WO2023083706A1 - Procédé de synthèse de nanoparticules d'au moins un élément du groupe formé par le groupe des métaux non précieux et de l'antimoine, et nanoparticules - Google Patents

Procédé de synthèse de nanoparticules d'au moins un élément du groupe formé par le groupe des métaux non précieux et de l'antimoine, et nanoparticules Download PDF

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WO2023083706A1
WO2023083706A1 PCT/EP2022/080782 EP2022080782W WO2023083706A1 WO 2023083706 A1 WO2023083706 A1 WO 2023083706A1 EP 2022080782 W EP2022080782 W EP 2022080782W WO 2023083706 A1 WO2023083706 A1 WO 2023083706A1
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nanoparticles
precursors
group
precursor
antimony
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PCT/EP2022/080782
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German (de)
English (en)
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Katherine Ann MAZZIO
Baris AKDUMAN
Philipp Adelhelm
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Helmholtz-Zentrum Berlin Für Materialien Und Energie Gmbh
Humboldt-Universität Zu Berlin
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Publication of WO2023083706A1 publication Critical patent/WO2023083706A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/14—Treatment of metallic powder
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/0433—Nickel- or cobalt-based alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/0483—Alloys based on the low melting point metals Zn, Pb, Sn, Cd, In or Ga

Definitions

  • the invention relates to nanoparticles and a method for producing nanoparticles which are formed from at least one element from the group consisting of the base metals and antimony.
  • Sodium ion batteries are attractive alternatives to lithium ion batteries (LIBs) because of the high abundance and low cost of sodium (Na).
  • the cathodes do not require cobalt and their fabrication can be made similar to that of LIBs, optimizing production.
  • a challenge associated with the development of NIBs is that cost reduction must offset the lower energy densities relative to LIBs, and hence there is a strong trend towards the development of alloy anodes for NIBs due to their high storage capacity and favorable redox potentials.
  • Base metal nanoparticles such as tin (Sn) particles seem to be an attractive option to increase the capacity of NIB anodes.
  • the group of base metals within the meaning of this invention is made up of metals whose redox pairs have a negative standard potential (relative to the normal hydrogen electrode).
  • the invention also affects nanoparticles of antimony, which is usually not counted among the base metals.
  • the invention thus relates to nanoparticles and their synthesis from elements from the group formed from the group of base metals and antimony.
  • Nanoparticles within the meaning of the invention are nanoparticles which have a diameter in a range from 10 nanometers to 200 nanometers.
  • Tin has a redox potential of about 0.2 V versus Na + /Na, which is very suitable for use as an anode, combined with a very high theoretical capacity of 847 mAh/g and high efficiency. Nanostructuring can further help prevent cracking and powdering of electrodes caused by volume expansion during alloying. Achieving the combination of chemical and mechanical toughness during electrochemical cycling ultimately enhances the maximum capacity and lifetime of electrodes employing these materials.
  • Bottom-up synthesis methods are based on chemical strategies that use various precursor materials (chemical compounds), so-called precursors, and chemical reducing agents, as starting materials, for the production of nanomaterials, as products. These methods have been successfully used for the production of nanomaterials good control of their dimensions, dispersity, morphology and composition.
  • Mechanochemistry is a technique that is commonly used on an industrial scale for the production of battery anode materials, but almost exclusively via top-down approaches, which rely on a comminution of bulk materials that does not allow specific control of the resulting morphology or composition.
  • the object of the invention is to specify a method for the synthesis of nanoparticles from at least one element from the group consisting of the base metals and antimony, with controlled dimensioning of the nanoparticles, which is also simplified compared to those known from the prior art Process for precious metals is to be carried out while being cost-effective and environmentally friendly. Furthermore, the nanoparticles made of base metal, which are produced by this method with the corresponding properties, are the subject of the invention.
  • base metal The representative singular (nanoparticles made of) "base metal” is usually used to classify nanoparticles as those formed from one or more metals that belong to the group of base metals, as the singular of the generic name "base metal”. which includes the plural.
  • base metal in the dative: base metal
  • base metals are used synonymously with the generic plural “base metals”.
  • a first aspect of the invention relates to a method for the synthesis of nanoparticles from at least one element from the group which is formed from the group of base metals and antimony, the method comprising a feed step as a pre-process in which only a precursor or a Mixture of precursors which, in their respective chemical compound, contain in particular one or more different elements which can be attributed to the base metals and/or antimony, and a Reducing agents, in particular an inorganic hydride, advantageously a hydride of a boron group element, such as a borohydride or an aluminum hydride, of which sodium or lithium borohydride is particularly suitable, are provided.
  • the base metals that are contained in the chemical compounds that form the precursors correspond to those that are to be represented as nanoparticles, as products, using the method according to the invention.
  • nanoparticles are synthesized which consist of alloys of the different base metals of the precursors used.
  • the method further comprises a dry milling step, wherein in the dry milling step only the precursor or precursors and the reducing agent are milled so that a powder mixture is obtained which comprises the base metal nanoparticles or the base metal nanoparticles and one or more additional components from the group comprising one or more by-products and/or one or more unreacted species (educts).
  • the size of a base metal nanoparticle produced by the method is about 10 nanometers to 200 nanometers. In particular, this means a diameter of a corresponding nanoparticle of approximately 10 nanometers to 200 nanometers.
  • the precursors are advantageously halides.
  • metal salts or organometallic compounds also come into consideration as precursors.
  • a mixture of precursors is provided in the feeding step, consisting of different chemical compounds, each of which contains base metals and/or antimony.
  • the mixture of precursors can include or consist of several halides.
  • the inventive method for the synthesis of base metal nanoparticles corresponds to a bottom-up approach.
  • the bottom-up approach can use atoms as building blocks and relies on nucleation, clustering, and/or growth.
  • the process is a bottom-up mechanochemical synthesis.
  • An advantage of the method according to the invention is that it is an environmentally friendly process that can easily be scaled up. Advantageously, it is also an efficient process in terms of yield and energy consumption.
  • the dry milling step is a mechanochemical processing step.
  • Mechanochemical processing is based on the activation of chemical reactions, structural changes and/or phase changes brought about by mechanical action.
  • the mechanochemical processing is based on the grinding of the reactants (precursors and reducing agents), which leads to repeated collisions of the reactant or reactants with grinding balls in the grinding device, causing a mechanically induced activation of the reaction.
  • the grinding device for use in the method according to the invention can be, for example, a high-energy mill.
  • a high energy mill can lead to different types of mechanical effects through shear, impact and friction forces. In particular, milling does not involve mass transfer. Milling can generally lead to amorphous or disrupted phases and lead to a reduction in nanoparticle, domain and/or grain size.
  • Reactive milling can generally result in solid-solid, solid-gas or solid-liquid reactions where initial reaction precursors (reactants) react to form products through the action of mechanical energy and/or incorporate them into metal/alloy matrices, for example.
  • a grinding device can also be a ball mill, a vibratory ball mill, a planetary ball mill, an attritor/string ball mill, a pin mill or a roller mill.
  • the dry grinding step can be carried out in a grinding bowl.
  • the grinding jar can be a ZrC>2 grinding jar, among other things.
  • the grinding jar is a stainless steel grinding jar.
  • the size of the base metal nanoparticles as a product of the process is controllable by adjusting at least one of the following parameters of the performance of the dry milling step.
  • One of these parameters of the dry milling step is the duration of the dry milling step, also referred to as milling time in the context of the present application.
  • Another parameter of the dry milling step is the size of the milling balls used.
  • a parameter for controlling particle growth in the dry milling step is the ratio of the weight of the milling balls to that of the powder mixture of precursor(s) and reducing agent.
  • the milling time in the dry milling step is advantageously shorter than 30 minutes and is in particular in a range between 5 minutes and 30 minutes Synthesis of Sn nanoparticles was observed.
  • the larger nanoparticles can crystallize out due to Ostwald ripening with longer milling times.
  • the grinding time consists of individual grinding intervals interrupted by breaks in the grinding process. The breaks are not included in the grinding time.
  • the grinding with breaks in the grinding process serves to prevent a temperature increase, which means a temperature that is above the melting points of the metals of the nanoparticles to be produced.
  • the duration of the grinding intervals and the pauses may need to be determined experimentally, since these depend on a number of parameters (metal, precursor, type of mill, etc.).
  • parts of the starting materials added cannot react and are therefore present in the end product.
  • the unreacted starting materials can be unreacted precursors and/or reducing agents.
  • reaction by-products can also form in the reaction taking place in the process.
  • a by-product can be addressed as MX, where M is the metal of the reducing agent and X is one from the group CI, Br or I, depending on the precursors used.
  • the reaction by-product can be NaX, for example. In this case Na comes from the reducing agent.
  • the reaction by-product can also be LiX, for example. In this case, Li also comes from the reducing agent.
  • the by-product can also be, for example, NaCl or LiCl depending on the starting materials.
  • the reducing agent is one of sodium borohydride, lithium borohydride, or lithium aluminum hydride, and advantageously sodium borohydride or lithium borohydride.
  • the reducing agent can be given, for example, by NaBH 4 (sodium borohydride).
  • the reducing agent NaBH 4 is a complex salt.
  • Sodium borohydride (NaBH 4 ) can be used as a mild reducing agent in organic chemistry because of its selective reducing properties.
  • the reducing properties of hydrides are strongly dependent on several parameters, such as the bonding between the metal and boron atoms, when large electronegativity differences lead to more ionic behavior. It should be emphasized in particular that the dry milling step in the method according to the invention is carried out without any liquid and therefore in particular also without a solvent, which corresponds to the designation as a dry milling step.
  • the dry grinding step in the process according to the invention since it is dry, is also carried out without liquids such as water or alcohol, this exclusion also including “capping agents”.
  • the term “without water” also means without water generation during the process and without hydrates of precursors. In particular, water is not a by-product of the process according to the invention.
  • the term “without an alcohol” also means without alcohol production during the process according to the invention.
  • liquids such as solvents during the synthesis of the present invention is particularly advantageous in that it means reduced waste generation and reduced disposal costs of contaminated solvents.
  • Normal solution-based syntheses also prevent large-scale production of materials, since there are usually no linear relationships between concentrations of reactants (educts) and solvents on a laboratory scale and on an industrial scale.
  • ligands which normally serve to mediate the growth of the nanoparticles and often have to be removed at the end.
  • the elimination of solvents during synthesis advantageously eliminates the use of ligands, which in turn eliminates a subsequent processing step (which is often time-consuming and energy-intensive).
  • the process - being dry - is also polar protic solvent free and most particularly is an anhydrous and alcohol free process, which has lower material costs compared to synthesis processes dependent on a polar protic solvent .
  • handling and processing are easier compared to synthetic methods that depend on a polar protic solvent.
  • the processing procedure can be compared to Synthesis methods that depend on a polar protic solvent can be easier.
  • the energy consumption is lower compared to synthesis methods that depend on a polar protic solvent.
  • the amount of waste is advantageously lower compared to synthesis processes that depend on a polar protic solvent.
  • the hazard and toxicity associated with organic solvents can be advantageously lower compared to synthesis methods that depend on a polar protic solvent.
  • the synthesis can advantageously be carried out in an inert atmosphere in the process according to the invention.
  • the base metal of the precursor or the base metals of the precursors are selected in such a way that, below the melting point (melting temperature) of the base metal/base metals of the product, the Gibbs free energy of the synthesis is negative.
  • the reaction requires that the temperature in the ball mill is below the melting point of the nanoparticles (otherwise they may tend to agglomerate and some size control may be lost).
  • Melting points of base metals (in the solid state) of interest are listed in Table 1 below. Melting points of metals can decrease with decreasing nanoparticle size. This means that the melting point for the corresponding nanoparticles can differ from the melting points given here in the solid body.
  • the base metal of the precursor or the base metals and/or antimony of the precursors is selected from the group consisting of tin, zirconium, iron, molybdenum, nickel, iridium, germanium, cobalt, bismuth, zinc, lead, indium, antimony and cadmium.
  • tin, zirconium, iron, molybdenum, nickel, iridium, germanium, cobalt, bismuth, antimony and zinc in particular from the group consisting of tin, cobalt, zirconium, antimony and iron.
  • the precursor or precursors are formed from halides, in particular chloride, bromide or iodide.
  • the precursor or precursors include, for example, chloride and the base metals of the precursor or precursors is selected from the group consisting of tin, iron, molybdenum, nickel, iridium, germanium, cobalt, bismuth, zinc, antimony, lead, indium, cadmium, in particular Tin, Iron, Molybdenum, Nickel, Iridium, Germanium, Cobalt, Bismuth, Zinc, Antimony, Lead, Indium.
  • the synthesis, carried out at room temperature comprises, for example, at least one chloride precursor and the base metal of the precursor being selected from the group consisting of Sn 2+ , Sn 4+ , Fe 2+ , Mo 2+ , Ni 2+ , Ir 2+ , Ge 2+ , Ge 4+ , Co 2+ , Bi 3+ , Sb 3+ , Pb 2+ , ln 2+ , Cd 2+ , in particular Sn 2+ , Sn4+, Fe2+, Mo 2+ , Ni 2+ , lr 2+ , Ge 2+ , Ge 4+ , Co 2+ , Bi 3+ , Sb 3+ , Pb 2+ , Inn 2+ .
  • the synthesis further comprises at least one precursor of bromide and wherein the base metal of the precursor is selected from the group consisting of tin, iron, molybdenum, nickel, iridium, germanium, cobalt, bismuth, zinc, antimony, lead.
  • the synthesis, carried out at room temperature, comprises as a further example at least one precursor of bromide and wherein the base metal of the precursor or precursors is selected from the group consisting of Sn 2+ , Sn 4+ , Fe 2+ , Mo 2+ , Ni 2 + , lr 2+ , Ge 2+ , Ge 4+ , Co 2+ , Bi 3+ , Sb 3+ , Pb 2+ .
  • one or more precursors is an iodide and the base metal and/or antimony of the precursor or precursors is selected from the group consisting of tin, iron, molybdenum, nickel, iridium, germanium, cobalt, bismuth, antimony.
  • one or more precursors comprise an iodide and the base metal and/or antimony of the precursor is selected from the group of Sn 2+ , Sn 4+ , Fe 2+ , Mo 2+ , Ni 2+ , lr 2+ , Ge 2+ , Ge 4+ , Co 2+ , Bi 3+ , Sb 3+ .
  • the precursor or precursors is/are selected from the group consisting of SnCl2, SnBr2, Snl2, SnCk, SnBr4, Snl4, FeCl2, FeBr2, Fek, MoCl2, MoBr2, MoI2, NiCl2, NiBr2, NH2, lrCl2, lrBr2, Irk, GeCh, GeBr2, Gel2, GeCU, GeBr4, Gek, C0Cl2, CoBr2, C0I2, BiCh, BiBr 3 , Bil 3 , SbCl 3 , SbBr 3 , Sbl 3 , PbCl 2 , PbBr 2 , lnCl 2 .
  • the method comprises a separation step after the dry milling step, wherein in the separation step the base metal nanoparticles are separated from the additional components of the powder mixture.
  • the method comprises a separation step after the dry milling step, wherein in the separation step at least one solvent or a mixture of solvents is added to the powder mixture in order to remove the additional components by dissolving salts and/or quenching the unreacted reducing agent, wherein in a subsequent step, the solvent is removed, in particular by a centrifugation step, thereby obtaining the base metal nanoparticles.
  • the method comprises a cleaning step after the separation step, wherein in the cleaning step at least one additional solvent or a mixture of additional solvents is added to the powder mixture in order to remove the additional components by dissolving salts and/or quenching the unreacted reducing agent wherein in a subsequent step the further solvent is removed, in particular by a centrifugation step, whereby the base metal nanoparticles are obtained, the further solvent being the same solvent as in the previous separation step or different from the solvent of the previous separation step.
  • the separation step and/or the purification step are advantageously carried out with cooling and/or with stirring.
  • Another parameter of the dry milling step is the milling speed, which influences the energy to obtain an activation energy required to start the reaction.
  • the activation energy and thus a possible grinding speed is dependent on the materials that are provided in the process, in particular the precursors.
  • high-energy ball milling or vibrating ball milling should be used for the synthesis.
  • the dry milling step is carried out using milling balls, in particular stainless steel milling balls.
  • a second aspect of the invention relates to nanoparticles which are formed from at least one element from the group which is formed from the group of base metals and antimony and which are produced by the method according to the invention and which are characterized in that the nanoparticles have a have a clean surface, where a clean surface means a surface without ligands.
  • the nanoparticles also show a particle size distribution that corresponds to a normal distribution.
  • the synthesis can also be carried out in a closed medium, with the ambient atmosphere being a controllable parameter.
  • the milling atmosphere is, for example, provided by inert Ar, which means that there is no oxidation of the base metal nanoparticles, which is confirmed by XRD and TEM studies.
  • the synthesis in the process according to the invention is based in its underlying reduction reaction on a redox couple, namely the precursor or precursors on the one hand and the reducing agent on the other.
  • a redox couple namely the precursor or precursors on the one hand and the reducing agent on the other.
  • the synthesis can also be carried out with compounds which are equivalent to the reducing agent and to the precursor or precursors.
  • the method according to the invention to produce nanoparticles from an alloy of base metals or base metals and antimony, e.g. an alloy of Sn and Sb by a bottom-up process in which two different precursors as a mixture, each comprising one of the base metals of the alloy to be formed in the process, are provided in the feed step of the process.
  • the bottom-up process for alloyed nanoparticles provided by the invention also constitutes an alternative to the coprecipitation process for forming nanoparticles from base metal alloys as provided by wet chemistry and is a particularly noteworthy advantage of the invention.
  • NPs nanoparticles
  • the method according to the invention enables the formation of composite structures during the milling process, namely, simultaneously with the redox reaction.
  • One of the greatest advantages of the bottom-up mechanochemical synthesis of the method of the invention is that it eliminates the requirement of using a solvent medium, which normally allows ion dissociation and thus promotes NaBH 4 oxidation.
  • the synthesis according to the invention also requires, as evidenced by a TEM analysis, that the number-weighted size distribution of the nanoparticles produced shows a normal distribution and in particular no tails (asymmetric broadening) as in “top-down syntheses”.
  • the formation of larger nanoparticles can be prevented by selecting an appropriate grinding time and grinding ball size.
  • Ball milling methods are empirical methods for which no generalized relationships between the parameters can be set up, with which a specific result can be determined in advance. It is therefore up to the person skilled in the art to use common methods for characterizing the chemical and physical properties, in particular X-ray diffraction (XRD), TEM and IR spectroscopy, in order to control and optimize the notified products from the process, and to adjust the parameters accordingly by adjust success.
  • XRD X-ray diffraction
  • TEM TEM and IR spectroscopy
  • the framework conditions that are specified by a mill itself are specified as limits for the person skilled in the art.
  • the ratio of precursors and reducing agent should at least correspond to that required for stoichiometric conversion.
  • An excess of reducing agent is not a hindrance to the process.
  • An excess of reducing agent can speed up the reaction, but also requires a more extensive work-up at the end. It is up to those skilled in the art to strike a balance here.
  • BPR ball-to-powder weight ratio
  • size and number of grinding balls and thus their weight as well as the grinding speed essentially determine the energy input and must be adjusted experimentally.
  • these parameters all depend strongly on one another and influence one another, so that certain restrictions, for example given by a device, have to be compensated for by changing other parameters.
  • Various aspects of the parameters and the control of results in ball milling processes are discussed, for example, in the review article by P. Baläz et al. (Hallmarks of mechanochemistry: from nanoparticles to technology, Chemical Society Reviews, Vol 42, 2013, pp. 7571-7637). An upper limit for the parameters is ultimately always given by the mills used.
  • a lower limit is given by the fact that the interaction of the parameters "BPR - size and/or number of grinding balls - grinding speed" must be sufficient to bring about an energy input sufficient for a reaction to be activated. This is experimental by characterizing the products can be checked after grinding. A sluggish reaction can always be brought to an end by a longer milling time or a higher energy input.
  • Fig. 3 X-ray diffractograms of two products of the process according to the invention with different with the same milling time of 30 min.
  • Fig. 5 TEM images of some products of the method according to the invention, carried out with different parameters.
  • Fig. 6 Background-corrected, Fourier-transformed infrared spectroscopy (FT-IR) spectra of nanoparticles from synthesis with different milling times as synthesized (top) and processed (bottom).
  • FT-IR Fourier-transformed infrared spectroscopy
  • Fig. 7 Proposed reaction mechanisms in the mechanochemical synthesis of the method according to the invention.
  • Fig. 8 X-ray diffractograms of the crude reaction products for different syntheses of NPs from Sn x /Sbi. x alloy with the method according to the invention using SnCl2 and SbBr2 as starting materials.
  • precursor and reducing agent in which the precursor used is SnCl2 and the reducing agent is sodium borohydride.
  • Sodium borohydride (NaBH 4 ) (ReagentPlus® with a purity of 99%) was purchased from Sigma Aldrich (CAS number: 16940-66-2). The original bottle was opened in an open atmosphere and immediately transferred to an argon-filled glove box ( ⁇ 0.1 ppm O2 and H2O). The precursor SnCh (MW: 189.62 g/mol) was weighed in an open atmosphere and transferred to an argon-filled glove box inside the ball milling jar with an amount of 10 mm diameter stainless steel milling balls such that a ball/powder weight ratio of 20 (Ball/powder ratio: BPR).
  • Table 2 Embodiments of methods according to the invention with sodium borohydride as reducing agent and SnCh as precursor in a molar ratio of precursor (MP) to reducing agent ( RA ), MP: RA of 1:4, ball/powder weight ratio (BPR) of 20, 500 rpm milling speed and milling time interval of 1 min milling - 2 min rest for all examples.
  • MP precursor
  • RA reducing agent
  • BPR ball/powder weight ratio
  • the grinding procedures were carried out using a Fritsch Pulverisette 7 planetary ball mill with an 80 mL stainless steel grinding bowl.
  • Each milling procedure consisted of milling intervals (counting to the meal) of 1 min separated by pauses of 2 min (pauses, not counted to the meal) in consecutive cycles at 500 rpm.
  • the grinding jar was transferred to an Ar-filled glove box and approx 0.4 g sample and 2 stainless steel grinding balls were taken to keep the BPR constant. After resealing the ball milling jar in an inert atmosphere, the milling operation was continued for the next magazine.
  • the synthesized powders contained unreacted reactants, reaction byproducts, and reduced Sn metal. Therefore, an additional preparation procedure for further material characterization and for electroanalytical measurements is necessary in the example.
  • the preparation procedure consisted of five main steps, illustrated in Figure 1 and described below. It should be noted that the treatment procedure can be adapted in each case to the amount and, if appropriate, the type of reaction by-products.
  • the toluene (on top of the solution due to immiscibility and low density) was removed from the solution using a glass pipette.
  • the remaining solution, containing the dissolved species and precipitated nanoparticles, was then transferred to a 50 mL centrifuge tube and subjected to a three-stage subjected to centrifugation. Initially, the centrifugation process was performed in the treatment solution mixture (which contained isopropanol, ethanol, and DI-H2O (deionized water)). In the second step, DI-H2O itself was used to remove remaining water-soluble species.
  • ethanol was used for the final centrifugation to help precipitation and collection of the reduced Sn NPs. Centrifugation was carried out at 500 rpm for 10 min in each step. After decanting ethanol, the precipitates were collected in a glass vial with a small amount of ethanol and allowed to dry at room temperature for 24 hours to prevent temperature-assisted growth of the NPs.
  • the products were initially synthesized starting from 30 min to 360 min milling time. Due to the rapid reactions observed, additional syntheses of a new batch were performed examining synthesis times spanning 5 min to 30 min milling times.
  • the time-resolved X-ray diffractograms obtained (from XRD) of the synthesized reaction mixtures are shown in FIG.
  • X-ray diffractograms in the range 28-32.5° 26 for the products from milling times of 30 minutes each from two different batches are shown in FIG.
  • the reduction reaction takes place within 5 minutes and is reflected in an intensity ratio of the SnCh and Sn peaks.
  • the observations on the amount of gas evolved during the initial milling time are also reasonable and no liquid phase formation is observed.
  • TEM samples were prepared by spotting diluting solutions onto the conditioned nanoparticles of distilled H 2 O on 200-mesh Cu TEM grids coated with ultra-thin carbon and Lacey carbon support films (PLANO, GmbH). All TEM data analysis was performed using ImageJ software (for images) or Velox software (for spectra).
  • FIG. 5 shows TEM images for Sn NPs after different milling times.
  • the observed NPs have well-defined spherical shapes. Nucleation and growth are faster and nanoparticles even begin to experience a top-down comminution process from 60 min milling time and reaching sizes over 100 nm based on TEM analysis.
  • Figure 5(h) two coalescing nanoparticles are visible for the 5 min sample.
  • the high resolution TEM micrographs shown in Fig. 5 correspond to the samples with milling times of a, f and h 5 min, b and g 30 min, c and i 60 min and d and j 120 min showing irregularly shaped clumps of nanoparticles (i.e ) after 120 min milling time.
  • Table 3 lists the changes in volume weighted mean diameter D 4 3 with respect to milling time based on TEM analysis performed with ImageJ software.
  • 360 84.66 0.65 114.62 0.81 6 shows background-corrected Fourier-transformed infrared spectroscopy (FT-IR) spectra of samples after various milling times.
  • FT-IR Fourier-transformed infrared spectroscopy
  • FIG. 7A A proposed reaction mechanism is given in FIG.
  • Figure 7B a general reaction mechanism is provided,
  • M is the metal of the reducing agent.
  • X can be CI, Br or I depending on the precursor used.
  • the precursors and NaBH 4 are always given in molar ratio with excess NaBH 4 and a bead/powder weight ratio (BPR) of 20,500 rpm at milling speed and milling time intervals of 1 min milling - 2 min pause for all examples.
  • BPR bead/powder weight ratio
  • the second example describes methods according to the invention for synthesizing nanoparticles from base metal, in which the metal halides correspond to CoBr2 or Fe2 as precursors.
  • the example shows the effectiveness of the reaction with the two different metals and halides.
  • Both syntheses of the example were carried out with NaBH 4 as the reducing agent and under an Ar atmosphere.
  • the other parameters corresponded to those mentioned in Example 1 (see Table 1).
  • X-ray diffractograms of the syntheses were recorded after 5 min and 30 min for Fe and after 5 min, 30 min and 60 min for Co. It turns out that Fe NPs were found in the X-ray diffraction pattern along with the expected Nal salt formation.
  • NaBr was observed as a product in the Co NP synthesis, but no obvious Co reflections could be observed in the X-ray diffractograms, indicating the formation of an amorphous product.
  • SEM/EDX studies were performed on a prepared batch of Co NPs, showing that the expected materials were formed.
  • the SnSb alloy products have mixed crystal structures.
  • both cubic and tetragonal phases of the Sn x Sbi. x - products observed.
  • the cubic phase is expected to be in stoichiometric ratio.
  • Sb is to be expected substoichiometrically.
  • the diffractograms in FIG. 8 show the reaction products of different nanoparticle syntheses from Sn x Sbi. x alloy after 120 minutes milling time.
  • the 100% Sb sample shows some Sb 2 Os contamination due to improper sealing of the ball mill jar, underscoring the importance of an inert atmosphere during the synthesis. Alloying occurs in all cases for 0.01 > x > 0.99, as evidenced by the shift of the main reflex from Sb at 28.6° 20 to 29.1° 20 with increasing Sn concentration. Some elemental Sn content can also be observed in the reflections appearing at 30.6°20 and 35.1°20. However, EDX analysis of all samples shows compositions consistent with the employed precursor stoichiometry, supporting alloy formation. As Precursors SnCl 2 and SbBr2 were provided in the molar ratio of the envisaged stoichiometry with NaBH4 as the reducing agent in the feed step.
  • CosNisySnss was chosen.
  • the CosNisySnss stoichiometry was chosen in particular because it forms a single-phase q-alloy with a similar Crystal II structure as q-phase Ni 3 Sn 2 .
  • CoBr 2 , NiCl 2 and SnCl 2 were provided as precursors in accordance with the ratio of the stoichiometry of the envisaged alloy with NaBH 4 as the reducing agent in the feed step.
  • FIG. 10 shows the diffractograms of the crude reaction product after milling for 30, 60, 90 and 120 minutes.

Abstract

L'invention concerne un procédé de synthèse de nanoparticules à partir d'au moins un élément du groupe formé par le groupe des métaux non précieux et de l'antimoine ainsi que des nanoparticules, le procédé comprenant une étape d'amenée dans laquelle exclusivement un précurseur ou un mélange de précurseurs et un agent de réduction, en particulier un hydrure inorganique sont fournis. Le procédé comprend une étape de broyage à sec dans laquelle le précurseur et l'agent de réduction sont broyés pour obtenir un mélange pulvérulent qui contient les nanoparticules constituées de métal non précieux et/ou d'antimoine ou les nanoparticules et un ou plusieurs composants supplémentaires, en particulier un ou plusieurs sous-produits et/ou une ou plusieurs espèces qui ne sont pas mises en réaction. L'invention concerne en outre des nanoparticules produites selon ledit procédé.
PCT/EP2022/080782 2021-11-10 2022-11-04 Procédé de synthèse de nanoparticules d'au moins un élément du groupe formé par le groupe des métaux non précieux et de l'antimoine, et nanoparticules WO2023083706A1 (fr)

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