polyacrylonitrile-sulfur composite material, elemental sulfur, electrically conductive additives and binders can yield in particular a total of 100 percent by weight.
  • the cathode material in particular in the form of a cathode material slip for producing a cathode, may comprise at least one solvent, for example N-methyl-2-pyrrolidone.
  • a cathode material slurry can be applied, for example by knife coating, to a carrier material, for example an aluminum plate or foil.
  • the solvents of the cathode material slip are preferably removed again after the application of the cathode material slip 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.
  • a lithium metal anode for example in the form of a plate or foil of metallic lithium
  • an electrolyte can be added.
  • the electrolyte may comprise, for example, 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, especially cyclic or acyclic carbonates, lactones, ethers, especially cyclic or acyclic ethers, and combinations thereof.
  • the electrolyte solvent may include diethyl carbonate (DEC), dimethyl carbonate (DMC), propylene carbonate (PC), ethylene carbonate (EC), 1,3-dioxolane (DOL), 1,2-dimethoxyethane (DME), or a combination thereof consist of it.
  • DEC diethyl carbonate
  • DMC dimethyl carbonate
  • PC propylene carbonate
  • EC ethylene carbonate
  • DOL 1,3-dioxolane
  • DME 1,2-dimethoxyethane
  • the salt can for example be selected from the group consisting of Lithiumhe- hexafluorophosphate (LiPF 6), lithium bis (trifluormethylsulphonyl) imide (LiTFSI), lithium thiumtetrafluoroborat (LiBF 4), lithium trifluoromethanesulfonate (LiCF 3 S0 3), Li thiumchlorat (LiCI0 4 ), Lithium bis (oxalato) borate (LiBOB), lithium fluoride (LiF), lithium nitrate (LiNO 3 ), lithium hexafluoroarsenate (LiAsF 6 ), and combinations thereof.
  • LiPF 6 Lithiumhe- hexafluorophosphate
  • LiTFSI lithium bis (trifluormethylsulphonyl) imide
  • LiBF 4 lithium thiumtetrafluoroborat
  • LiCF 3 S0 3 lithium trifluoromethanesulfonate
  • the electrolyte solvent is preferably selected from the group consisting of cyclic carbonates, acyclic carbonates, and combinations thereof.
  • Lithium hexafluorophosphate (LiPF 6 ) is preferably used as conductive salt.
  • the electrolyte solvent is preferably selected from the group consisting of cyclic ethers, acyclic ethers and combinations thereof.
  • Lithium bis (trifluoromethylsulphonyl) imide is preferably used as conductive salt.
  • Another object of the present invention is an alkali-sulfur cell or battery, in particular lithium-sulfur cell or battery, with an alkali-containing, in particular lithium-containing, anode and a cathode, wherein the cathode comprises a cathode material according to the invention.
  • 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 may comprise an electrolyte, in particular described above.
  • the alkali-sulfur cell comprises an electrolyte of at least one electrolyte solvent and at least one conducting salt.
  • the electrolyte solvent is selected from the group consisting of cyclic carbonates, acyclic carbonates and combinations thereof, and / or the conductive salt lithium hexafluorophosphate (LiPF 6 ).
  • LiPF 6 lithium hexafluorophosphate
  • the electrolyte solvent is selected from the group consisting of cyclic ethers, acyclic ethers and combinations thereof, and / or the conductive salt lithium bis (trifluoromethylsulphonyl) imide (LiTFSI).
  • LiTFSI lithium bis (trifluoromethylsulphonyl) imide
  • an energy storage in particular mobile or stationary energy storage, which comprises an inventive alkali-sulfur cell or battery, in particular lithium-sulfur cell or battery.
  • the energy store may be an energy store for a vehicle, such as an electric or 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 telecommunications device as a cellphone, PDA, or a high energy storage system for a home or facility. Since the alkali-sulfur cells according to the invention or Batteries have a very high energy density, these are particularly suitable for vehicles and stationary storage systems, such as high energy storage systems for houses or facilities.
  • Sulfur and polyacrylonitrile were mixed in a weight ratio of 3: 1 and reacted in an argon atmosphere at 300 ° C to form a polyacrylonitrile-sulfur composite.
  • Sulfur and polyacrylonitrile were mixed in a weight ratio of 3: 1. To this was added 4% by weight of zinc oxide (ZnO). The mixture was reacted by heating for six hours at 250 ° C to a polyacrylonitrile-sulfur composite.
  • ZnO zinc oxide
  • Sulfur and polyacrylonitrile were mixed in a weight ratio of 3: 1. To this was added 4% by weight of zinc oxide (ZnO). The mixture was first heated to 330 ° C for 30 minutes and then to 200 ° C for 5.5 hours, converting to a polyacrylonitrile-sulfur composite.
  • ZnO zinc oxide
  • Sulfur and polyacrylonitrile were mixed in a weight ratio of 3: 1. To this was added 4% by weight of zinc oxide (ZnO) and 0.75% by weight of tetramethylthiuram disulfide. The mixture was first heated to 330 ° C for 30 minutes and then to 200 ° C for 5.5 hours, converting to a polyacrylonitrile-sulfur composite.
  • ZnO zinc oxide
  • tetramethylthiuram disulfide tetramethylthiuram disulfide
  • Sulfur and polyacrylonitrile were mixed in a weight ratio of 3: 1 and reacted in an argon atmosphere at 300 ° C to form a polyacrylonitrile-sulfur composite.
  • the product obtained was mixed in a weight ratio of 1: 2 with sulfur and 4 wt .-% zinc oxide (ZnO).
  • the mixture was converted to a polyacrylonitrile-sulfur composite by heating for six hours at 150 ° C.
  • Tetramethylthiuramdisulfid 0.75 wt .-% Tetramethylthiuramdisulfid mixed. The mixture was passed through heating for six hours at 150 ° C to a polyacrylonitrile-sulfur composite.

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  • General Chemical & Material Sciences (AREA)
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  • Engineering & Computer Science (AREA)
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Abstract

La présente invention concerne un procédé de fabrication d'un matériau composite polyacrylonitrile-soufre. L'objectif de l'invention est de préparer un matériau composite polyacrylonitrile-soufre présentant une grande proportion de soufre lié par covalence et ainsi d'augmenter la capacité, respectivement la densité d'énergie, d'une pile alcaline au soufre, notamment d'une pile au lithium-soufre, comportant ledit matériau composite polyacrylonitrile-soufre en tant que matériau de cathode. A cette fin, dans le cadre du procédé, du polyacrylonitrile est mis en réaction avec du soufre au moins temporairement en présence d'un catalyseur afin d'obtenir un matériau composite polyacrylonitrile-soufre. L'invention concerne également un matériau composite polyacrylonitrile-soufre, un matériau de cathode, une pile alcaline au soufre, respectivement une batterie alcaline au soufre, ainsi qu'un accumulateur d'énergie.
PCT/EP2012/053857 2011-05-02 2012-03-07 Matériau composite polyacrylonitrile-soufre WO2012150062A1 (fr)

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DE102011075053A DE102011075053A1 (de) 2011-05-02 2011-05-02 Polyacrylnitril-Schwefel-Kompositwerkstoff
DE102011075053.3 2011-05-02

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CN111226333A (zh) * 2017-10-31 2020-06-02 株式会社艾迪科 有机硫系电极活性物质的制造方法
CN112803003A (zh) * 2021-01-26 2021-05-14 浙江大学 一种具有高循环稳定性与高库伦效率的锂硫二次电池
CN116284516A (zh) * 2023-02-07 2023-06-23 国科广化精细化工孵化器(南雄)有限公司 一种萜烯多硫低聚物/聚丙烯腈复合材料及其制备与应用

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DE102015224194A1 (de) 2015-12-03 2017-06-08 Robert Bosch Gmbh Polyacrylnitril-Schwefel-Komposit mit erhöhter Kapazität
DE102015224204A1 (de) 2015-12-03 2017-06-08 Robert Bosch Gmbh Verfahren zu SPAN-Synthese mit konstantem Schwefelgehalt während der gesamten Reaktionszeit
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