TW201251187A - Composite materials, production thereof and use thereof in electrical cells - Google Patents

Abstract

The present invention relates to composite materials comprising a reaction product of (A) at least one organic polymer, (B) sulfur, (C) carbon in a polymorph which comprises at least 60% sp2-hybridized carbon atoms, and (D) 2-20% by weight of a perfluorinated or partly fluorinated polymer, based on the total weight of components (A), (B) and (C) used before reaction, and also to a process for producing inventive composite materials and to the use of inventive composite materials.

Description

201251187 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a composite material comprising a reaction product of the following components: (A) at least one organic polymer, (B) sulfur, (C) including at least 60 % sp2 - a polymorphic carbon of a mixed carbon atom, and (D) a 2 to 20% by weight total perfluorinated or partially fluorinated polymer based on the component used before the reaction and the total weight of (c). The invention further relates to a method of making a composite of the invention and to the use of the composite of the invention. [Prior Art] A battery or a rechargeable battery is merely an embodiment that can store electrical energy after generation and use it when needed. Due to the significantly better power density, it has recently evolved from water-based batteries to the development of charge cells in batteries that are completed by lithium ions. However, the density of conventional lithium ion batteries having a carbon anode and a metal oxide based cathode is limited. A new perspective on energy density has been opened up by lithium-sulfur batteries. In the sulphur battery, the sulfur in the sulfur cathode is reoxidized by the polysulfide '(iv) to reduce the sulfur-bonding bond when the battery is charged. • However, the problem is the solubility of polysulfides (such as Li2S4 and Li2S6), which can be colder in the agent and can migrate to the anode. The results can include: loss of capacitance and electrical insulation deposited on the sulfur particles of the electrode. The migration from the cathode to the anode can ultimately result in the discharge of the affected battery and the failure of the battery in the battery pack. The undesired migration of such polysulfide ions is also referred to as "shutuing", and 164545.doc 201251187 is a term also used within the scope of the present invention. There are many attempts to suppress this shuttle. For example, j Wang et al. propose a reaction product of adding sulfur and polyacrylonitrile to the cathode; Adv Funct. Mater. 2003, 13, 487 ff. Thus, a product is formed which is formed by the removal of hydrogen from polyacrylonitrile to simultaneously form hydrogen sulfide. It has also been proposed to use sulfur compounds instead of sulfur, such as CuS, FeS2* 2,5-dimercapto-1,3,4-thiadiazole. However, the capacitance of such batteries is not satisfactory. See, for example, P. Wang, */. five s〇c. 2002, 149 and J. Wang et al., 乂 2〇〇4, 138, 2Ί\. It is also proposed to use sulfur in a finely divided form; see j Wang et al, J. Pwa仏 2004, 27 However, at high current densities, fluctuations in efficiency were observed, which the authors expected to deposit on the (tetra) crystal. This can be cumbersome because it can cause internal short circuits. It is also proposed to mix the reaction product of sulfur and polyacrylonitrile with carbon black and press it to the electrode; J. Wang et al., Shi (10) 2〇〇2, ^(6) ff. When these electrodes were combined with the polymer as electrolysis (4), a decrease in the shuttle mechanism was observed. However, many polymer electrolytes have low electrical conductivity. SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a cathode material that is easy to prepare and that avoids the disadvantages of the prior art. Another object of the invention is to provide a method for preparing a corresponding cathode material. Therefore, the material defined at the beginning has been found. [Embodiment] 164545.doc 201251187 Japan: The bright material is a composite material, and is also referred to as a hair-recovering σ material within the scope of the present invention. Composite material is understood to mean a solid mixture material that is not artificially dissociable and has properties that are different from the individual components. The material of the invention is in particular a particulate composite. The composite of the present invention comprises the reaction product of the following components: (Α) at least one organic polymer, abbreviated as polymer (Α) or organic polymer (Α). Within the scope of the present invention, the phrase polymer includes a homopolymer. And copolymer, (Β) sulfur (C) includes at least 60. /. Sp2_mixed carbon atom in the form of polymorphic carbon and (D) based on the total weight of components (A), (B) and (C) used before the reaction, 2 to 20% by weight of perfluorinated or partially fluorine Polymer. The polymer (A) may be selected from any of organic polymers and copolymers, and is preferably selected from polymers which can be obtained by anion or radical (co)polymerization. The organic polymer or copolymer preferably consists of atoms of elemental carbon and hydrogen (and optionally nitrogen, 4, oxygen, sulfur and/or gas), especially elemental carbon and hydrogen (and optionally nitrogen, oxygen and/or gas). The atom of 'especially nitrogen'. The "(co)polymerization" means homopolymerization or copolymerization. The term "(co)polymer" means a homopolymer or a copolymer. In another variation, the polymer (A) may be selected from the group consisting of organic polyesters, especially aliphatic polyesters. In one embodiment of the invention, the polymer is selected from (co)polymers obtainable by anionic, catalytic or free radical (co)polymerization, especially polyethylene, polypropylene, polyacrylonitrile, polybutylene Diene, polystyrene and at least 164545.doc 201251187 Two copolymers selected from the group consisting of ethylene, propylene, styrene, (meth) propylene (especially acrylonitrile) and 1,3-butadiene a copolymer of monomers. Further, polyisoprene and polyacrylate are also suitable. Polyacrylonitrile is especially preferred and is also known as polyacrylonitrile (A) within the scope of the present invention. Within the scope of the present invention, polyacrylonitrile should not be understood merely to mean a polyacrylonitrile homopolymer, and means a copolymer of acrylonitrile with hydrazine, 3-butadiene or styrene. A polyacrylonitrile homopolymer is preferred. In one embodiment of the invention, the polyacrylonitrile (A)' is present after the reaction, i.e., in the composite of the present invention, at least partially in the form of a cyclization of formula (1). (I) , , , N, everyone, within the scope of the present invention, polyethylene is understood to mean not only homopolyethylene, but also ethylene copolymer 'which comprises at least 50 mol% of ethylene in copolymerized form and Up to 50 mol% of at least one other comonomer, such as an alpha olefin (such as propylene, butene (1-butene), 1-hexene, octene, decene, decadiene, 1-pentyl Ole and isobutylene), vinyl aromatic compounds (such as styrene) and (mercapto) acrylic acid, ethyl acetate vinegar, ethyl vinegar propionate (meth)acrylic acid 0:1 to (:1〇 Alkyl esters (especially decyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, 2-ethylhexyl acrylate, n-butyl methacrylate Ester, mercaptopropionic acid 2_ethylhexanoic acid) and maleic acid, maleic anhydride and itaconic acid needle. Polyethylene can be Hdpe or LDPE. 164545.doc 201251187 Within the scope of the invention 'polypropylene It is understood to mean homopolypropylene, and is understood to mean a propylene copolymer comprising at least 50 mol% of propylene in copolymerized form and up to 5 〇 magnetic to Another comonomer such as ethylene and < olefins such as butene, hexene, octene, 1-decene, 1 - decene and 1,4-pentene. The polypropylene is preferably isotactic or basic. Superconducting polypropylene. - Within the scope of the present invention, polystyrene is understood to mean not only a homopolymer of styrene but also styrene and acrylonitrile, butadiene, (meth)acrylic acid, Copolymer of CiiCi decyl (meth) acrylate, divinyl benzene, 1,2-diphenylethylene or α-methyl phenylethylidene (especially with propylene or bismuth-butadiene) Another preferred polymer (Α) is a polybutadiene. In the embodiment of the invention, the compound (4) is selected from the group consisting of 50 〇〇〇 to 5 刖 in the reaction enthalpy. The average molecular weight of g/m〇1 (preferably to 25〇〇〇〇g/m〇i) is ^1~^ In one embodiment of the invention, the polyacrylonitrile (A) is selected from the group consisting of Polyacrylonitrile having an average molecular weight Mw in the range of 10 000 to 500 000 g/m 〇 1 (especially 5 〇〇〇〇 to 250 000 g/mol) before the reaction. The polymer (A) may be crosslinked or Non-crosslinked (co)polymerization • Sulfur (B) is known per se and may also be referred to as sulfur in the context of the present invention. 'Including at least 60% sp2_mixed carbon atoms (preferably at least 75% sp2-mixed carbon atoms) The carbon of the form, also referred to as carbon (C) in the scope of the present invention, is known per se as a conductive polymorph of carbon (C). For example, carbon (C) may be graphite. All impurities (c) included in the composite 164545.doc 201251187 material of the present invention under chemical reaction conditions include any impurities and represent weight percentages. In one embodiment of the invention, the carbon is carbon black. The carbon black can, for example, be selected from the group consisting of lamp black, furnace black, flame carbon black, thermally cracked carbon black, acetylene black, and industrial carbon black. The carbon black may include impurities such as hydrocarbons (especially aromatic hydrocarbons) or oxygenates or oxygen-containing groups (e.g., hydrazine H groups). In addition, sulfur black or iron-containing impurities may be present in the carbon black. The carbon (c) used to prepare the reaction product of the composite of the present invention is preferably selected from carbon black. In a variant, carbon (C) is a partially oxidized carbon black. In an embodiment of the invention, the carbon (C) comprises a carbon nanotube. Nanocarbon camps (reduced CNTs), such as single-walled carbon nanotubes (sw CNTs) and preferably multi-walled carbon nanotubes (MW CNTs), are known per se. The preparation thereof and some of its properties are described, for example, by A. Jess et al. in c/zemz.e / «geWew 2006, 7 < §, 94-100. In one embodiment of the invention, the carbon nanotubes have a diameter in the range of 〇4 to 5 〇 nm (preferably 1 to 25 nm). In one embodiment of the invention, the carbon nanotubes have a 10 nm to The length in the range of 丨mm (preferably 100 nm to 500 nm). The carbon nanotubes can be prepared by a method known per se. For example, a volatile carbon compound (such as decane or carbon monoxide, acetylene or ethylene) or a mixture of volatile carbon compounds (such as a synthesis gas) may be used in one or more reducing agents (eg, hydrogenated milk and/or another gas, Decomposition in the presence of, for example, nitrogen). Another suitable gas mixture is a mixture of nitric oxide and ethylene. A suitable temperature for decomposition is 164545.doc 201251187 (for example) in the range of 400 to 1000 ° C, preferably 500 to 800 ° C. Suitable pressure conditions for decomposition are, for example, in the range of standard pressures up to 1 mbar (preferably to 1 mbar). Single-walled or multi-walled carbon nanotubes can be obtained, for example, by decomposing carbon-containing compounds under arcing, in particular in the presence or absence of a decomposition catalyst. In one embodiment, the decomposition of the volatile carbonaceous compound or carbonaceous compound is carried out in the presence of a decomposition catalyst (e.g., Fe, or preferably oxime). The starting mixture for the preparation of the reaction product of the composite of the invention comprises, as component (D), from 2 to 20% by weight (preferably from 3 to 15% by weight, in particular from 4% by weight); based on the components used before the reaction. A perfluorinated or partially fluorinated polymer based on the total weight of (A), (B) and (c). An example of the perfluorinated or partially fluorinated polymer (D) may be a fluorinated homopolymer or copolymer. The polymer (D) is preferably selected from the group consisting of polytetrafluoroethylene, polyvinyl fluoride, polydifluoroethylene, tetrafluoroethylene hexafluoropropylene copolymer, and difluoroethylene-hexafluoropropylene copolymer (PVdF-HFp). , difluoroethylene ethylene_tetrafluoroethylene copolymer, perfluoroalkyl vinyl ether copolymer, ethylene_tetrafluoroethylene copolymer, difluoroethylene-trifluoroethylene polymer and ethylene-fluorovinyl chloride copolymer A group of disastrous polymers of the group. The perfluorinated or partially polymerized polymer (D) is preferably used in the form of a powder. It is especially preferred to use a powder having an average particle size of 0.1 to 1 () _ (especially G5 to 2 _). Within the scope of the present invention, polytetramethylene glycol homopolymer, and means tetrafluoroethylene copolymer, and tetrafluoroethylene, hexaene are understood to mean not only polytetrafluoroethylene and hexafluoropropylene or two Fluorinated fluoropropene and difluoroethylene are composed of a ternary copolymer of 164545.doc 201251187. The perfluorinated or partially fluorinated polymer (D) is preferably polytetrafluoroethylene, especially a polytetrafluoroethylene homopolymer. At least two of the above-mentioned starting materials have been chemically reacted with each other during the preparation of the composite of the present invention, preferably polymer (A) and sulfur. In this case, the polymer (A) and sulfur do not need to form a covalent bond with each other. For example, sulfur can only act as an oxidant and be removed from the reaction mixture as Hj. In one embodiment of the invention, polymer (A) and sulfur (B) form a covalent bond during formation of the composite of the invention. In a preferred embodiment, the composite of the present invention further comprises particles or domains. Containing sulfur (Β)-filled carbon (C)e In this embodiment of the invention, the sulfur is preferably dispersed in the carbon by the particles or domain molecules, for example in the form of a h ring or in the form of a linear sulfur molecule. (eg line type & numerator). Such particles or domains can be detected, for example, by electron probe microanalysis. In one embodiment of the invention, the pores of carbon (c) in such particles or domains are at least partially filled with sulfur (B). These particles or domains may have an average diameter in the range of 10 to 1 〇〇 μπι (preferably to 7 〇 μηη). These particles can be mechanically removed from the composite of the present invention. The domain cannot be mechanically removed from the composite of the present invention. The domains and particles are easily identifiable under the microscope. In one embodiment of the invention, the particles or domains comprise carbon (c) and sulfur (helium) in a weight ratio ranging from 2:1 to US (preferably from 1:1.5 to 1:10). Preferably, the above particles or domains are black to the human eye. 164545.doc 201251187 In one embodiment of the invention, the above particles or domains comprise no more than 5% by weight of polymer (4) or no more than 5% by weight of the above reaction product. In a particular embodiment of the invention, neither the compound (4) nor the above reaction product is detectable in the particles or domains described above. The composite of the present invention may further comprise particles or domains comprising a significant proportion of the above reaction product, for example up to at least 1 Torr. / The extent of 〇. The latter particles or domains may have a diameter in the range of 5 to 75 μηι, preferably 10 to 5 μ μη. It is preferably smaller than the previous particles or domains. In one embodiment of the invention, the composite of the invention comprises, by elemental analysis, sulfur in the range of from 20 to 80% by weight, preferably from 30 to 7% by weight. In one embodiment of the invention, the composite of the invention comprises from 〇. 丨 to 3 重量% by weight, preferably from 1 to 20 重量. /. Carbon (C) within the range. This carbon can also be determined, for example, by elemental analysis, although carbon which is also incorporated into the composite of the invention via the polymer (Α) must be taken into account in the evaluation of the elemental analysis. The reaction product of the composite of the invention having the desired sulfur content from components (A), (Β), (C) and (D) must be considered to form a gaseous state due to the reaction of sulfur with the hydrogen atom of the polymer (Α). Loss of sulfur used due to hydrogen sulfide. The proportion of the component (Α) (especially in the case of polyacrylonitrile) is preferably 4, 9 to 45% by weight before the reaction, based on the total weight of the components (A), (Β) and (C) used before the reaction. In particular, from 10 to 40% by weight, the proportion of the component (β) is preferably from 35 to 95% by weight, particularly from 45 to 85% by weight, before the reaction, and the proportion of the component (the ratio of ruthenium is preferably 0.1 before the reaction). Up to 20% by weight, especially 5 to 15% by weight. In another embodiment of the invention, the composite material of the invention may further comprise 164545.doc 201251187 comprising at least one binder (E). The binder (E) is mainly used The composite of the present invention is mechanically stabilized. In one embodiment of the invention, the binder (E) is selected from the group consisting of organic (co)polymers. Examples of suitable organic (co)polymers may be either functional or toothless. Examples are polyethylene oxide (PEO), cellulose, carboxymethyl cellulose, polyvinyl alcohol 'polyethylene, polypropylene, polytetrafluoroethylene, polyacrylonitrile-methyl methacrylate copolymer, benzene. Ethylene-butadiene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, difluoroethylene-hexafluoropropylene copolymer (P VdF-HFP), difluoroethylene-tetrafluoroethylene copolymer, perfluoroalkyl vinyl ether copolymer, ethylene·tetrafluoroethylene copolymer, difluoroethylene-trifluoroethylene copolymer, ethylene-fluorine gas Ethylene copolymer, ethylene-acrylic acid copolymer (optionally at least partially neutralized with alkali metal salt or ammonia), ethylene thioglycolic acid copolymer (optionally at least partially neutralized with alkali metal salt or ammonia), ethylene _ (A Acrylic vinegar copolymer, polyimine and polyisobutylene. Suitable binders are, in particular, polyvinyl alcohol and halogenated (co)polymers, such as polyethylene oxide or polydiethylene vinylene, especially fluorinated (total) Polymers, such as polyethylene and especially polydifluoroethylene and polytetrafluoroethylene. The average molecular weight Mw of the binder (E) can be selected from a wide range, suitable examples are 20 〇〇〇g/m〇l to 1 〇〇〇〇〇〇g/m〇l. If the binder (E) is used to prepare the composite material of the present invention, the composite material of the present invention preferably comprises 〇.1 to 1% by weight based on the mass of the final composite material. 'More preferably 5 to 10% by weight and most preferably 7 to 8% by weight of adhesion (E). The binder may be by a variety of methods (E) is incorporated in the composite material of the present invention. For example 'may be soluble binder (E) (such as polyvinyl alcohol) was dissolved in a suitable solvent 164545.doc

S 201251187 A solvent or solvent mixture (e.g., water/isopropanol suitable for polyvinyl alcohol) and a suspension prepared with its ruthenium cathode component. After application to a suitable substrate, the solvent or solvent mixture (e. g., evaporation) is removed to provide a composite of the present invention. A suitable solvent for polydifluoroethylene is Nmp. If it is desired to use a poorly soluble polymer as the binder (E) (for example, other perfluorinated or partially fluorinated (co)polymers such as polytetrafluoroethylene or tetrafluoroethylene-hexafluoropropylene copolymer) A suspension of the binder and other components of the cathode is discussed and compressed under thermal conditions. In one embodiment of the invention, the composite of the invention additionally comprises carbon incorporated into the composite under non-reactive conditions. This additional carbon may be selected from the same materials as carbon (C). It may be the same or different in carbon (c) in each case; for example, carbon (C) and the selected additional carbon may be two different carbon blacks or graphites. In one embodiment of the invention, the composite of the invention additionally comprises carbon black which is not reactive with the organic polymer (A) or polyacrylonitrile (A) and sulfur (B). In one embodiment of the invention, the composite of the invention comprises from 0.1 to 10% by weight of additional carbon, preferably additional carbon black, based on the mass of the final composite. The composite materials of the invention are particularly suitable for use in or for the preparation of electrodes, particularly for the preparation of electrodes for lithium-containing battery packs. The invention provides the use of the composite of the invention as or for the preparation of electrodes for batteries. The invention further provides a battery comprising at least one electrode that has been prepared from (or used in) at least one composite of the invention. In one embodiment of the invention, the electrode discussed is a cathode, which may also be referred to as a sulfur cathode or a s cathode, 164545.doc • 13-201251187. Within the scope of the present invention, an electrode referred to as a cathode has a reducing action upon discharge (operation). In an embodiment of the invention, the composite of the invention is treated to provide an electrode, for example in the form of a continuous strip that is processed by a battery manufacturer. The electrode prepared from the composite of the present invention may, for example, have a thickness of from 2 Å to 5 Å μm, preferably from 40 to 2 Å μηη. They may, for example, have a rod configuration, or be arranged in the form of a circle, an ellipse or a square cylinder or in the form of a cube, or as a flat electrode. In one embodiment of the invention, the battery of the present invention comprises, in addition to the composite of the present invention, at least one electrode comprising metallic zinc, metallic sodium or preferably metallic lithium. In one embodiment of the present invention, the battery of the present invention comprises, in addition to the composite material of the present invention and another electrode, at least one non-aqueous solvent, which may be liquid or solid at room temperature, preferably selected from the group consisting of polymers, A cyclic ether or acyclic ether 'cyclic or acyclic acetal, a cyclic or acyclic organic carbonate, and an ionic liquid. Examples of suitable polymers are, in particular, polyalkylene glycols, preferably polyCl_c4^diols and especially polyethylene glycols. Such polyethylene glycols may comprise up to 2 mole% of one or more of the Cl_C4 alkanediols in copolymerized form. The polyalkylene glycol is preferably a polyalkylene glycol terminated with a methyl group or an ethyl group at both ends. Suitable polystyrenes and especially suitable polyethylene glycols may have a molecular weight Mw of at least 400 g/mol, a suitable polyhydric alcohol and especially a suitable polyethylene glycol having a molecular weight Mw of up to 5 000 000 g/mol, preferably up to 2 000 000 g/m〇i. 164545.doc

SJ such as diisopropyl ether, di-n-butyl ether, ethoxyethane, preferably 1,2-dimethoxy 201251187. Examples of suitable acyclic mysteries are (example 1,2-dimethoxyethane) , 1 7 A, bis-diylethane. Examples of suitable cyclic ethers are tetraf-oxygens and south, and 1,4 - two

Dioxolane. Examples of suitable acyclic organic carbonic acid salts are carbonic acid di- and 1,4-dioxane. For example, dimethanol methyl chain, diethanol [~ ethoxy ethoxy). Dioxane and especially hydrazine, 3-ethyl ester and diethyl carbonate. Example of a suitable cyclic organic carbonated vinegar, which is a compound of the formula

R FT

Wherein 'R1, R2 and R3 may be the same or different' and are selected from hydrogen &Ci_C4•alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second The base and the third butyl group, wherein R2 and R3 are preferably different, are a third butyl group. In a particularly preferred embodiment, R is methyl' and R and R3 are each hydrogen, or r 1 , R 2 and R 3 are each hydrogen. 164545.doc •15· 201251187 Another preferred cyclic organic carbonate is a carbonic acid extending vinyl ester of the formula (ιν). Further, 0 0 W ον) The solvent is preferably used in a so-called anhydrous state, that is, the water content is in the range of 1 ppnl to 〇. 1 weight °/〇, which can be, for example, by Karl Fischer titration. To determine enthalpy In one embodiment of the invention, the electrochemical cell of the present invention comprises one or more conductive salts 'preferably a lithium salt. Examples of suitable lithium salts are LiPF6, LiBF4,

LiC104, LiAsF6 'LiCF3S03, LiC(CnF2n+1S〇2)3, lithium iminoide such as LiN(CnF2n+iS02)2 (where n is an integer from 1 to 20), LiN(S02F)2, Li2SiF6, LiSbF6, LiAlCl4 And a salt of the formula (CnF2n+1S02)m XLi' wherein m is defined as follows: when X is selected from oxygen and sulfur, m = 1, when X is selected from nitrogen and helium, m = 2, and when The X system is selected from the group consisting of carbon and Shixia, and m=3. Preferably, the conductive salt is selected from the group consisting of LiC(CF3S02; h, LiNKCF3S〇2)2, LiPF6, LiBF4, LiC104', and particularly preferably LiPF6&LiN(CF3S02)2. In one embodiment of the invention, the electrochemical cell of the present invention comprises one or more spacers for mechanically separating the electrodes. Suitable separators are polymeric membranes, especially porous polymeric membranes which do not react with metallic lithium and lithium sulfide and lithium polysulfide. Particularly suitable separator materials are polyolefins, especially porous polypropylene in the form of a film and porous polypropylene in the form of a film. Separator made of polyolefin (especially made of polyethylene or polypropylene) 164545.doc -16 201251187

shuttle. The battery of the present invention is extremely suitable for use in automobiles, electric valleys, and even in repeated charging. It is extremely effective in suppressing wear, aircraft, watercraft or static energy storage. These uses form part of the subject matter of the present invention. The invention further provides a process for the preparation of the composite of the invention which is also referred to as the process of the invention within the scope of the invention. The preparation method of the present invention comprises at least one process step wherein (A) at least one organic polymer, (B) sulfur, (C) comprises at least 60% sp2 of a polymorphic carbon of a mixed carbon atom, and (D) 2 to 2 Å by weight of the perfluorinated or partially fluorinated polymer at 150 to 400 ° C (preferably 200 to 350 ° C) based on the total weight of the components (A), (B) and (c) used. In the range of temperature, the organic polymer (A), sulfur (B), carbon (germanium and perfluorinated or partially fluorinated polymer (D) are respectively defined as above, especially A preferred embodiment. The organic polymer (A) is preferably selected from the group consisting of polyethylene, polypropylene, polyacrylonitrile, polybutadiene, polystyrene, and at least two selected from the group consisting of ethylene, propylene, and benzene 164545.doc 17 201251187 Copolymer of comonomers of ethylene, acrylonitrile and 1,3-butadiene (optimally selected from acrylonitrile). Components (A), (B), (C) and (D) are in thermal reaction. Those skilled in the art can start with the desired final composition after the thermal reaction and consider gaseous by-products that may form in the thermal reaction (specifically, such as nitrogen sulfide) The ratios calculated in a simple manner are combined with each other. The preparation method of the present invention can be carried out in the presence of a solvent such as toluene or ethanol. However, it is preferred to carry out the preparation method of the present invention in the absence of a solvent. The preparation method of the present invention is carried out under ambient pressure (ie, under standard pressure). In another embodiment of the present invention, the preparation method of the present invention is carried out under high pressure (for example, at 1:1 to 1 Torr). In another embodiment of the present embodiment, the method of the present invention is carried out under autogenous pressure for this purpose, any pressure (e.g., bar or standard pressure) can be established 'and in a pressure vessel (e.g., autoclave). The reaction is carried out in. The gaseous by-product formed (especially HzS) can increase the pressure during the reaction, for example up to a pressure of up to 100 bar or higher. If it is desired to carry out the preparation process according to the invention under autogenous pressure, it can be used The pressure measurement is used to monitor the reaction. In one embodiment of the present invention, the preparation method of the present invention can be carried out for a period of time ranging from 10 minutes to 100 hours, preferably Preferably, after completion of the reaction, the resulting composite of the invention is free, for example degassed. Degassing can be carried out, for example, by vacuuming or by using an inert gas (for example with nitrogen or The rinsing is accomplished by an inert gas such as argon. The composite of the invention is typically obtained in powder form. 164545.doc

S 201251187 The invention further provides a method of operating a car, aircraft, vessel or static energy storage using at least one of the inventive batteries. The invention is illustrated by the following non-limiting examples. Values expressed in % are by weight unless otherwise indicated. 1. Synthetic composite material 1,1 synthetic control composite material C-CM.1 (carbon black-PAN-S complex) 20 g sulfur, 1 〇g polyacrylonitrile and 6 g carbon black (purchased by Ketjen Black) It was homogenized in a mortar and introduced into a 3 〇〇 ml autoclave. The conversion was carried out at 280 c under autogenous pressure while stirring (300 rpm) for 12 hours. During this period, the pressure rose to 43 bar. Subsequently, the formed H2S was discharged through a NaOH scrubber, and the composite was washed with nitrogen for 24 hours. Obtained 29.4 g of a hard dark gray to black powder C-CM. Elemental analysis: C = 43.5 g / 100 g S = 45.8 g / 100 g N = 7.5 g / l 〇〇 g H = 1.4 g / l 〇〇 g. 1.2 Synthesis of the composite material CM 2 of the invention (pTFE_carbon black_pAN_s complex) 19.1 g sulfur, 6.4 g polyacrylonitrile, 45 g carbon black (commercially available from Ketjen Biack) and 2.1 g have an average particle size of ΐμπι The Teflon powder was homogenized in a mortar and introduced into a 3 Torr autoclave. The conversion was carried out at 280 ° C under autogenous pressure while stirring (3 rpm) for 12 hours. During this period, the pressure rose to 21 bar. Subsequently, the formed 164545.doc -19·201251187 HZS was discharged through a Na〇H scrubber, and the complex was washed with nitrogen for 24 hours. 25 2 of this fine powder material CM_2 was obtained. ' Elemental analysis: C = 35.3 g/l 〇〇 g S = 50.0 g/l 〇〇 g N=6.3 g/lOOg H=<0.5 g /l 〇〇g. II. Preparation of electrode II_1 Preparation of control cathode c-c.l from C.CM.l For preparation of ink, 0.09 g of Teflon, o 〇5 g of graphite (purchased from KS6)

Timcal AG, 6743 Bodio, Switzerland) and 1.67 g C-CM.1 were added to the water/isopropanol and stirred. For dispersion, the mixture was transferred to a stainless steel grinding vessel and then stirred using a ball mill (Pulverisette from FHtsch) using a stainless steel ball at 300 rpm for 3 minutes. The dispersion operation produces an extremely homogeneous ink with a slight grease. The ink was sprayed onto the aluminum foil by means of a spray method on a vacuum adsorption platform (temperature: 60 〇). Spray with nitrogen. A solid loading of 2.5 mg/cm2 was obtained. II.2 Preparation of cathode c.2 of the invention from CM.2 To prepare ink '0.04 g of graphite (purchased from Sigma 6 from Timcal AG, 6743 Bodio, Switzerland) and 1.69 g of CM.2 to 17.0 g of water/isopropanol Mix and stir the mixture. For dispersion, the mixture was transferred to a stainless steel grinding vessel, and then a ball mill (pulverisette from Fritsch) was used, and a stainless steel ball was used to scramble for 30 minutes at 300 rpm. The dispersion operation produces an extremely homogeneous ink with a consistency of oil. The ink was sprayed onto the aluminum foil by means of a spray method on a vacuum adsorption platform 164545.doc -20- 201251187 (temperature: 6 Torr. 〇. Spraying with nitrogen to obtain a solid loading of 2.5 mg/cm2. III. The test cathode in the battery is obtained by comparing the electrochemical characteristics of the cathode CC.1 and the cathode C.2 of the present invention. The electrochemical cell is assembled according to Fig. 1. For this purpose, except for the cathode prepared in II. The following components were used: Anode. Crypt, thickness 50 μηι, spacer: microporous, three-layer film (ΡΡ/ΡΕ/ΡΡ), thickness 38 μπι (commercially available from Celgard® 2340) Cathode: According to Example II Electrolyte: 1M LiTFSI (LiN(S02CF3)2) is contained in a mixture of dioxolane and dimethoxyethane (1:1). Figure 1 shows the disassembled electrochemical cell used to test the composite of the present invention. The schematic structure in Fig. 1 means: 1, 模 die 2, 2' nut 3, 3' * seal ring one of two in each case, here is not shown the second one in each case Small sealing ring. 4 coil spring 5 output conductor made of nickel 6 housing in 1.8 Charging and discharging of a specific battery using a current of 7.50 mA at a potential of 2.5 V. The results are summarized in Table 1, 164545.doc 21 201251187 Table 1: Test Results of the Invention and Non-Inventive Electrochemical Cell Example Discharge Capacity 5 cycles [mA-h/g S] discharge capacity 50th cycle [mA-h/g S] discharge capacity 100th cycle [mA-h/g S] Cathode CC.1 based on C-CM.1 830 690 (Battery pack collapse) Cathode C.2 870 850 700 based on CM.2 [Schematic description of the drawing] Fig. 1 shows a schematic structure of a disassembled electrochemical cell for testing the composite material of the present invention. 1 Die Γ Die 2 Nut 2' Nut 3 Sealing ring 3' Sealing ring 4 Coil spring 5 Nickel output conductor 6 Housing 164545.doc -22-

Claims (1)

201251187 VII. Patent Application Range: 1 · A composite material comprising the reaction products of the following components: (A) at least one organic polymer, (B) sulfur, (C) including at least 60. /〇 sp2 - a polymorphic carbon of a mixed carbon atom, and (D) 2 to 20% by weight of a perfluorinated or partially fluorinated polymerization based on the total amount of the component used before the reaction, (B) and the total weight thereof Things. 2. The composite of claim 1 wherein the composite comprises particles or domains comprising sulfur (B) filled carbon (C). 3. The composite material of claim 1 or 2, wherein the organic polymer is selected from the group consisting of polyethylene, polypropylene, polyacrylonitrile, polybutadiene, polystyrene, and at least two selected from the group consisting of ethylene, propylene, and stupid ethylene. Copolymer of acrylonitrile and ruthenium, a comonomer of 3-butadiene. 4. The composite of claim 1 wherein the organic polymer (A) is selected from the group consisting of polyacrylonitrile. 5. The composite material of claim 4 wherein polyacrylonitrile (A) is present in the form of at least a portion of the cyclized product of formula I after the reaction 6. The composite of claim 4 or 5, wherein the polyacrylonitrile (A) has an average molecular weight mw in the range of from 50 Å to 250 000 g/mol before the reaction. The composite of any one of the claims i, 2, 4 and 5, wherein the carbon (C) is selected from the group consisting of carbon black. 164545.doc 201251187 8. 9. 10, 11. 12. 13. Division: The composite or partially gasified polymer (9) of any of items 1, 2, 4 and 5 is polytetraethylene. And a battery comprising at least one of the electrodes prepared or used in the composite material of any one of claims 1 to 8. The battery of claim 9, which is the electrode of the cow. The step comprises at least one battery comprising metal lithium as claimed in claim 9 or 1 'which comprises at least one selected from the group consisting of polymers, cyclo- or acyclic, acyclic or cyclical and cyclic or acyclic organic A non-aqueous solvent for carbonates. A method of preparing a composite material comprising at least one process step, wherein (A) at least one organic polymer, (B) sulfur, (C) comprises at least 60% sp2·mixed carbon atoms in a polymorphic carbon And (D) 2 to μ% by weight of the perfluorinated or partially fluorinated polymer at a temperature in the range of 150 to 400 eC, based on the total weight of the components (A), (B) and (c) used. React with each other. A method of preparing a composite material according to any one of the preceding claims, comprising at least one process step, wherein (A) at least one organic polymer, (B) sulfur, (C) comprises at least 60% 邛2 _ a carbon of a polymorphic carbon of a mixed carbon atom, and (D) a total of 2 to 2% by weight of perfluorinated or partially fluorine based on the total weight of the components (A)' (B) and (c) used Polymer 164545.doc S -2- 201251187 14. Aircraft and ships react with each other at temperatures ranging from 150 to 400 °C. A use of a battery according to any one of claims 9 to 11 for car or static energy storage. I64545.doc