WO2015165762A1 - Procédé de production de corps monolithique de matière de carbone poreuse, corps monolithiques de matières de carbone poreuses spéciales et leur utilisation - Google Patents

Procédé de production de corps monolithique de matière de carbone poreuse, corps monolithiques de matières de carbone poreuses spéciales et leur utilisation Download PDF

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WO2015165762A1
WO2015165762A1 PCT/EP2015/058468 EP2015058468W WO2015165762A1 WO 2015165762 A1 WO2015165762 A1 WO 2015165762A1 EP 2015058468 W EP2015058468 W EP 2015058468W WO 2015165762 A1 WO2015165762 A1 WO 2015165762A1
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sulfur
carbon material
monolithic body
carbon
silica particles
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PCT/EP2015/058468
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Heino Sommer
Artur Schneider
Torsten Brezesinski
Juergen Janek
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Basf Se
Karlsruher Institut Für Technologie (Kit)
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Publication of WO2015165762A1 publication Critical patent/WO2015165762A1/fr

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Definitions

  • the present invention relates to a process for producing a monolithic body of a porous carbon material, to monolithic bodies of special porous carbon materials comprising a carbon phase and a pore phase of interconnected pores in the carbon phase, to composite materials comprising sulfur and said monolithic bodies of special porous carbon materials or fragments of said monolithic bodies of special porous carbon materials, to a process for producing said composite materials and to metal-sulfur cells comprising said composite materials.
  • Secondary batteries, accumulators or “rechargeable batteries” are just some embodiments by which electrical energy can be stored after generation and used when required. Owing to the significantly better energy density, there has in recent times been a move away from the water- based secondary batteries toward development of those batteries in which the charge transport in the electrical cell is accomplished by lithium ions.
  • shuttling a term which is also used in the context of the present invention.
  • Porous carbon materials are important components of the cathodes of lithium sulfur cells contributing significantly to the overall performance of lithium sulfur cells in particular with respect to coulombic efficiency, degree of capacity fading, self-discharge, durability or cycle life.
  • Said process comprises producing a monolithic template from inorganic matrix material having pores connected to each other, infiltrating the pores of the template with carbon or a carbon precursor substance forming a green body framework containing carbon surrounded by matrix material and calcining the green body framework forming the porous car- bon product
  • W013027155 discloses an electrode material for an electrical cell comprising activated carbon fibers as component (A) which have been impregnated with elemental sulfur as component (B). Cathode could be prepared without the use of any additional binder.
  • porous carbon materials and the sulfur-containing electroactive composites comprising said porous carbon materials which are described in the literature, still have shortcomings with regard to one or more of the properties desired for such materials and the electrochemical cells produced therefrom.
  • Desirable properties are, for example, high electrical conductivity of the cathode materials, maintenance of cathode capacity during lifetime, reduced self-discharge of the electrochemical cells during storage, an increase in the lifetime of the electrochemical cell, an improvement in the mechanical stability of the cathode or a reduced change in volume of the cathodes during a charge-discharge cycle.
  • the desired properties mentioned also make a crucial contribution to improving the economic viability of the electrochemical cell, which, as well as the aspect of the desired technical performance profile of an electrochemical cell, is of crucial significance to the user.
  • the object was to find a simple, flexible and economic method for the preparation of monolithic bodies of well-defined, highly porous carbon materials. It was also an object to find new monolithic bodies of carbon materials, which improve the performance of cathodes of lithium sulfur cells and the performance of the corresponding lithium sulfur cells themselves, particular in view of an improved electrical conductivity, combined with high cathode capacity, high mechanical stability and long lifetime.
  • step (d) optionally increasing the content of carbon material in the monolithic body obtained in process step (c) by repeating at least once the consecutive steps of infiltration under reduced pressure of the monolithic body comprising silica particles and carbon material with at least one carbon precursor substance, which is liquid during the infiltration step, followed by carbonization of the carbon precursor substance, and
  • a monolithic body refers to a massive, unchanging structure that does not permit individual variation.
  • a monolithic body has a three-dimensional geometric shape wherein the smallest of the three spatial dimensions (extents) is recognizable to the naked eye.
  • the inventive process allows the preparation of monolithic bodies of a porous carbon material, wherein the size of the monolithic body, the pore structure and the chemical composition of the carbon material can be varied in a wide range.
  • the size of the monolithic body of a porous carbon material can be varied depending on the size of the initially formed porous body comprising silica particles in process step (a)
  • the inventive process is characterized in that the monolithic body of a porous carbon material has a three-dimensional geometric shape wherein the smallest of the three spatial dimensions (extents) is in the range from 10 ⁇ to 10 m, preferably in the range from 100 ⁇ to 1 m, more preferably in the range from 1000 ⁇ to 0.1 m.
  • the chemical composition of the carbon material can be adjusted by choosing a carbon precursor substance that comprises beside carbon also heteroatoms, which remain after the carbonization in the formed carbon material. This allows the generation of heteroatom enriched carbon materials.
  • Preferred heteroatoms are selected from the group consisting of boron, nitrogen, phosphorus and sulfur, in particular nitrogen.
  • the content of the heteroatoms in carbon material can be chosen in a wide range depending on the amount of the respective heteroatom in the carbon precursor substance.
  • the mass fraction of the chemical element selected from the group consisting of boron, nitrogen, phosphorus and sulfur, in particular nitrogen is adjusted in the range from 0.01 to 0.25, based on the total mass of the porous carbon material of the monolithic body.
  • the mass fraction of these chemical elements is particularly preferred in the range from 0.01 to 0.1
  • nitrogen the mass fraction of nitrogen is particularly preferred in the range from 0.05 to 0.15.
  • the pore structure of the carbon material can be adjusted by choosing silica particles of an adequate size.
  • the size of the silica particles can be chosen in wide range, e.g. the average particle diameter can be varied in the range from 1 nm to 1000 ⁇ .
  • the porous carbon material is a nanoporous material, wherein nanoporous material in general are subdivided into 3 categories, namely microporous materials having pores in the range from 0.2 to 2 nm, mesoporous materials having pores in the range from 2 to 50 nm and macroporous materials having pores in the range from 50 to1000 nm.
  • Particularly preferred porous carbon materials are mesoporous carbon material.
  • the inventive process is characterized in that porous carbon material is a mesoporous carbon material which is enriched with a chemical element selected from the group consisting of boron, nitrogen, phosphorus and sulfur, in particular nitrogen.
  • the monolithic body of a porous carbon material obtainable or obtained by the inventive process preferably comprises a carbon phase and a pore phase of interconnected pores in the carbon phase, wherein the average pore diameter is in the range from 2 to 50 nm determined by Scanning or Transmission Electron Microscopy and the pore size distribution shows a d95- value in the range from 2 to 50 nm determined by means of a NLDFT calculation based on Ni- trogen Physisorption Measurements.
  • porous carbon materials are mesoporous carbon material, wherein the pore size distribution is a unimodal distribution.
  • the monolithic body of the porous carbon material shows a total pore volume in the range from 0.5 to 2.5 cm 3 g _1 and a specific BET surface area in the range from 50 to 1000 m 2 g -1 , preferably in the range from 300 to 500 m 2 g- 1 .
  • a porous body which comprises silica particles, which touch each other, is formed by compacting silica particles, followed optionally by washing and drying steps.
  • silica particles determine finally the pore structure of the porous carbon material of the monolithic body.
  • Silica particles of various sizes are known or commercially available.
  • the inventive process is characterized in that the silica particles used in process step (a) have an average particle diameter in the range from 2 to 50 nm, more preferably 5 to 50 nm.
  • Silica particles having an average particle diameter in the range from 2 to 50 nm, more preferably 5 to 50 nm, are commercially available as aqueous colloidal dispersions of silica particles, for example under the tradename Ludox ® from Grace. These aqueous colloidal dispersions of silica particles usually show a unimodal particle size distribution.
  • the silica particles forming the porous body in process step (a) can in principle be also chosen from mixtures of at least two different kinds of silica particles, each having a unimodal particle size distribution, but having different average particle diameters.
  • the silica particles used in process step (a) have a unimodal particle size distribution.
  • the inventive process is characterized in that the silica particles used in process step (a) have an average particle diameter in the range from 2 to 50 nm and the particle size distribution of the silica particles is a unimodal distribution.
  • the inventive process is characterized in that in process step (a) the compacting of the silica particles is achieved by means of centrifugation.
  • the compacted silica particles touch each other and form a porous body, wherein the pores are defined as the space that is not occupied by silica particles.
  • the obtained porous body is optionally washed with suitable solvents and afterwards dried in order to remove all liquid out of the pores of the porous body.
  • the porous body of compacted silica particles obtained in process step (a) is sintered under formation of a porous monolithic body comprising silica particles, which are fused together. While the porous body of process step (a) is a fragile body which can be easily crushed under recovery of the initial silica particles, the porous monolithic body is a single stable body, because the silica particles are now fused together to its ad- joining particles.
  • the fusion of individual silica particles which is accompanied by the formation of covalent chemical bonds, in particular the formation of Si-O-Si bonds, that means the formation of additional silica (S1O2) in the contact area, is responsible for the formation of a porous monolithic body.
  • the sintering of the silica particles can take place in wide temperature range, depending on applied pressure and duration of that process step.
  • the sintering of the porous body of compacted silica particles takes place at a temperature in the range from 200 °C to 800 °C, preferably in the range from 500 °C to 600 °C.
  • the volume fraction of the pore volume decreases while the volume fraction of the silica increases.
  • the sintering time and the pressure during sintering can be each varied in wide range.
  • the sintering process takes place at atmospheric pressure in the range from 0.5 to 1.06 bar depending on the weather and the altitude above the sea level.
  • the time of sintering is preferably in the range from 1 min to 1 week, more preferably in the range from 10 min to 12 hours, in particular in the range from 30 min to 2 hours.
  • the inventive process is characterized in that in process step (b) the sintering of the porous body of compacted silica particles takes place at a temperature in the range from 200 °C to 800 °C, preferably in the range from 500 °C to 600 °C.
  • a monolithic body comprising silica particles, which are fused together, and carbon material, is formed by infiltrating the porous monolithic body, which was obtained in process step (b), under reduced pressure with at least one carbon pre- cursor substance, which is liquid during the infiltration step, followed by carbonization of the carbon precursor substance.
  • reduced pressure refers to a pressure below atmospheric pressure, preferably in the range from 0 bar to 0.5 bar, in particular in the range from 10 "6 bar to 10 "2 bar.
  • Methods of infiltrating a porous body with liquid or gaseous substances are known in the prior art; special mention should here be made of immersing, pumping and swiveling. Infiltration under reduced pressure facilitates the complete filling of all accessible voids with fluid substance.
  • Carbon precursor substances which are liquid in the temperature range below the carbonization temperature, are known in the prior art.
  • Non-limiting examples of carbon precursor substance are solutions of phenols, formaldehyde and optionally melamine, which are able to form resins, solutions of mesophase pitch or naphthol(s), solutions of carbohydrates such as saccharose, fructose or glucose, ionic liquids or mixtures of said carbon precursor substance.
  • Preferred carbon precursor substances are ionic liquids, which also offer a smart way to introduce heteroatoms into the final carbon phase, for example boron, nitrogen, phosphorus or sulfur in particular nitrogen. While the cations of ionic liquids usually comprise nitrogen as a heteroa- tom, the anions of ionic liquids might comprise also boron, nitrogen, phosphorus or sulfur.
  • J. Phys. Chem. Ref. Data, Vol. 35, No. 4, 2006, 1475-1517 describes not only the physical data of many ionic liquids, but also different cations and anions.
  • preferred ionic liquids, which are used as carbon precursor substances are those, wherein the anions are dicyana- mide (dca) or tricyanomethide (tern) or the cations are selected from pyridinium, pyrrolidonium and imidazolium derivatives.
  • Examples of such preferred ionic liquids are 1 -ethyl-3- methylimidazolium dicyanamide (EMIM-DCA), 3-methyl-N-butyl-pyridinium dicyanamide (3MBP- DCA), 1 -butyl-3-methyl-imidazolium dicyanamide (BMIM-DCA), 1 -decyl-3-methyl-imidazolium dicyanamide (DMIM-DCA), 1 -hexyl-3-methyl-imidazolium dicyanamide (HMIM-DCA), 1 -ethyl-3- methylimidazolium tricyanomethanide, 1 -cyanomethyl-3-methylimidazolium
  • MNIM-Tf2N bis(trifluoromethylsulfonyl) imide
  • An ionic liquid as a carbon precursor substance can be either used alone, mixed with further ionic liquids, e.g. in order to adjust the content of heteroatoms in the final carbon phase, or mixed with alternative carbon precursors, which are soluble in the ionic liquid, like cellulose or urea.
  • Particularly preferred carbon precursor substances are ionic liquids, wherein the cation is a nitrogen-containing organic cation and the anion is a nitrogen-containing organic anion.
  • the inventive process is characterized in that the carbon precursor substance is an ionic liquid, wherein the cation is a nitrogen-containing organic cation and the anion is a nitrogen-containing organic anion.
  • the conditions for the carbonization of the infiltrated carbon precursor sub- stance or mixture of carbon precursor substances are known to the person skilled in the art.
  • the temperature for the carbonization can be varied in a wide range, usually depending on nature of the used carbon precursor substance.
  • the carbonization is performed at a temperature in the range from 200 to 2000°C, preferably in the range from 400 to 1600°C, more preferably in the range from 600 to 1200°C, especially in the range from 800 to 1000°C.
  • the duration for the carbonization may vary within a wide range and depends on factors including the temperature at which the carbonization is performed.
  • the time for the carbonization may be from 0.1 to 50 h, preferably from 0.2 to 10 h, especially 0.4 to 2 h.
  • the carbonization of the carbon precursor substances can in principle be performed under re- symbolized pressure, for example under vacuum, under standard pressure or under elevated pressure, for example in a pressure autoclave.
  • the carbonization is performed at a pressure in the range from 0.01 to 100 bar, preferably in the range from 0.1 to 10 bar, especially in the range from 0.5 to 5 bar or 0.7 to 2 bar.
  • the carbonization can be performed in a closed system or in an open system in which volatile constituents which form are removed in a gas stream, inert gases or reducing gases.
  • the carbonization of the carbon precursor substances in process step (c) is therefore performed in one or more stages, preferably in one stage, with sub- stantial or complete, preferably complete, exclusion of oxygen.
  • Complete exclusion of oxygen means in this context that not more than 0.5% by volume, preferably less than 0.05% by volume and especially less than 0.01 % by volume of oxygen is present in the gas space.
  • the carbonization of the porous carbon material in process step (c) is performed in the presence of a protective or reactive gas selected from Ar, N2, H2, NH3, CO and C2H2, and mixtures thereof.
  • the formed monolithic body which comprises silica particles, which are fused together, and carbon material, usually still comprises voids, because the volume of the formed carbon material is usually smaller than the volume of the infiltrated carbon precursor substances.
  • the inventive process is characterized in that in process step (d) the content of carbon material in the monolithic body obtained in process step (c) is increased by repeating at least once, preferably 1 to 4 times, more preferably 1 to 3 times, in particular 3 times, the consecutive steps of infiltrating the monolithic body comprising silica particles and carbon material under reduced pressure with at least one carbon precursor substance, which is liquid during the infiltration step, and of carbonization of the carbon precursor substance.
  • silica is removed from the monolithic body comprising silica particles, which are fused together, and carbon material obtained in process step (c) or (d), optionally followed by washing and drying steps.
  • silica by dissolving silica by a chemical reaction is known in the state of the art.
  • Silica can be dissolved for instance either by the reaction with hydrofluoric acid or strong bases like aqueous solutions of NaOH or KOH.
  • process step (e) the conditions for removing silica, more precisely for dissolving silica, can be varied in a wide range, in particular with respect to temperature, reaction time and concentration of the reagents, which react with silica under formation of soluble reaction products.
  • the obtained monolithic body of a porous carbon material is usually washed with suitable solvents, like water, acetone, methanol, ethanol or mixtures thereof, preferably water, and afterwards dried, usually at elevated tempera- tures, preferably in combination with reduced pressure, for example in a vacuum oven.
  • suitable solvents like water, acetone, methanol, ethanol or mixtures thereof, preferably water
  • the inventive process is characterized in that the porous carbon material is a mesoporous nitrogen enriched carbon material, in particular wherein the mass fraction of nitrogen is in the range from 0.05 to 0.15, and wherein the silica particles used in process step (a) have an average particle diameter in the range from 2 to 50 nm, more preferably 5 to 50 nm, and wherein the carbon precursor substance is an ionic liquid, wherein the cation is a nitrogen-containing organic cation and the anion is a nitrogen-containing organic anion.
  • the inventive process allows in particular the preparation of monolithic bodies of special porous carbon materials, which are very useful for the preparation of cathodes for metal-sulfur cells, especially for the preparation of alkali metal-sulfur cells, in particular lithium-sulfur cells.
  • the present invention further also provides a monolithic body of a porous carbon material com- prising a carbon phase and a pore phase of interconnected pores in the carbon phase, wherein the average pore diameter is in the range from 2 to 50 nm, preferably in the range from 15 to 30 nm, determined by Scanning Electron Microscopy and the pore size distribution shows a d95- value in the range from 2 to 50 nm, preferably in the range from 15 to 30 nm, determined by means of a NLDFT calculation based on Nitrogen Physisorption Measurements.
  • Particularly preferred porous carbon materials are mesoporous carbon materials, wherein the pore size distribution is a unimodal distribution.
  • the size of the monolithic body of the porous carbon material can be varied depending on the size of the initially formed porous body comprising silica particles in process step (a) of the inventive process as described above.
  • the inventive monolithic body of the porous carbon material is characterized in that the monolithic body of a porous carbon material has a three- dimensional geometric shape wherein the smallest of the three spatial dimensions (extents) is in the range from 10 ⁇ to 10 m, preferably in the range from 100 ⁇ to 1 m, more preferably in the range from 1000 ⁇ to 0.1 m.
  • heteroatom enriched carbon materials are of particular interest in the field of cathode materials for metal-sulfur cells, especially for lithium- sulfur cells.
  • Preferred heteroatoms are selected from the group consisting of boron, nitrogen, phosphorus and sulfur, in particular nitrogen.
  • the inventive monolithic body of the porous carbon material is characterized in that the porous carbon material is a mesoporous carbon material which is enriched with a chemical element selected from the group consisting of boron, nitro- gen, phosphorus and sulfur, in particular nitrogen.
  • the mass fraction of the chemical element selected from the group consisting of boron, nitrogen, phosphorus and sulfur, in particular nitrogen is in the range from 0.01 to 0.25, based on the total mass of the porous carbon material of the inventive monolithic body.
  • the mass fraction of these chemical elements is particularly preferred in the range from 0.01 to 0.1
  • nitrogen is particularly preferred in the range from 0.05 to 0.15.
  • the inventive monolithic body of the porous carbon material is characterized in that the monolithic body of the porous carbon material shows a total pore volume in the range from 0.5 to 2.5 cm 3 g _1 and a specific BET surface area in the range from 50 to 1000 m 2 g -1 , preferably in the range from 300 to 500 m 2 g- 1 .
  • the inventive monolithic body of the porous carbon material is characterized in that the porous carbon material is a mesoporous carbon material which is enriched with a chemical element selected from the group consisting of boron, nitrogen, phosphorus and sulfur, in particular nitrogen, wherein the mass fraction of the chemical element selected from the group consisting of boron, nitrogen, phosphorus and sulfur, in particular nitrogen is in the range from 0.01 to 0.25, preferably in the range from 0.01 to 0.1 for bo- ron, phosphorus and sulfur and in the range from 0.05 to 0.15 for nitrogen, based on the total mass of the porous carbon material of the inventive monolithic body,
  • the inventive monolithic body of a porous carbon material comprising a carbon phase and a pore phase of interconnected pores in the carbon phase, wherein the average pore diameter is in the range from 2 to 50 nm, preferably in the range from 15 to 30 nm, determined by Scanning Electron Micro
  • inventive monolithic bodies of special porous carbon materials as described above are very useful for the preparation of cathodes for metal-sulfur cells, especially for the preparation of lith- ium-sulfur cells, in particular for the preparation of cathodes comprising elemental sulfur.
  • inventive monolithic bodies of special porous carbon materials as described above can be used as obtained after production, in particular production by the inventive process as described above, or the inventive monolithic bodies can first be divided into fragments, e.g. in the form of slices by cutting or in the form of irregular bodies obtained by grinding.
  • the inventive monolithic bodies of special porous carbon materials can first be combined with elemental sulfur and afterwards the monolithic bodies comprising elemental sulfur are divided into fragments.
  • the present invention further also provides a composite material comprising elemental sulfur and at least one inventive monolithic body of a porous carbon material as describe above or fragments of said monolithic body.
  • Elemental sulfur is known as such, e.g. ⁇ -Ss as the most commonly found allotrope in nature.
  • ⁇ -Ss as the most commonly found allotrope in nature.
  • the description and preferred embodiments of the inventive monolithic bodies of porous carbon materials correspond to the above description of this component for the composite material of the present invention.
  • the size of the fragments of the monolithic bodies of special porous carbon materials can be varied in a wide range depending on the size of the initially produced monolithic bodies and the applied method for fragmentation.
  • the inventive composite material is characterized in that the fragments of the above described monolithic bodies of the special porous carbon mate- rial have a three-dimensional geometric shape wherein the smallest of the three spatial dimensions (extents) is in the range from 0.1 ⁇ to 50 ⁇ , preferably in the range from 0.5 ⁇ to 20 ⁇ , more preferably in the range from 1 ⁇ to 10 ⁇ . Elemental sulfur and the inventive monolithic bodies of porous carbon material or fragments of said monolithic bodies can be combined in different manners. Preferred are methods wherein at the end the elemental sulfur is located in the pores of the porous carbon material. In one embodiment of the present invention, the inventive composite material is characterized in that the porous carbon material has been infiltrated with elemental sulfur.
  • Either complete inventive monolithic bodies of special porous carbon materials or fragments of said monolithic bodies can be infiltrated with elemental sulfur. Methods of infiltration and the appropriate conditions, in particular temperature, pressure and induction period are known to the person skilled in the art.
  • the carbon content determined by elemental analysis and the sulfur content determined by elemental analysis in the inventive composite material can be varied in a wide range.
  • the carbon content determined by elemental analysis is in the range from 1 to 45%, preferably in the range from 5 to 30%
  • the sulfur content determined by elemental analysis is in the range from 55 to 99%, preferably in the range from 65 to 95%, in particular in the range from 70 to 90% based in each case on the total weight of the composite material.
  • the sum of the mass fractions of elemental sulfur and of the special porous carbon materials based on the inventive composite material can be varied in a wide range depending on the amount of components in addition to elemental sulfur and porous carbon materials.
  • the sum of the mass fractions of elemental sulfur and of the special porous carbon materials based on the inventive composite material is in the range from 0.5 to 1 , preferably in the range from 0.8 to 1 , in particular in the range from 0.9 to 1.
  • the present invention further provides a process for producing a composite material, comprising the provision of at least one inventive monolithic body of a porous carbon material as described above or fragments of said monolithic body, followed by infiltrating said inventive monolithic body of a porous carbon material or fragments of said monolithic body with dissolved, melted or gaseous elemental sulfur.
  • inventive monolithic bodies of porous carbon materials in the inventive process correspond to the above description of these inventive com- ponents.
  • inventive monolithic bodies of porous carbon materials or fragments of said monolithic bodies can be contacted with solutions of sulfur like sulfur in carbon disulfide or toluene, with melted sulfur or with sulfur vapor in order to infiltrate the monolithic bodies of porous carbon or fragments thereof.
  • sulfur itself or solutions of sulfur are adsorbed by the porous carbon and occupy the pores inside of the porous carbon.
  • the infiltration of the mon- olithic bodies of porous carbon with solutions of sulfur can be done at a temperature below the boiling point of the corresponding solvent, which later can also be removed at a temperature below the boiling point of said solvent
  • the infiltration of the monolithic bodies of porous carbon with liquid sulfur or sulfur vapor is preferably done at a temperature close to or above the melt- ing point of sulfur, for example at a temperature in the range from 100 to 300 °C.
  • the impregnation of the monolithic bodies of porous carbon with liquid sulfur or sulfur vapor can in principle be done in an open or a closed system, in vacuum or under pressure.
  • the time of the infiltration is not critical. Sulfur and monolithic bodies of porous carbon or frag- ments thereof can be heated for example for a time period from 1 sec to 72 h, preferably from 5 sec to 24 h, particularly preferably 10 sec to 8 h.
  • the production of the above described inventive composite material can be done in a single process step or several process steps.
  • the infiltration can be performed at different temperatures for different time periods under different pressure.
  • inventive composite material comprising elemental sulfur and at least one inventive monolithic body of a porous carbon material as describe above or fragments of said monolithic body can ultimately be used as an essential constituent of a cathode for a metal-sulfur cell.
  • the present invention further provides the use of a composite material as described above as constituent of a cathode for metal-sulfur cells.
  • the present invention further also provides cathodes for metal-sulfur cells, in particular lithium- sulfur cells, comprising at least one inventive composite material as described above.
  • the electrode where during discharging a net negative charge occurs is called the anode and the electrode where during discharging a net positive charge occurs is called the cathode.
  • inventive cathodes might comprise the inventive composite material either as a monolithic body, e.g. in form of thin disk or in prismatic form directly connected to an output conductor (binder- free cathode), or as particulate composite material based on fragments of the inventive monolithic bodies in combination with additional typical cathode ingredients, like conductive carbons or binders, forming a cathode material.
  • Inventive particulate composite materials based on fragments of the inventive monolithic bodies of porous carbon materials are preferably combined with a carbon, which improves the electrical conductivity of the cathode material, and optionally at least one binder, which is typically an or- ganic polymer.
  • the binder serves principally for mechanical stabilization of the components of the electrode, by virtue of particulate composite material based on fragments of the inventive monolithic bodies and carbon particles being bonded to one another by the binder, and also has the effect that the cathode material has sufficient adhesion to an output conductor.
  • the binder is preferably chemically inert toward the chemicals with which it comes into contact in an electrochemical cell.
  • the present invention further also provides a cathode material for a metal-sulfur cell comprising
  • (C) optionally at least one polymer as a binder.
  • the cathode material for a metal-sulfur cell comprises in addition to the particulate composite material (A) based on fragments of the inventive monolithic bodies of porous carbon materials as described above, as a second component, carbon in a polymorph comprising at least 60% sp 2 -hybridized carbon atoms, also referred to hereinafter as carbon (B) for short, and optionally as component (C) a polymer as a binder, also referred to hereinafter as binder (C) for short.
  • component (C) a polymer as a binder, also referred to hereinafter as binder (C) for short.
  • Carbon (B) which improves the electrical conductivity of the inventive cathode material, can be selected from graphite, carbon black, carbon nanotubes, graphene or mixtures of at least two of the aforementioned substances. Suitable carbons in a conductive polymorph are described in WO 2012/168851 page 4, line 30 to page 6, line 22.
  • the inventive cathode material for a metal-sulfur cell is characterized in that carbon (B) is selected from graphite, graphene, activated carbon and especially carbon black.
  • the inventive cathode material for a metal-sulfur cell comprises at least one polymer as a binder.
  • Binder (C) can be selected from a wide range of organic polymers. Suitable binders are described in WO 2012/168851 page 6, line 40 to page 7, line 30.
  • Particularly suitable binders for the inventive cathode material for a metal-sulfur cell are especially polyvinyl alcohol, poly(ethylene oxide), carboxymethyl cellulose (CMC) and halogenated (co)polymers, for example polyvinyl chloride or polyvinylidene chloride, especially fluorinated (co)polymers such as polyvinyl fluoride and especially polyvinylidene fluoride, lithiated Nafion and polytetrafluoroethylene.
  • the inventive cathode material for a metal-sulfur cell comprises in the range from 10 to 80% by weight, preferably 30 to 75% by weight, of sulfur, determined by elemental analysis, based on the total weight of the cathode material for a metal- sulfur cell.
  • the inventive cathode material for a metal-sulfur cell comprises in the range from 0.1 to 60% by weight of carbon in a conductive polymorph, preferably 1 to 30% by weight based on the total weight of the cathode material for a metal- sulfur cell.
  • This carbon can likewise be determined by elemental analysis, for example, in which case the evaluation of the elemental analysis has to take into account the fact that carbon also arrives in organic polymers representing binders, and possibly further sources.
  • the inventive cathode material for a metal-sulfur cell comprises in the range from 0.1 to 20% by weight of binder, preferably 1 to 15% by weight and more preferably 3 to 12% by weight, based on the total weight of the cathode material for a metal-sulfur cell.
  • Particulate composite material (A) based on fragments of the inventive monolithic bodies of porous carbon materials as described above and inventive cathode material are particularly suitable as or for production of cathodes, especially for production of cathodes of lithium-containing batteries.
  • the present invention provides for the use of particulate composite material (A) or inventive cathode materials as or for production of cathodes for metal-sulfur cells.
  • the present invention further also provides a cathode which has been produced from or using a cathode material as described above.
  • the inventive cathode may have further constituents customary per se, for example an current collector, which may be configured in the form of a metal wire, metal grid, metal mesh, expanded metal, metal sheet, metal foil or carbon paper/cloth. Suitable metal foils are especially aluminum foils.
  • the inventive cathode has a thickness in the range from 25 to 200 ⁇ , preferably from 30 to 100 ⁇ , based on the thickness without current collector.
  • particulate composite material (A) or inventive cathode materials are preferably stable over at least 30 cycles, more preferably over at least 50 cycles, even more preferably over at least 100 cycles, especially over at least 200 cycles or over at least 500 cycles.
  • particulate composite material (A) or inventive cathode material is processed to cathodes, for example in the form of continuous belts which are processed by the battery manufacturer.
  • Inventive cathodes produced from particulate composite material (A) or inventive cathode material may have, for example, thicknesses in the range from 20 to 500 ⁇ , preferably 40 to 200 ⁇ .
  • the present invention further provides metal-sulfur cells, more preferably alkali metal-sulfur cells, in particular lithium sulfur cells comprising at least one inventive cathode as described above, which has been produced from or using at least one particulate composite material (A) or at least one inventive cathode material as described above.
  • inventive cathode comprises usually a mixture of different electroactive sulfur-containing materials since more and more S-S- bonds are formed.
  • inventive metal-sulfur cells comprise, as well as inventive cathode, which comprises inventive electroactive composite (A) respectively inventive cathode material, at least one anode comprising at least one metal, preferably magnesium, aluminum, zinc or an alkali metal like lithium, sodium or potassium.
  • inventive cathode which comprises inventive electroactive composite (A) respectively inventive cathode material, at least one anode comprising at least one metal, preferably magnesium, aluminum, zinc or an alkali metal like lithium, sodium or potassium.
  • inventive metal-sulfur cell comprises an alkali metal, in particular lithium.
  • the metal of the anode of the inventive metal-sulfur cell can be present in the form of a pure metal phase, preferably a pure alkali metal phase, in form of an alloy together with other metals or metalloids, in form of an intercalation compound or in form of an ionic compound comprising at least one metal, preferably an alkali metal and at least one transition metal.
  • the anode of the inventive metal-sulfur cell, in particular of the inventive lithium-sulfur cell can be selected from anodes being based on various active materials.
  • Suitable active materials are metallic lithium, carbon-containing materials such as graphite, graphene, charcoal, expanded graphite, in particular graphite, furthermore lithium titanate (Li4Ti 5 0i2), anodes comprising In, Tl, Sb, Sn or Si, in particular Sn or Si, for example tin oxide (Sn02) or nanocrystalline silicon, and anodes comprising metallic lithium.
  • the metal-sulfur cell is characterized in that the anode of the inventive metal-sulfur cell is selected from graphite anodes, lithium titanate anodes, anodes comprising In, Tl, Sb, Sn or Si, and anodes comprising metallic lithium.
  • the inventive metal-sulfur cell is characterized in that the metal of the anode is lithium.
  • the anode of the inventive metal-sulfur cell can further comprise a current collector. Suitable current collectors are, e.g., metal wires, metal grids, metal gauze and preferably metal foils such as copper foils.
  • the anode of the inventive metal-sulfur cell can further comprise a binder. Suitable binders can be selected from organic (co)polymers. Suitable organic (co)polymers may be halogenated or halogen-free.
  • Examples are polyethylene oxide (PEO), cellulose, carboxymethyl cellulose, polyvinyl alcohol, polyethylene, polypropylene, polytetrafluoroethylene, polyacrylonitrile-methyl methacrylate, styrene-butadiene copolymers, tetrafluoroethylene-hexafluoropropylene copoly- mers, vinylidene fluoride-hexafluoropropylene copolymers (PVdF-HFP), vinylidene fluoride- tetrafluoroethylene copolymers, perfluoroalkyl vinyl ether copolymers, ethylene- tetrafluoroethylene copolymers, vinylidene fluoride-chlorotrifluoroethylene copolymers, ethylene- chlorofluoroethylene copolymers, ethylene-acrylic acid copolymers, optionally at least partially neutralized with alkali metal salt or ammonia, ethylene-methacrylic acid copolymers, optional
  • Suitable binders are especially polyvinyl alcohol and halogenated (co)polymers, for example polyvinyl chloride or polyvinylidene chloride, especially fluorinated (co)polymers such as polyvi- nyl fluoride and especially polyvinylidene fluoride and polytetrafluoroethylene.
  • the average molecular weight M w of binder may be selected within wide limits, suitable examples being 20,000 g/mol to 1 ,000,000 g/mol.
  • the anode of the inventive metal-sulfur cell can have a thickness in the range of from 15 to 200 ⁇ , preferably from 30 to 100 ⁇ , determined without the current collector.
  • the inventive metal-sulfur cell further comprises, as well as the inventive cathode and an anode, at least one electrolyte composition comprising at least one solvent and at least one alkali metal salt.
  • the solvents of the electrolyte composition can be chosen from a wide range of solvents, in particular from solvents which dissolve alkali metal salts easily.
  • Solvents or solvent systems, which dissolve alkali metal salts are for example ionic liquids, polar solvents or combinations of apolar solvents combined with polar additives like crown ethers, like 18-crown-6, or cryptands.
  • Example of polar solvents are polar protic solvents or dipolar aprotic solvents.
  • Examples of polar protic solvents are water, alcohols like methanol, ethanol or iso-propanol, carbonic acids like acetic acid, ammonia, primary amines or secondary amines.
  • Polar protic solvents can only be used in metal-sulfur cell comprising an anode, which comprises an alkali metal, if any contact between that anode and the polar protic solvent is strictly precluded by an appropriate separator.
  • dipolar aprotic solvents examples include organic carbonates, esters, ethers, sulfones like DMSO, sulfamides, amides like DMF or DMAc, nitriles like acetonitrile, lactams like NMP, lactones, linear or cyclic peralkylated urea derivatives like TMU or DMPU, fluorinated ether, fluori- nated carbamates, fluorinated carbonated or fluorinated esters.
  • Suitable solvents of the electrolyte composition may be liquid or solid at room temperature and are preferably liquid at room temperature.
  • the inventive metal-sulfur cell is characterized in that the solvent is a dipolar aprotic solvent.
  • a suitable solvent is preferably selected from polymers, cyclic or noncyclic ethers, cyclic or noncyclic acetals, cyclic or noncyclic organic carbonates and ionic liquids.
  • the inventive metal-sulfur cell is characterized in that the solvent is selected from polymers, cyclic or noncyclic ethers, noncyclic or cyclic acetals and cyclic or noncyclic organic carbonates.
  • suitable polymers are especially polyalkylene glycols, preferably poly-Ci-C4- alkylene glycols and especially polyethylene glycols.
  • Polyethylene glycols may comprise up to 20 mol% of one or more Ci-C4-alkylene glycols in copolymerized form.
  • Polyalkylene glycols are preferably doubly methyl- or ethyl-capped polyalkylene glycols.
  • the molecular weight M w of suitable polyalkylene glycols and especially of suitable polyethylene glycols may be at least 400 g/mol.
  • the molecular weight M w of suitable polyalkylene glycols and especially of suitable polyethylene glycols may be up to 5 000 000 g/mol, preferably up to 2 000 000 g/mol.
  • noncyclic ethers are, for example, diisopropyl ether, di-n-butyl ether, 1 ,2- dimethoxyethane, 1 ,2-diethoxyethane, preference being given to 1 ,2-dimethoxyethane.
  • Suitable cyclic ethers are tetrahydrofuran and 1 ,4-dioxane.
  • noncyclic acetals are, for example, dimethoxymethane, diethoxymethane, 1 ,1 -dimethoxyethane and 1 ,1 -diethoxyethane.
  • suitable cyclic acetals are 1 ,3-dioxane and especially 1 ,3-dioxolane.
  • noncyclic organic carbonates examples include dimethyl carbonate, ethyl methyl carbonate and diethyl carbonate.
  • Suitable cyclic organic carbonates are compounds of the general formulae (X) and (XI)
  • R 1 , R 2 and R 3 may be the same or different and are each selected from hydrogen and Ci-C4-alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert- butyl, where R 2 and R 3 are preferably not both tert-butyl.
  • R 1 is methyl and R 2 and R 3 are each hydrogen, or R 1 , R 2 and R 3 are each hydrogen.
  • Another preferred cyclic organic carbonate is vinylene carbonate, formula (XII).
  • alkali metal salts which are used as conductive salts, have to be soluble in the solvent.
  • Preferred alkali metal salts are lithium salts or sodium salts, in particular lithium salts.
  • the inventive metal-sulfur cell is characterized that the alkali metal salt is a lithium salt or sodium salt, preferably a lithium salt.
  • Suitable alkali metal salts are especially lithium salts. Examples of suitable lithium salts are LiPF 6 , LiBF 4 , UCIO4, LiAsFe, UCF3SO3, LiC(C n F 2 n + iS02)3, LiNOs, lithium imides such as
  • LiN(C n F2n+iS02)2 where n is an integer in the range from 1 to 20, LiN(S02F)2, Li2SiF6, LiSbF6, LiAICU, and salts of the general formula (C n F2n+iS02)mXLi, where m is defined as follows:
  • m 3 when X is selected from carbon and silicon.
  • Preferred alkali metal salts are selected from LiC(CF 3 S0 2 ) 3 , LiN(CF 3 S0 2 ) 2 , LiPF 6 , LiBF 4 , LiCI0 4 , L1NO3 and particular preference is given to LiPF6 and LiN(CF3S02)2.
  • inventive metal-sulfur cells comprise one or more separators by which the electrodes are mechanically separated from one another.
  • Suitable separators are polymer films, especially porous polymer films, which are unreactive toward metallic lithium and toward lithium sulfides and lithium polysulfides.
  • Particularly suitable materials for separators are polyolefins, especially porous polyethylene films and porous polypropylene films.
  • Polyolefin separators especially of polyethylene or polypropylene, may have a porosity in the range from 35 to 45%. Suitable pore diameters are, for example, in the range from 30 to 500 nm.
  • the separators selected may be separators composed of PET nonwovens filled with inorganic particles. Such separators may have a porosity in the range from 40 to 55%. Suitable pore diameters are, for example, in the range from 80 to 750 nm.
  • inventive metal-sulfur cells can contain additives such as wetting agents, corrosion inhibitors, or protective agents such as agents to protect any of the electrodes or agents to protect the salt(s).
  • inventive metal-sulfur cells can have a disc-like shape. In another embodiment, inventive metal-sulfur cells can have a prismatic shape.
  • inventive metal-sulfur cells can include a housing that can be from steel or aluminium.
  • inventive metal-sulfur cells are combined to stacks including electrodes that are laminated. In one embodiment of the present invention, inventive metal-sulfur cells are selected from pouch cells.
  • Inventive metal-sulfur cells in particular rechargeable lithium sulfur cells, comprising the in- ventive electroactive composite (A) have overall advantageous properties. They exhibit good capacity, a low capacity fade rate per cycle, and good cycling stability on extended cycling.
  • a further aspect of the present invention refers to batteries, in particular to rechargeable lithium sulfur batteries, comprising at least one inventive metal-sulfur cell, for example two or more.
  • inventive metal-sulfur cells can be combined with one another in inventive batteries, for example in series connection or in parallel connection. Series connection is preferred.
  • Inventive batteries in particular rechargeable lithium sulfur batteries, have advantageous properties. They exhibit good capacity, a low capacity fade rate per cycle, and good cycling stability on extended cycling.
  • inventive metal-sulfur cells or inventive batteries can be used for making or operating cars, computers, personal digital assistants, mobile telephones, watches, camcorders, digital cameras, thermometers, calculators, laptop BIOS, communication equipment or remote car locks, and stationary applications such as energy storage devices for power plants.
  • a further aspect of the present invention is a method of making or operating cars, computers, personal digital assistants, mobile telephones, watches, camcorders, digital cameras, thermometers, calculators, laptop BIOS, communication equipment, remote car locks, and stationary applications such as energy storage devices for power plants by employing at least one inventive battery or at least one inventive electrochemical cell.
  • a further aspect of the present invention is the use of the electrochemical cell as described above in motor vehicles, bicycles operated by electric motor, aircraft, ships or stationary energy stores.
  • inventive electrochemical cells in devices gives the advantage of prolonged run time before recharging and a smaller loss of capacity in the course of prolonged run time. If the intention were to achieve an equal run time with electrochemical cells with lower energy density, a higher weight for electrochemical cells would have to be accepted.
  • the present invention further provides a device comprising at least one inventive electrochemical cell as described above.
  • mobile devices such as are vehicles, for example automobiles, bicycles, aircraft, or water vehicles such as boats or ships.
  • Other examples of mobile devices are those which are portable, for example computers, especially laptops, tele- phones or electrical power tools, for example from the construction sector, especially drills, battery-driven screwdrivers or battery-driven tackers.
  • the invention is illustrated by the examples which follow, but these do not restrict the invention.
  • the silica body was immersed into 1 -ethyl-3-methylimidazolium dicyanamide (EMIM-DCA) and a vacuum over 12 h was applied to achieve complete filling of the pore structure.
  • the infiltrated material was then carbonized at 900 °C for 30 min in an argon atmosphere. These two steps were repeated 3 times.
  • the silica template was dissolved using an aqueous potassium hydroxide solution (3 M) and stirring at 70 °C for 48 h.
  • the product (C1 ) was washed with deionized water and subsequently dried in a vacuum oven.
  • Figure 2 shows a nitrogen isotherm of N-enriched porous carbon with a unimodal pore size distribution (C1 ) - (A: Relative Pressure p/ ⁇ ; B: Adsorbed Volume [cm 3 /g])
  • Figure 3 NLDFT-calculated pore diameter distribution of inventive unimodal N-enriched carbon (C1 ) - (A: Pore diameter [nm]; B: dV(d) [cm 3 /nm/g])
  • Figure 4 XPS detail spectrum of the N1 s region of inventive unimodal N-enriched carbon (C1 ) - (A: Binding energy [eV]; Intensity [a.u.])
  • FIG. 5 Raman spectrum of inventive unimodal N-enriched carbon (C1 ) - (A: Raman shift [cm- 1 ]; Intensity [a.u.]) 1.2
  • C-C2 Hierarchical pore size distribution
  • 0.9 g urea were added to 10 ml of a 0.01 M aqueous solution of acetic acid. The mixture was cooled in an ice bath and stirred for 15 min.
  • TMOS tetramethylorthosilicate
  • the monoliths were placed in 1 -ethyl-3-methylimidazolium dicyanamide (EMIM- DCA) and a vacuum was applied over 12 h in order to achieve complete filling of the pore structure.
  • the impregnated material was then carbonized at 900 °C for 30 min in an argon atmosphere. This step was repeated 3 times.
  • the silica template was dissolved using an aqueous potassium hydroxide solution (3M) and stirring at 70 °C over 48 h.
  • the material (C-C2) was carefully washed with deionized water and dried in a vacuum oven.
  • cathodes (E1 ) comprising CSCM-1
  • a typical cathode slurry was prepared by mixing 75 % of ground CSCM-1 obtained in experiment 11.1 with 20 % conductive carbon (Super P and Printex XE2 1 :1 ) and 5 % poly (vinyl alcohol) binder in water/isopropyl alcohol/1 -methoxy-2-propanol (65/30/5).
  • the slurries were coated on 8 ⁇ -thick carbon-primered (containing 2/3 Super C65 and 1/3 SelvolTM 425) aluminium current collector using the doctor blading tech- nique.
  • After drying at 60 °C in a vacuum oven over 12 h the cathodes (E1 ) were cut into 13 mm diameter discs and dried again at 60 °C under vacuum over 12 h.
  • a typical cathode slurry was prepared by mixing 71 % of ground C-CSCM-2 obtained in experiment 11.2 with 24 % conductive carbon (Super P and Printex XE2 1 :1 ) and 5 % poly (vinyl alcohol) binder in water/isopropyl alcohol/1 -methoxy-2-propanol (65/30/5). After homogenization (ball-milling for 20 h) the slurries were coated on 8 ⁇ -thick carbon-primered (containing 2/3 Super C65 and 1/3 SelvolTM 425) aluminium current collector using the doctor blading technique. After drying at 60 °C in a vacuum oven over 12 h the cathodes (C-E2) were cut into 13 mm diameter discs and dried again at 60 °C under vacuum over 12 h.
  • C-E2 cathodes
  • inventive carbon C1 was conducted according to 1.1 .
  • a typical cathode slurry was prepared by mixing 60 % of commercially available sulfur (Aldrich, reagent grade) with 15 % inventive carbon C1 , 20 % conductive carbon (Super P and Printex XE2 1 :1 ) and 5 % poly (vinyl alcohol) binder in water/isopropyl alcohol/1 -methoxy-2-propanol (65/30/5). After homogenization (ball-milling for 20 h) the slurries were coated on 8 ⁇ -thick carbon-primered (containing 2/3 Super C65 and 1/3 SelvolTM 425) aluminium current collector using the doctor blading technique. After drying at 60 °C in a vacuum oven over 12 h the cathodes (E3) were cut into 13 mm diameter discs and dried again at 60 °C under vacuum over 12 h.
  • the preparation of the comparative carbon C-C2 was conducted according to 1.2.
  • a typical cathode slurry was prepared by mixing 60 % of commercially available sulfur (Aldrich, reagent grade) with 1 1 % comparative carbon C-C2, 24 % conductive carbon (Super P and Printex XE2 1 :1 ) and 5 % poly (vinyl alcohol) binder in water/isopropyl alcohol/1 -methoxy-2-propanol (65/30/5).
  • After homogenization ball-milling for 20 h) the slurries were coated on 8 ⁇ -thick carbon-primered (containing 2/3 Super C65 and 1/3 SelvolTM 425) aluminium current collector using the doctor blading technique.
  • the cathodes (C-E4) were cut into 13 mm diameter discs and dried again at 60 °C under vacuum over 12 h.
  • the slurry was then coated onto ⁇ 8 ⁇ -thick primed aluminum (containing 2/3 Super C65 and 1/3 SelvolTM 425) with a doctor blade and dried in vacuum at 40 °C for 16 h.
  • the sulfur content in the final electrode (C-E5) was -60%.
  • Electrochemical Testing Test cells (coin-type cells) containing the electrodes mentioned above and lithium foil as counter electrode were assembled in an argon-filled glove box using a solution of 0.325 M LiTFSI and 0.625 M L1NO3 in DOL/DME (50/50 wt.%) as electrolyte and a porous monolayer polyethylene membrane (thickness: 20 ⁇ ; porosity: 45%) as separator.
  • the cycling experiments were conducted in the potential range of 1.7 V - 2.5 V vs Li/Li + .
  • a rate of 0.05 C was used and the subsequent cycles were conducted at a constant rate of 0.2C.
  • C-rate test different rates were applied.
  • Inventive cathodes E1 and E3 were used to produce inventive electrochemical cells EC1 and EC3 while comparative cathodes C-E2, C-E4 and C-E5 were used to produce comparative electrochemical cells C-EC2, C-EC4 and C-EC5.
  • Table 1 Specific Discharge Capacities of cells (EC1 and C-EC2) as a function of cycle number
  • Table 2 Specific Discharge Capacities of cells (EC1 , EC3 and C-EC5) as a function of cycle number

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Abstract

La présente invention concerne un procédé de production de corps monolithique de matière de carbone poreuse, des corps monolithiques de matières de carbone poreuses spéciales comprenant une phase de carbone et une phase de pores de pores interconnectés dans la phase de carbone, des matières composites comprenant du soufre et lesdits corps monolithiques de matières de carbone poreuses spéciales ou des fragments desdits corps monolithiques de matières de carbone poreuses spéciales, un procédé de production desdites matières composites et des cellules métal-soufre comprenant lesdites matières composites.
PCT/EP2015/058468 2014-04-30 2015-04-20 Procédé de production de corps monolithique de matière de carbone poreuse, corps monolithiques de matières de carbone poreuses spéciales et leur utilisation WO2015165762A1 (fr)

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EP3244472A1 (fr) * 2016-05-10 2017-11-15 Basf Se Composites comprenant des microsphères creuses d'oxyde de vanadium pour des cellules lithium-soufre
CN112723334A (zh) * 2019-10-28 2021-04-30 中国科学院上海硅酸盐研究所 一种利用含氟高分子制备氮掺杂碳材料的方法
WO2022149454A1 (fr) * 2021-01-07 2022-07-14 株式会社Ｇｓユアサ Matériau actif d'électrode négative pour éléments de stockage d'énergie à électrolyte non aqueux, électrode négative pour éléments de stockage d'énergie à électrolyte non aqueux, élément de stockage d'énergie à électrolyte non aqueux et dispositif de stockage d'énergie
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EP3244472A1 (fr) * 2016-05-10 2017-11-15 Basf Se Composites comprenant des microsphères creuses d'oxyde de vanadium pour des cellules lithium-soufre
CN112723334A (zh) * 2019-10-28 2021-04-30 中国科学院上海硅酸盐研究所 一种利用含氟高分子制备氮掺杂碳材料的方法
WO2022149454A1 (fr) * 2021-01-07 2022-07-14 株式会社Ｇｓユアサ Matériau actif d'électrode négative pour éléments de stockage d'énergie à électrolyte non aqueux, électrode négative pour éléments de stockage d'énergie à électrolyte non aqueux, élément de stockage d'énergie à électrolyte non aqueux et dispositif de stockage d'énergie
CN117275959A (zh) * 2023-09-21 2023-12-22 武汉中科先进材料科技有限公司 一种高硫掺杂的多孔碳材料及其制备方法和应用

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