EP2560918A1 - Procédé de production de nanomatériaux en sandwich bidimensionnels à base de graphène - Google Patents

Procédé de production de nanomatériaux en sandwich bidimensionnels à base de graphène

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Publication number
EP2560918A1
EP2560918A1 EP11715000A EP11715000A EP2560918A1 EP 2560918 A1 EP2560918 A1 EP 2560918A1 EP 11715000 A EP11715000 A EP 11715000A EP 11715000 A EP11715000 A EP 11715000A EP 2560918 A1 EP2560918 A1 EP 2560918A1
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EP
European Patent Office
Prior art keywords
particles
precursor compounds
metal
graphene
graphene oxide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP11715000A
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German (de)
English (en)
Inventor
Sorin Ivanovici
Shubin Yang
Xinlang Feng
Klaus MÜLLEN
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Max Planck Gesellschaft zur Foerderung der Wissenschaften eV
Original Assignee
BASF SE
Max Planck Gesellschaft zur Foerderung der Wissenschaften eV
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Priority to EP11715000A priority Critical patent/EP2560918A1/fr
Publication of EP2560918A1 publication Critical patent/EP2560918A1/fr
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/194—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/198—Graphene oxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00—Structure or properties of graphene
    • C01B2204/02—Single layer graphene

Definitions

  • the present invention relates to a method for producing two-dimensional (2D) nanomaterials and sandwich nanomaterials based on graphene or graphene oxide with coatings of carbon, metals or metal oxides and the sandwich materials produced in this way. Furthermore, the present invention relates to the use of the 2D sandwich nanomaterials as a template for the production of further 2D sandwich materials, their use in catalysts, sensors, capacitors, primary and secondary electrochemical cells and fuel cells and for the production of graphite particles and a method for production of graphene single layers of 2D sandwich nanomaterials produced according to the invention.
  • Two-dimensional (2D) nanomaterials are substances which in principle have an infinite extent in two dimensions, but in the third dimension (thickness) only have an extent in the nanometer range. This results in a very high ratio of length to thickness of these mostly particulate substances.
  • the 2D nanomaterials also include graphene, which is a plane layer of sp 2 -hypridized carbon atoms condensed into six-membered rings. The graphite structure is made up of these graphene layers. Graphene has a very high mechanical strength and a high electrical conductivity. However, a broad application of graphene and graphene-based, functionalized 2D nanomaterials is hindered by the difficulties in producing graphene.
  • Another method is Chemical Vapor Deposition (CVD), in which a C source is vaporized and deposited on a catalytic support.
  • CVD Chemical Vapor Deposition
  • a C source is vaporized and deposited on a catalytic support.
  • supported graphite particles can be obtained, but no suspension of "free” graphite particles in a medium.
  • Graphene can also be obtained by epitaxial growth on metallic substrates. Furthermore, the heating of SiC leads to temperatures above 1 100 ° C to graphene. In both methods graphene-coated surfaces are obtained, but no "free” graphene particles.
  • graphite particles Another possibility for the production of graphite particles is the chemical decomposition of graphite in a solvent (solution exfoliation), in which graphite in organic solvents such as N-methylpyrrolidone is split into graphite particles due to the positive interactions between the solvent and the graphite surface. Due to the particular solvents required for this, further processing is problematic, for example, by the application of further layers for functionalizing the graphene. In addition, only low yields of monolayers are obtained because the graphite particles tend to rapidly re-stack.
  • solvent solution exfoliation
  • graphene particles can be obtained by chemical reduction of graphene oxide particles in aqueous suspension, but always a certain amount of oxidized groups remains in the graphene.
  • graphene oxide is readily dispersible in water due to the many O groups, it has an intrinsic incompatibility with inorganic compounds such as SiO 2 because of its resulting anionic character.
  • graphene suspensions produced by reduction of aqueous graphene oxide suspensions are extremely difficult to obtain individual graphite particles, since they are not or only very poorly dispersible in water and therefore aggregate.
  • Graphene oxide can also be converted thermally into graphene (Aksay, Chem. Mater. 2007, 19, pages 4396-4404).
  • the graphene particles agglomerate at the high temperatures, so that it is difficult to obtain individual graphene particles.
  • WO 2010/014215 A2 describes a process for the preparation of nanocomposites based on graphene and metal oxides. For this purpose, graphite flakes are chemically oxidized and the resulting graphite oxide is split by rapid thermal expansion and partially converted to graphene.
  • the split-up graphite particles are used to prepare aqueous dispersions which contain sodium dodecyl sulfate for stabilizing the particles.
  • a metal oxide precursor is added and deposited on the dispersed graphite particles. separated to form the nanocomposite material.
  • the graphite particles have a carbon / oxygen ratio of 10 to 500 because of their production process. Due to the oxygen atoms contained in the graphite particles, it is not easy to adsorb the anionic surfactant on their surface.
  • Graphene oxide which can be prepared by oxidation of graphene and graphite and consists of a layer of carbon atoms condensed into six-membered rings, containing oxygen-containing groups, also serves as the basis for the preparation of functionalized 2D nanomaterials.
  • step (b) adding at least one sol precursor compound to the mixture of step (a),
  • step (c) reacting the mixture of step (b) in a sol / gel process with formation of gel from the at least one sol-precursor bond on the graphene oxide particles or the graphite particles,
  • the present invention also relates to a method for the production of 2D sandwich nanomaterials comprising the steps (a) to (d) and further the steps
  • the invention further provides 2D sandwich nanomaterials which can be prepared by the novel processes and their use as templates for the preparation of further nanosheet materials, their use as catalysts, sensors, capacitors, primary and secondary electrochemical cells and fuel cells and catalysts, sensors , Capacitors, primary and secondary electrochemical cells and fuel cells containing the 2D sandwich nanomaterials according to the invention.
  • step (b) the at least one sol precursor compound also is selected from Si0 2 - precursor compounds and continue to step
  • step (h) removing Si0 2 , wherein step (e) is carried out if a mixture according to (a1) is provided in step (a).
  • the production method according to the invention for 2D nanomaterials and 2D sandwich nanomaterials based on graphene or graphene oxide is simple and can be carried out with comparatively high throughputs and leads to high yields of coated 2D nanomaterials. In doing so, 2D nanomaterials can be produced with a wide variety of different coatings. After the "nanocasting" process, it is also possible to produce coatings which can not be obtained directly by impregnation and removal. For example, using 2D sandwich nanomaterials made of SiCV-coated graphene, nano-casting is used to produce coated graphite particles coated with mesoporous Co 3 O 4 .
  • other metal- and metal oxide-coated 2D nanomaterials can be produced, for example with Sn, Ge, Co, SnO 2 , TiO 2 , Fe 2 O 3 , and Fe 3 O 4 coated 2D nanomaterials.
  • the embodiment of the invention in which a mixture according to (a1) is provided in step (a) and in which the graphene oxide is converted into graphene in step (d) represents a simple route to coated 2D nanomaterials based on graphene in which the relatively inexpensive and readily available starting material graphene oxide is assumed. This route is also very suitable for the production of graphene oxide graphene.
  • the 2D sandwich nanomaterials which can be produced according to the invention have a very high length-to-thickness ratio and have a very high specific surface area with very regularly formed mesoporous structures, which is due to the surfactant molecules originally used in step (a) and the use of different surfactants can be varied.
  • 2D sandwich nanomaterials prepared by the process according to the invention have good application properties, for example graphoprotein-coated graphite particles according to the invention show very good properties as anode material in lithium-ion accumulators. In the following, the invention will be described in detail.
  • graphite means carbon which consists of many planar, superimposed layers which are formed by condensed six-membered rings of sp 2 -hybridized carbon atoms.
  • graphene is understood as meaning a single carbon layer of the graphite structure, ie a single layer of hexagonal condensed rings consisting of six carbon atoms with sp 2 hybridization , preferably from up to 5 layers, more preferably from up to 2 layers and in particular from 1 layer of hexagonal arranged, each consisting of 6 sp 2 -hybridized carbon atoms, condensed rings are formed.
  • graphite oxide is understood to mean a three-dimensional layer-structured structure whose individual layers consist of condensed C 6 rings which are partially hydrogenated. Were functionalized with carbonyl, carboxyl, alcohol and epoxy groups. The individual layers are no longer just as in the graphite, but project partially or completely, depending on the degree of oxidation, zigzag-shaped out of the plane.
  • graphene oxide is understood as meaning materials which are formed from up to 10 layers, preferably from up to 5 layers, particularly preferably from up to 2 layers and in particular from a single layer, which are formed from condensed C 6 rings oxygen-functional groups such as epoxide, alcohol, carboxyl and / or carbonyl groups carry.
  • nanomaterials is used in the context of the present invention as a collective term for graphene oxide particles and graphite particles.
  • "Two-dimensional nanomaterials and sandwich nanomaterials” in the context of the present invention are platelet-shaped particles which in principle have an infinite extent in two directions, in the third However, in the direction of expansion in the range of 0.3 nm to 500 nm, including possibly existing coating, measured by electron microscopy.
  • the sandwich particles based on graphene or graphene oxide according to the invention are coated on the upper side and the lower side and have a layered structure in the manner of a sandwich with the sequence coating / graphene or graphene oxide / coating.
  • the coating may consist of one or more layers.
  • step (a) of the process according to the invention a mixture is prepared according to
  • (a1) contains graphene oxide particles, water and at least one cationic surfactant and / or nonionic surfactant,
  • (a2) graphous particles at least one solvent which can be used for chemical decomposition of graphite, and contains at least one cationic surfactant and / or nonionic surfactant.
  • graphite oxide particles are used for the provision of the mixture according to (a1).
  • graphite oxide particles are used for the provision of the mixture according to (a1).
  • graphite oxide particles are produced by oxidation of graphite. By oxidation, oxygen atoms are incorporated into the graphite, resulting mainly alcohol, epoxy, carbonyl and carboxyl groups. Through these groups, the distances between the individual layers are widened and the layers can be left easier to separate from each other.
  • the oxidized graphite layers are also rendered more hydrophilic by the oxygen-containing groups and more readily dispersible in water.
  • oxidized graphite The production of oxidized graphite is known to the person skilled in the art, it usually takes place by treating graphite with an oxidizing agent and an acid, in particular a strong acid.
  • the oxidizing agents used are in particular chlorates and permanganates, in particular sulfuric acid and nitric acid as the acid.
  • L. Staudenmaier, Ber. Dt. Chem. Ges. 31, (1898), 1481, and L. Staudenmaier, Ber. Dt. Chem. Ges. 32, (1899), 1394 describe the preparation of oxidized graphite, referred to therein as graphitic acid, by reacting graphite with potassium chlorate in the presence of fuming nitric acid and concentrated sulfuric acid.
  • W. S. Hummers, R.E. Offeman, J. Am. Chem. Soc. 80 (1958), 1339 describe the preparation of oxidized graphite by reacting graphite with sodium nitrate and potassium permanganate in the presence of sulfuric
  • expandable graphite which is also called expandable graphite
  • the graphite is expanded in the first step.
  • the product obtained is then z. B. ground in a ball mill.
  • the chemical modification is carried out as described above either by the thermal oxidation or by the oxidation in the presence of sulfuric acid.
  • the mixture contains water and at least one cationic surfactant and / or nonionic surfactant. Suitable surfactants are described below.
  • the graphite oxide particles are at least partially decomposed into graphene oxide particles such that the mixture contains graphene oxide particles.
  • graphite particles are usually suspended in at least one suitable solvent.
  • the graphite particles in the organic solvent are chemically split into individual layers, so that a suspension of graphite particles in the at least one aprotic solvent is obtained.
  • solvents whose surface energy corresponds approximately to that of graphene.
  • solvents with a surface energy of 55 to 90 mJ / m 2 should allow the splitting of graphite particles into graphite particles (Hernandez et al., ArXiV: 0805.2850 vi).
  • suitable solvents are N, N-dimethylacetamide, ⁇ -butyrolactone, 1,3-dimethyl-2-imidazolidinone and N-methylpyrrolidone.
  • Also suitable for the solution exfoliation of graphite are the solvents dimethylformamide, dimethylsulfoxide, tetrahydrofuran, dimethylacetamide and cyclohexane.
  • solvents selected from the group consisting of N-methylpyrrolidone, dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, dimethylacetamide and cyclohexane; dimethylformamide is particularly preferred.
  • Naturally occurring graphite and artificially produced graphite can be used as the graphite; pyrographite, electrographite and expanded graphite are particularly suitable.
  • the mixture according to (a1) or (a2) provided in (a) contains at least one cationic surfactant and / or one nonionic surfactant.
  • the at least one nonionic surfactant is preferably selected from the group of ethylene oxide-containing C2-C 4 -Alkylenoxidblockcopolymere, as sold for example under the name Pluronic ® from BASF SE.
  • Pluronic ® ethylene oxide-containing C2-C 4 -Alkylenoxidblockcopolymere
  • the presence of the at least one cationic and / or nonionic surfactant avoids problems with respect to the incompatibility of graphene or graphene oxide and inorganic materials as well as agglomeration problems.
  • the cationic surfactants or the nonionic surfactants are electrostatically adsorbed on the surface of the highly negatively charged graphene oxide or via interactions with the ⁇ -electrons of the graphene structure on the surface of the graphene and organize themselves in regular microstructures on the top and bottom the graphite particles or graphene oxide particles.
  • cetyltrimethylammonium bromide on graphene oxide particles forms tubular micelles which, upon application of the coating, yield mesopores about 2 nm in size.
  • the respective mixture from graphite oxide particles or graphite particles is usually treated by energy input in order to facilitate the splitting of the graphite particles or graphite particles in the respective mixture to graphene oxide particles or graphene oxide particles and improve. This is achieved, for example, by means of ultrasound, stirring, shaking and further methods known to the person skilled in the art.
  • stirring, grinding and dispersion can be used as an Ultra-Turrax ® stirrer to the expert.
  • the concentration of the at least one cationic surfactant and / or nonionic surfactant is preferably 0.1 to 10 wt .-%, particularly preferably 0.2 to 5 wt .-% and most preferably 0.2 to 1 wt .-%, based on the total weight of Mixture.
  • the mixture according to (a2) preference is given in accordance with the invention to a mixture containing 0.01% by weight of graphite particles, more preferably 0.5% by weight of graphite particles and most preferably 1% by weight of graphite particles, based on the total weight of the Mix, gone out.
  • the mixture contains preferably 0.1 to 10 wt .-%, particularly preferably 0.2 to 5 wt .-% and most preferably 0.2 to 1 wt .-% of at least one cationic and / or nonionic surfactant, based on the total weight of Mixture.
  • the graphite oxide particles or graphite particles are split into single-layer graphene oxide or graphene particles when the mixture is prepared, at least some of the undissolved particles may be separated from the mixture, for example by careful centrifugation.
  • the mixture prepared in step (a1) preferably contains 0.005 to 5% by weight, particularly preferably 0.01 to 5% by weight of graphene oxide particles, the mixture provided in step (a2) 0.001 to 5% by weight, particularly preferably 0.01 to 1 wt .-% graphite particles, each based on the total weight of the mixture.
  • step (b) of the process according to the invention at least one sol precursor compound is added to the mixture obtained from step (a).
  • sol-precursor compound is understood to mean a compound which forms a sol under the conditions prevailing in the respective mixture, the term “sol” being understood as meaning in the context of the "sol-gel” method known to the person skilled in the art.
  • sol-gel a sol precursor is first converted to a sol and subsequently to a gel.
  • the sol-gel method is described, for example, in W. Stober et al., J. Colloid Interf. 26 (1968), page 62.
  • the at least one sol precursor compound is according to the invention is preferably selected from the group consisting of Si0 2 precursor compounds, Zr0 2 - precursor compounds, Ti0 2 precursor compounds, precursor compounds Ce0 2, AI 2 0 3 precursor compounds, Fe 2 0 3 precursor compounds, Fe 3 0 4 - Precursor compounds, MgO precursor compounds, ZnO precursor compounds, chromium oxide precursor compounds, Co 2 O 3 precursor compounds, Mo oxide precursor compounds, W oxide precursor compounds, Hf oxide precursor compounds, Y 2 O 3 precursor compounds and water-soluble, crosslinkable polymers and polymer precursors selected.
  • the at least one sol precursor compound is preferably selected from the group consisting of metal halides, metal nitrates, metal carboxylates, metal oxysulfates, metal acetyl acetonates and metal alcoholates and water glass for Si, where the metal is selected from the group consisting of Zn, Mg, Al, Y, Fe, Cr, Co, Si, Zr, Ti, Ce, Mo, W and Hf.
  • R C to C 8 alkyl, which may be substituted by one or more OH groups and wherein R may be the same or different.
  • the water-soluble crosslinkable polymers and polymer precursors are preferably selected according to the invention from melamine-formaldehyde resin precursors and resorcinol formaldehyde resin precursors.
  • the at least one sol-precursor compound in step (b) is usually added slowly in the liquid state to the preparation of step (a). It can be added in bulk or in solution.
  • the concentration of the added at least one sol precursor compound in step (b) is usually from 0.1 to 10% by weight, preferably from 0.2% by weight to 5% by weight, particularly preferably from 0.2 to 1% by weight. %, based on the graphene oxide particles or graphite particles contained in the mixture (a).
  • catalysts for sol and / or gel formation such as acids or bases can be added in or before step (b).
  • the surfactant molecules self-assembled on the graphene oxide particles or graphene particles and self-organized in mesoporous structures form a molecular template for the controlled nucleation and growth of the sol or gel resulting from the at least one sol precursor compound on the surface of the graphene oxide particles or the graphite particles.
  • step (c) of the process according to the invention the mixture obtained from step (b) is allowed to react in a sol-gel process, whereby the gel becomes soluble in a heterogeneous nucleation process due to the surfactant molecules adsorbed on the surface of the graphene oxide or graphene particles Surface of graphene oxide or graphene particles deposited instead of settling into a homogeneous nucleation process in the solvent.
  • This process is known to the person skilled in the art as a liquid-crystalline template mechanism (GS Arttard, Nature 378 (1995), pages 366-368).
  • the sol precursor compound converts to the sol and on to the gel.
  • Step (c) is usually carried out over a period of 0.5 hours to 2 days, preferably 1 hour to 24 hours, and more preferably from 2 hours to 18 hours.
  • the temperature in step (c) is usually from 10 to 80 ° C., depending on the system, in particular on the solvent or dispersant used.
  • the graphene oxide particles or graphite particles then each have a coating with the respective gel on the upper side and the lower side.
  • the gel has thereby arranged according to the template, which is formed by the at least one cationic surfactant and / or nonionic surfactant on the surfaces of the particles. This results in a homogeneous and structured coating of the surfaces of the particles with the gel.
  • the coated graphene oxide particles or graphite particles can now be further processed, for example separated off and / or dried.
  • the surfactant molecules in step (d) are removed by washing or heating from the coated graphene oxide particles or coated graphite particles, respectively.
  • the coated particles can be washed, for example, with water or solvents such as methanol, ethanol and propanol.
  • the surfactant molecules can also be removed by heating to temperatures of 50 to 500 ° C in an inert atmosphere. Removal of the surfactant particles may also be done by heating the graphene oxide particles in step (e) to convert graphene oxide to graphene so that steps (d) and (e) are performed together. Even if the calcination step has been carried out (see below), the surfactant molecules can be removed.
  • a further calcining process can be connected in which the coated particles are calcined at elevated temperatures in the presence of an oxygen-containing gas or an inert gas.
  • Si0 2 -coated particles are suitable for calcination at 5 to 600 ° C. for several hours, for example 2 to 8 hours, in the presence of air.
  • the coated particles usually contain in the dry state 75 wt .-% to 95 wt .-%, preferably 80 wt .-% to 92 wt .-% and particularly preferably 85 wt .-% to 90 wt .-%, graphene oxide or Graphene and usually 5 wt .-% to 25 wt .-%, preferably 8 wt .-% to 20 wt .-% and particularly preferably 10 wt .-% to 15 wt .-% of formed from the gel coating, based on the total weight of the coated particles.
  • the coated graphene oxide particles are optionally heated for at least 1 minute to at least 500 ° C under an inert gas atmosphere to reduce the graphene oxide to graphene (step (e)).
  • the coated graphene oxide particles are preferably heated for at least 30 minutes and more preferably for at least one hour under an inert gas atmosphere.
  • the heating is usually carried out for not longer than 12 hours, and preferably not longer than 6 hours.
  • the temperature is preferably 500 ° to 1000 ° C.
  • the method comprises the steps
  • step (b) adding at least one sol precursor compound to the mixture of step (a), (c) reacting the mixture of step (b) in a sol / gel process to form the gel on the graphene oxide particles
  • step (e) is performed.
  • the processes described above are carried out such that in step (b) the at least one sol precursor compound is selected from Si0 2 precursor compounds, in particular from water glass and from Si (OR) 4 with R selected from H, CH 3 , C 2 H 5 , C 2 H 4 OH, nC 3 H 7 , 1-C 3 H 7 , nC 4 H 9 and tC 4 H 9 , where R may be the same or different.
  • the Si0 2 coated graphene-based or graphene oxide-based 2D sandwich nanomaterials according to the invention are particularly well suited for use as templates for the production of further 2D sandwich nanomaterials.
  • a further subject of the present invention is therefore a process comprising the steps described above, in which, in step (b), the at least one sol precursor compound is selected from SiO 2 precursor compounds and which furthermore comprises the following steps:
  • the method according to this embodiment thus comprises altogether steps (a) providing
  • step (b) adding at least one sol precursor compound selected from Si0 2 precursor compounds to the mixture from step (a), (c) reacting the mixture of step (b) in a sol / gel process with formation of gel from the at least one sol-precursor bond on the graphene oxide particles or the graphite particles,
  • step (f) the Si0 2 -coated graphene oxide particles or the Si0 2 -coated graphene particles are impregnated with at least one metal oxide precursor compound, a metal precursor compound and / or a carbon precursor compound.
  • the respective precursor compounds fill out the spaces or pores of the SiO 2 coating that were originally filled in by the surfactant molecules.
  • the at least one metal oxide precursor compound and / or the at least one metal precursor compound is preferably selected from the group of metal halides, metal nitrates, metal alcoholates, metal sulfates, metal carboxylates and metal oxysulfates.
  • the at least one carbon precursor compound is preferably selected from the group of sucrose, glucose and pitch.
  • the impregnation of the Si0 2 -coated particles can be carried out by the customary methods known to the person skilled in the art for such processes. These include, for example, the "wet impregnation” method, in which the porous material to be impregnated is suspended in an excess of the corresponding precursor solution and stirred for some time, for example 1 to 24 hours and the excess solution is then removed by filtration. Also suitable is the 'Incipient Wetness' method, in which the solution to be impregnated porous material is mixed with a solution of the corresponding precursor compound, wherein the amount of the solution of the corresponding precursor compound corresponds to the pore volume of the porous material. The suspension obtained can be mechanically mixed.
  • solvents for the metal and / or metal oxide precursor compound or the carbon precursor compound water and / or alcohols such as methanol, ethanol and propanol can be used.
  • concentration of precursor compound (s) in the impregnating solution is usually 10 to 30 wt .-%, preferably 15 to 25 wt .-%, based on the total weight of the impregnating solution.
  • the precursor compound is usually used in a weight ratio of precursor compound to uncoated particles of 0.1: 1 to 50: 1, preferably 0.5: 1 to 20: 1, particularly preferably 1: 1 to 10: 1.
  • the particles are usually separated, optionally washed and dried.
  • step (g) the impregnated particles are treated at elevated temperatures to convert the respective precursor compound to the desired compound.
  • Particles impregnated with carbon precursor compounds are usually heated to 600 to 900 ° C, preferably to 650 to 850 ° C, more preferably to 700 to 800 ° C in inert gas atmosphere, usually for 1 h to 5 h, preferably for 2 h to 4 h .
  • the impregnated particles are usually heated to 200 to 500 ° C, preferably 300 to 400 ° C in an oxygen-containing atmosphere, for example, air for usually 2 to 10 hours, preferably 4 to 8 hours.
  • the impregnated coated particles are usually at 200 ° C to 600 ° C, preferably 300 ° C to 500 ° C in a reductive atmosphere, for example in the presence of hydrogen usually for 4 h to 10 h, preferably for 5 h heated to 8 h.
  • step (h) the silicon dioxide is removed, for example by dissolving in sodium hydroxide or HF.
  • the coated particles can be stirred in an excess of aqueous sodium hydroxide solution for 12 to 24 hours at room temperature with multiple changes of the aqueous sodium hydroxide solution.
  • steps (f) to (h) is known in principle to the person skilled in the art and is referred to as "nanocasting." A description of this method can be found, for example, in A. Rumplecker et al., Chem. , Page 485.
  • steps (f), (g) and (h) may be repeated independently, singly or jointly, one or more times.
  • an impregnation step can be carried out several times in order to achieve a high loading of the coated particles with the precursor compounds.
  • the conversion of the at least one precursor compound can also be carried out several times in order to achieve as complete a conversion as possible.
  • Step (h) can likewise be carried out several times in succession, it being possible in each case for the same or different solvent to be used for the SiO 2 .
  • the coated particles usually contain in the dried state 70% by weight to 95% by weight, preferably 80% by weight to 95% by weight and particularly preferably 85% by weight to 90% by weight, of graphene oxide or Graphene and usually 5 wt .-% to 30 wt .-%, preferably 5 wt .-% to 20 wt .-% and particularly preferably 10 wt .-% to 15 wt .-% coating selected from carbon, metals and / metal oxides , based on the weight of the coated particles.
  • Another object of the present invention are two-dimensional sandwich nanomaterials prepared by the methods described above.
  • the present invention is the use of the sandwich nanomaterials preparable by the processes described above as templates for the preparation of further nanosheet materials. This may be done according to the principles already known to those skilled in the art as “nanocasting.” In each case, “positives” and “negatives” of the structures formed by the self-assembling surfactant molecules in step (a) are prepared.
  • Si0 2 is a coating in which, after removal of the surfactant molecules, for example by impregnation with a carbon precursor compound, the spaces or pores originally filled by the surfactant molecules are filled in.
  • the carbon precursor compound can then be converted to carbon having the three-dimensional structure, such as The Si0 2 may then be removed to leave a microporous carbon structure, which may now also be re-impregnated with a precursor compound, such as a metal oxide precursor compound which may be carbon H heating in an oxygen-containing atmosphere are removed and a metal oxide layer with the structure of the original Si0 2 layer remains.
  • a precursor compound such as a metal oxide precursor compound which may be carbon H heating in an oxygen-containing atmosphere are removed and a metal oxide layer with the structure of the original Si0 2 layer remains.
  • Another object of the present invention is the use of the two-dimensional sandwich nanomaterials, which can be prepared by the methods described above, in catalysts, sensors, capacitors, primary and secondary electrochemical cells and fuel cells and catalysts, sensors, capacitors, primary and secondary electrochemical cells and fuel cells containing two-dimensional sandwich materials, preparable according to the methods described above.
  • the method according to the preferred embodiment described above comprises steps (a) to (e), in which the at least one sol precursor compound in step (b) is selected from Si0 2 precursor compounds. If a mixture according to (a1) is provided in step (a), step (e) is carried out in order to convert the graphene oxide particles into graphite particles. Step (e) is then followed directly by step (h) (removal of the Si0 2 from the graphene oxide particles). More specifically, this embodiment of the invention includes the following steps
  • step (b) adding at least one sol precursor compound selected from Si0 2 precursor compounds to the mixture from step (a),
  • step (c) reacting the mixture of step (b) in a sol / gel process with formation of the gel on the graphene oxide particles or the graphite particles,
  • step (e) optionally, heating the coated graphene oxide particles for at least 1 minute to at least 500 ° C under an inert gas atmosphere to reduce the graphene oxide to graphene if a mixture according to (a1) is provided in step (a), and
  • the graph particles are particularly preferably produced from graphene oxide.
  • the method comprises the steps
  • step (b) adding at least one sol precursor compound selected from Si0 2 precursor compounds to the mixture from step (a),
  • step (c) reacting the mixture of step (b) in a sol / gel process with formation of the gel on the graphene oxide particles
  • the present invention also encompasses the use of the two-dimensional sandwich nanomaterials preparable by the methods described above for producing graphite particles. In the following, the present invention will be explained by way of examples.
  • Example 1 Preparation of Si0 2 -coated graphene oxide particles.
  • Graphene oxide was prepared from natural graphite flakes according to the method of Hummers (Hummers, WS & Offeman, RE, J. Am. Chem. Soc 80 (1958), pages 1339 to 1 139.) 30 mg of the thus-synthesized graphene oxide was first prepared in an aqueous solution containing 1 g of cetyltrimethylammonium bromide, 40 mg of NaOH in 500 ml of demineralized water and sonicated for 3 hours, then the suspension was stirred for 2 hours at 40 ° C with a magnetic stirrer and 1 ml of tetraethyl orthosilicate (TEOS) slowly to the The mixture was allowed to react for 12 hours and the SCV coated graphene oxide particles were then washed with warm ethanol, separated and dried for 6 hours at 80 ° C.
  • TEOS tetraethyl orthosilicate
  • the thickness of the particles was determined by atomic force microscopy analysis, perpendicular to the major plane of the flat particles, resulting in a uniform thickness of 28 ⁇ 1 nm.
  • Example 2 Preparation of SiO 2 -coated graph particles of SiO 2 -coated graphene oxide particles.
  • the mesoporous SiO 2 -coated graphene oxide particles prepared according to Example 1 were prepared by pyrolysis of the coated graphene oxide particles at 800 ° C. for 3 hours in argon.
  • an effective reduction of the graphene oxide in graphene without aggregation of the particles is achieved because the particles are protected by the Si0 2 coating.
  • the morphology and structure of the Si0 2 coated graph particles remained stable during the heat treatment and the Mesoporous structure was retained during pyrolysis, as demonstrated by scanning electron micrographs and transmission electron micrographs.
  • the SiO 2 coated graph particles obtained from Example 2 were analyzed by nitrogen adsorption and showed a type IV nitrogen adsorption isotherm characteristic of uniform mesopores.
  • the pore size distribution was calculated to 2 nm according to Barrett-Joyner-Halenda.
  • the adsorption data revealed a very high specific surface area of 980 m 2 g "1 , which is comparable to conventionally produced mesoporous silica.
  • the Si0 2 -coated graph particles from Example 2 were repeatedly impregnated with a solution of sucrose in ethanol with stirring at 40 ° C, the ratio of sucrose to Si0 2 coated graphite particles in the final product was set to 2: 1.
  • the sucrose-impregnated particles were then dried and pyrolyzed at 700 ° C for 3 hours in argon atmosphere. Subsequently, the particles obtained were freed from the Si0 2 in aqueous NaOH solution. Mesoporous carbon coated graphite particles were obtained.
  • Electron microscopic examination of the carbon coated particles revealed that the carbon layers had high monodispersity of the structure of the same size as the template used, coated with Si0 2 particles.
  • X-ray examinations revealed that the carbon in the coating is amorphous. Examination by nitrogen adsorption and desorption yielded a specific surface area (according to Brunauer-Emmett-Teller) of 910 m 2 g -1 . The particles showed a type IV isotherm, indicating the existence of a large number of mesopores and micropores in the carbon-coated Graph particles indicates.
  • the Si0 2 -coated graph particles from Example 2 were impregnated with solutions of cobalt nitrate in ethanol several times with stirring at 40 ° C., the weight ratio of cobalt nitrate to SiO 2 -coated graphite particles being 2.3: 1.
  • the cobalt nitrate impregnated particles were heated at 350 ° C for 5 hours in air. Subsequently, the SiO 2 was removed from particles in aqueous NaOH solution. Examination with a high-resolution transmission electron microscope revealed that the Cu 3 O 4 had a mesoporous but crystalline structure.
  • Example 5 Use of Carbon Coated Graph Particles in Lithium-Ion Accumulators.
  • the electrochemical studies were carried out in 2032 button cells.
  • the working electrodes were prepared by mixing carbon-coated graph particles of Example 3, carbon black (Super-P) and poly (vinyldifluoride) (PVDF) in a weight ratio of 80: 10: 10 and brushing on copper foil (99.6%, Goodfellow) , Lithium foil was used as the counter electrode.
  • the electrolyte consisted of a one-molar solution of LiPF 6 in ethylene carbonate (EC) and dimethyl carbonate (DMC) (volume ratio of 1: 1, Industries Ltd).
  • the cells were assembled in an argon-filled glove box with the concentration of moisture and oxygen each below 1 ppm. Electrochemical performance was measured at various charge / discharge rates in the voltage range of 0.01 to 3.00V. The results are shown in Tables 1 and 2.

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Abstract

L'invention concerne un procédé de production de nanomatériaux bidimensionnels, comprenant les étapes suivantes : (a) production (a1) d'un mélange contenant des particules d'oxyde de graphène, de l'eau et au moins un composé tensio-actif cationique et/ou un composé tensio-actif non ionique, ou (a2) d'un mélange contenant des particules de graphène, au moins un solvant, qui peut être utilisé pour la dissociation chimique du graphite, et au moins un composé tensio-actif cationique et/ou un composé tensio-actif non ionique; b) addition d'au moins un composé précurseur de sol, au mélange de l'étape (a); (c) mise en réaction du mélange de l'étape (b) dans un processus sol-gel, avec formation d'un gel formé du ou des composés précurseurs de sol sur les particules d'oxyde de graphène ou les particules de graphène; (d) élimination du ou des composés tensio-actifs; et (e) éventuellement, chauffage des particules d'oxyde de graphène couvertes de gel, pendant au moins 1 min, à au moins 500°C, sous atmosphère de gaz inerte, afin de réduire l'oxyde de graphène en graphène.
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