CN104934631A - Metal nanoparticles synthesized by new reagents and application in electrochemical device - Google Patents

Metal nanoparticles synthesized by new reagents and application in electrochemical device Download PDF

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Publication number
CN104934631A
CN104934631A CN201510117757.3A CN201510117757A CN104934631A CN 104934631 A CN104934631 A CN 104934631A CN 201510117757 A CN201510117757 A CN 201510117757A CN 104934631 A CN104934631 A CN 104934631A
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zero
core
metal
reagent complex
electrode
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CN104934631B (en
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N·辛格
M·P·罗威
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Toyota Motor Corp
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Toyota Engineering and Manufacturing North America Inc
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/02—Layer formed of wires, e.g. mesh
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/387—Tin or alloys based on tin
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9041—Metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/023—Porous and characterised by the material
    • H01M8/0232—Metals or alloys
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention provides metal nanoparticles synthesized by new reagents and an application of the metal nanoparticles in electrochemical device, and particularly, provides a method of synthesizing metal nanoparticles and the nanoparticles prepared based on the method. The method includes the addition of a surfactant to a new reagent complex between zero-valent metal and a hydride. The nanoparticles produced by the method include oxide-free, zero-valent tin nanoparticles being useful preparing a battery electrode.

Description

Via the metal nanoparticle of novel agent synthesis and the application in electrochemical appliance
The cross reference of related application
The application is that the part of the application number 14/046,120 that on October 4th, 2013 submits to continues, and it is incorporated in full herein with it by reference.
Technical field
The present invention relates to the method for the nano particle of synthesis containing two or more zero-valent metals on the whole, and relates to the electrode comprising such nano particle and the electrochemical cell comprising such electrode on the whole.
Background technology
Metal nanoparticle, namely has the particle being in the elemental metals of pure or alloyed form being less than 100nm yardstick, has unique physics, chemistry, electricity, magnetic, optics and other character compared with the bulk metal corresponding with them.Therefore they are used and are developed in the field of e.g. particularly chemistry, medical science, energy and advanced electronics.
The synthetic method of metallic nanotubes particle is usually characterized by " top-down " or " bottom-up " and comprises various chemistry, physics even biological approach.Top-down technique relates to the particle that macro-scale or bulk metal physical decomposition are nanoscale by the various physical force of use.Bottom-up approach relates to by the atom be separated, molecule or bunch forms nano particle.
The physical force method of synthesizing for top-down metal nanoparticle comprises the spark erosion of the grinding of macro-scale metallic particles, the laser ablation of macro-scale metal and macro-scale metal.The chemistry route of bottom-up synthesis generally includes and metal salt back is become zero-valent metal, and combines and surround into the growth of core seed grain or spontaneous nucleation and grow into metal nanoparticle.
Although often kind of method in these methods can be effectively in some cases, often kind of method also has shortcoming or situation not applicable.Direct Ginding process can be limited to obtainable particle size (preparation is less than ~ particle of 20nm difficulty often) and can cause the forfeiture that the stoichiometric proportion of alloy controls.Other physical method can be expensive or is not revisable (unamenable) for commercial scale.
When the resistance to reduction of metal cation wherein, electronation technology may be invalid.Such as, well-known Mn (II) does not affect by electronation.Conventional means of chemical reaction also can be not suitable for for the preparation of to the nano particle being oxidized to extremely sensitive application.Such as, can be difficult to obtain by reduction approach the tin nanoparticles that is less than the size of 20nm and even when so obtaining, it tends to comprise the SnO of vast scale 2.
Tin is the promising material for battery terminal.Such as, as the anode in Li ion accumulator, tin can store about three times of the charge density of conventional graphite anode.Recently tin-based material is shown in the prospect being used as to have kept in the Mg ion insert type anode of high-energy-density Mg ion accumulator.Especially, the anode material made by ~ 100nm tin powder achieves high power capacity and be inserted into/extracts voltage.
When magnesium (it can occur at the duration of work of the Mg ion accumulator with bismuthino anode) of bismuth, think and define super-ionic electric conducting material Mg 3bi 2.By contrast, the tin of magnesium do not form super-ionic electric conducting material and as mention its for difference rate capability there is sensitiveness.As the active material of positive electrode of beneficial property including tin and bismuth in, such as Sn-Bi core-shell nanoparticles, can have and improve electrochemical cell on the whole and the ability of the particularly performance of Mg-ion electrochemical cell.
Summary of the invention
Provide the method via novel agent synthetic metals nano particle.Additionally provide the electrode of the core-shell structure copolymer metal nanoparticle comprised by the synthesis of disclosed method.Provide the electrochemical cell adopting such electrode in addition.
On the one hand, the method for synthetic metals nano particle is disclosed.The method comprises adds surfactant to prepare the step of core nano particle to core reagent complex, and this core reagent complex is described by formula I,
Wherein be zero-valent metal, wherein X is hydride molecule, and wherein y be greater than zero value.The method is also included in the step of adding surfactant under the existence of core nano particle to shell reagent complex, and this shell reagent complex is described by formula II,
Wherein that atomic number is different from zero-valent metal, wherein X ' is hydride molecule, and it can be identical or different with X, and wherein y be greater than zero value.
On the other hand, the electrode comprising core-shell structure copolymer metal nanoparticle is disclosed.Consist of the core-shell structure copolymer metal nanoparticle of this electrode a kind of method synthesis, the method comprises adds surfactant to prepare core nano particle to core reagent complex, and this core reagent complex is described by formula I,
Wherein be zero-valent metal, wherein X is hydride molecule, and wherein y be greater than zero value.The method is also included in the step of adding surfactant under the existence of nuclear particle nanometer to shell reagent complex, and this shell reagent complex is described by formula II,
Wherein that atomic number is different from zero-valent metal, wherein X ' is hydride molecule, and it can be identical or different with X, and wherein y be greater than zero value.
On the other hand, electrochemical cell is disclosed.This electrochemical cell has the electrode comprising core-shell structure copolymer metal nanoparticle.Consist of the core-shell structure copolymer metal nanoparticle of this electrode a kind of method synthesis, the method comprises adds surfactant to prepare core nano particle to core reagent complex, and this core reagent complex is described by formula I,
Wherein be zero-valent metal, wherein X is hydride molecule, and wherein y be greater than zero value.The method is also included in the step of adding surfactant under the existence of core nano particle to shell reagent complex, and this shell reagent complex is described by formula II,
Wherein that atomic number is different from zero-valent metal, wherein X ' is hydride molecule, and it can be identical or different with X, and wherein y be greater than zero value.
Accompanying drawing explanation
Describe various aspects of the present invention and advantage by following embodiment by reference to the accompanying drawings will become clear and be easier to understand, wherein:
Fig. 1 is the X-ray diffraction spectrum of the tin nanoparticles that the method by reporting herein is synthesized; With
Fig. 2 A is Sn 0the x-ray photoelectron power spectrum of powder;
Fig. 2 B is Sn (LiBH prepared by the method by reporting herein 4) 2the x-ray photoelectron power spectrum of complex compound; With
Fig. 2 C is the Sn of Fig. 2 A 0the X-ray energy spectrum of powder and the Sn (LiBH prepared by the method for Fig. 2 of Fig. 2 B 4) 2the x-ray photoelectron power spectrum of complex compound overlapping;
Fig. 3 is the first circulation magnesium curve of the Mg ion electrochemical cell of the anode of the Sn-Bi core-shell nanoparticles with the method synthesis comprised by reporting herein; With
Fig. 4 is the first circulation magnesium curve of the Mg ion electrochemical cell of the anode of the Bi-Sn core-shell nanoparticles with the method synthesis comprised by reporting herein.
Embodiment
Describe the method for synthetic metals nano particle, the nano particle synthesized like this and the electrochemical appliance comprising this nano particle.As explained in the following description, the method relates to surfactant and comprises the reaction between the novel agent complex compound of zero-valent metal and hydride." zero-valent metal " is alternatively described as elemental metals or is in the metal of zero oxidation state.Novel agent complex compound is alternatively described as complex compound.
As used herein, " metal " can mean alkaline-earth metal, alkali metal, transition metal or post transition metals.Phrase " transition metal " can mean any D district metal of the 3 to 12 race.Phrase " post transition metals " can mean any metal of the 13 to 16 race, comprises aluminium, gallium, indium, tin, thallium, lead or bismuth.In some variants, metal will be transition metal or post transition metals.In some instances, metal will be tin.
As used herein, " hydride " can be solid metal hydride (such as NaH or MgH 2), metalloid hydride (such as BH 3), composite metal hydride (such as LiAlH 4), or be also called metalloid hydride salt (the such as LiBH of hydride salt 4).Term " metalloid " can mean any metalloid in boron, silicon, germanium, arsenic, antimony, tellurium or polonium.In some instances, hydride will be LiBH 4.Any member in the group be made up of composite metal hydride and metalloid hydride salt can be described as " complex hydride ".Be to be understood that term hydride as used in this article also can comprise corresponding deuteride or tritide.
The method of synthetic metals nano particle comprises adds surfactant to prepare the step of core nano particle to core reagent complex, and this core reagent complex is described by formula I:
Wherein be zero-valent metal, wherein X is hydride molecule, and wherein y be greater than zero integer value or fractional value.In some cases, y is by the integer value for being equal to or less than four or fractional value.
The method of synthetic metals nano particle is included in another step of adding surfactant under the existence of core nano particle to shell reagent complex, and this shell reagent complex is described by formula II,
Wherein that atomic number is different from zero-valent metal, wherein X ' is hydride molecule, and it can be identical or different with X, and wherein y be greater than zero value.In many cases, y can be greater than zero and be less than or equal to four value.The value represented by y can be integer value or fractional value, and such as 2.5.The surfactant used in above-mentioned two steps can be identical or different.
In some variants of the method, with tin (ten) and bismuth will be selected from.In the variant that some are such, will for tin and it will be bismuth.In the variant that other is such, will for bismuth and to be tin.
Be not bound to any particular theory, think that the metal nanoparticle prepared by the method comprising two steps is above core-shell structure copolymer metal nanoparticle.As used in this article, phrase " core-shell structure copolymer " means a kind of character, wherein nano particle center of mass enrichment with relevant zero-valent metal, and surface enrichment with relevant zero-valent metal.In some cases, phrase " core-shell structure copolymer " can mean a kind of structure, Qi Zhongyu the discontinuous kernel of relevant zero-valent metal partially or completely surface-coated have with the discontinuity layer of relevant zero-valent metal.Therefore, sometimes will be called " core-shell structure copolymer metal nanoparticle " in this article by the metal nanoparticle of disclosed method synthesis.
Optionally, above-mentioned second step can be repeated so that synthesis has the nano particle of multiple shell.When adopting the order of shell reagent complex and surfactant to apply wherein, it is different in front applying immediately that applying subsequently should utilize from shell reagent complex shell reagent complex.
As used in this article, term " reagent complex " can mean core reagent complex, shell reagent complex or both.This reagent complex can be the complex compound of individual molecule entity, such as, with the single metal atom being in zero oxidation state of one or more hydride molecule complexing.Or this reagent complex can exist as molecular cluster, such as, be scattered with the metal atomic cluster being in zero oxidation state of hydride molecule, or be in the metal atomic cluster of zero oxidation state, this bunch of surface-coated has hydride molecule or hydride salt to intersperse among in whole bunch.
The method of synthetic metals nano particle some in, this reagent complex can be suspended with solvent or dicyandiamide solution and contact.In some variants, the suspended substance comprising wherein this reagent complex is continued stable those of being spaced apart of at least one day by suitable solvent or dicyandiamide solution in inert environments.In some variants, the suspended substance comprising wherein this reagent complex is continued stable those of being spaced apart of at least one hour by suitable solvent or dicyandiamide solution in inert environments.In some variants, the suspended substance comprising wherein this reagent complex is continued stable those of being spaced apart of at least five minutes by suitable solvent or dicyandiamide solution in inert environments.
Phrase as used herein " inert environments " can comprise for anhydrous atmospheric environment.Phrase as used herein " inert environments " can comprise oxygen-free atmospheric environment.Phrase as used herein " inert environments " can comprise not only anhydrous but also oxygen-free atmospheric environment.Phrase as used herein " inert environments " can comprise the obturator (enclosure) be in the ambiance comprising inert gas such as argon, or is in the obturator in space under vacuo.
Term " stable " as used in phrase " wherein this reagent complex continue be spaced apart stable " may imply that significantly dissociation or experience covalency change this reagent complex.
It is non-reacted material that the solvent adopted in some different aspect disclosed herein or dicyandiamide solution can be the hydride included in this reagent complex.As what use in phrase " be non-reacted material to hydride " above, term " non-reacted " may imply that this material and solvent or dicyandiamide solution are not participated in directly or cause the covalent reaction of the hydrogen compound of this reagent complex to the significant degree of thermodynamics.According to such standard, suitable solvent or dicyandiamide solution can be depending on used hydride and change.In some variants, this can comprise for non-proton, non-oxidizable or both solvent or dicyandiamide solution.
The limiting examples of suitable solvent or dicyandiamide solution component can comprise acetone, acetonitrile, benzene, n-butyl alcohol, 2-butanols, 2-butanone, the tert-butyl alcohol, carbon tetrachloride, chlorobenzene, chloroform, cyclohexane, 1,2-dichloroethanes, diethyl ether, diethylene glycol (DEG), diethylene glycol dimethyl ether (diethylene glycol (DEG), dimethyl ether), 1,2-dimethoxy-ethane (glyme, DME), dimethyl ether, dimethyl formamide (DMF), dimethyl sulfoxide (DMSO) (DMSO), diox, ethanol, ethyl acetate, ethylene glycol, glycerol, heptane, hexamethyl phosphoramide (HMPA), hexamethylphosphorictriamide (Hexamethylphosphorous triamide) (HMPT), hexane, methyl alcohol, methyl tertiary butyl ether (MTBE), carrene, METHYLPYRROLIDONE (pyrrol idinone) (NMP), nitromethane, pentane, benzinum (ligroin), 1-propyl alcohol, 2-propyl alcohol, pyridine, oxolane (THF), toluene, triethylamine, ortho-xylene, meta-xylene or paraxylene.
As limiting examples, the alkyl solvents of halo can be acceptable in some cases, and alkyl sulfoxide can be acceptable in some cases, can be acceptable in other cases containing ether solvents.In some variants, THF can be suitable solvent or solvent system component.
The method of synthetic metals nano particle some in, can by this surfactant suspend or be dissolved in solvent or dicyandiamide solution.Wherein this reagent complex and solvent or dicyandiamide solution are suspended and contact and this surfactant suspended or is dissolved in the different variants in solvent or dicyandiamide solution, can by this reagent complex with have and wherein to dissolve or the solvent of this surfactant that suspends or the solvent of the identical or different composition of dicyandiamide solution or dicyandiamide solution suspend and contact.
The method of synthetic metals nano particle some in, can in the absence of solvent this reagent complex and surfactant be merged.In some such situations, solvent or dicyandiamide solution can be added after such merging.In other side, can add to solvent or the dicyandiamide solution reagent complex contacted that suspends the surfactant not suspending or be dissolved in solvent or dicyandiamide solution.In yet another aspect, can add to the reagent complex contacted that do not suspend with solvent or dicyandiamide solution the surfactant suspending or be dissolved in solvent or dicyandiamide solution.
As used in this article, phrase " surfactant " can mean the surfactant for using in one or two step disclosed in the method for synthesis core-shell nanoparticles.Surfactant can be any surfactant known in the art.Available surfactant can comprise nonionic, cationic, anionic, both sexes, amphoteric ion type and polymeric surfactant and combination thereof.Such surfactant has lipophilic portion usually, this lipophilic portion be based on hydrocarbon, based on organosilan or based on fluorocarbon.Do not mean restriction, the example that can be suitable surfactant types comprises alkyl sulfate/ester and sulfonate/ester, oil and lignosulfonates/ester, phosphate, sulfosuccinate, carboxylate/ester, alcohol, the alcohol of ethoxylation and alkyl phenol, fatty acid ester, the acid of ethoxylation, alkanolamide, the amine of ethoxylation, amine oxide, alkylamine, nitrile, quaternary ammonium salt, carboxybetaine, sulfobetaines or polymeric surfactant.
In some cases, the surfactant adopted in the method for synthetic metals nano particle by for being oxidized, protonated or with the surfactant of the covalent modified hydride included in this reagent complex of other method.In some variants, surfactant can be carboxylate/ester, nitrile or amine.Surfactant can be octylame in some instances.
The method of synthetic metals nano particle or can be carried out under water-less environment, under oxygen-free environment under anhydrous and oxygen-free environment in some variants.Such as, the method for synthetic metals nano particle can under argon gas or be carried out under vacuo.Although zero-valent metal M 0can comprise some impurity such as metal oxide, but the method for synthetic metals nano particle can prepare the simple metal nano particle of oxide-free material in some cases.Such a situation is presented in Fig. 1 (the X-ray diffraction spectrum of the zeroth order tin nanoparticles prepared by the method).It should be noted that the difraction spectrum of Fig. 1 is pointed out the pure zeroth order tin of oxide-free and records the average largest particle yardstick of 11nm.
Reagent complex is prepared by any suitable method.The limiting examples preparing the appropriate method of reagent complex comprises the step with the preparation ball milling hydride be made up of zero-valent metal.In this article the method adopting this step for the preparation of reagent complex is called " illustrative methods ".In many cases, the preparation be made up of zero-valent metal adopted in this illustrative methods will have high surface area and the ratio of quality.In some cases, the preparation be made up of zero-valent metal will be metal dust.Be contemplated that the preparation be made up of zero-valent metal can be highly porous metal, have the metal of honeycomb or some other there is the preparation of the ratio of high surface area and quality.
In some cases, the preparation containing zero-valent metal can comprise Zero-valence transition metal.Suitable transition metal includes but not limited to cadmium, cobalt, copper, chromium, iron, manganese, gold, silver, platinum, titanium, nickel, niobium, molybdenum, rhodium, palladium, scandium, vanadium and zinc.In some cases, the preparation containing zero-valent metal can comprise metal after zero valent transition.Suitable post transition metals comprises aluminium, gallium, indium, tin, thallium, lead or bismuth.
The zero-valent metal that should be understood to transition metal, post transition metals, alkali metal or alkaline-earth metal will be in zero oxidation state.As used in this article, mean that this material can show obviously but need not zero oxidation state completely by " zeroth order " and " zero oxidation state ".Such as, the preparation containing zero-valent metal can comprise some surface impurities such as oxide.
Be contemplated that phrase " high surface area and the ratio of quality " surface area of wide region and the ratio of quality can be comprised and usual the adopted surface area of the preparation be made up of zero-valent metal and the ratio of quality by for required for the time restriction of this illustrative methods.In many cases, the preparation be made up of zero-valent metal of higher surface area and the ratio of quality will cause this illustrative methods to complete faster.Such as, when the preparation be made up of zero-valent metal is wherein metal dust, the metal dust of smaller particle size can tend to cause this illustrative methods and the preparation of reagent complex thus to complete faster.
The limiting examples being applicable to the hydride of this illustrative methods comprises sodium borohydride, lithium aluminium hydride reduction, diisobutylaluminium hydride (DIBAL), SuperHydride (super hydride), sodium hydride and hydrofining, calcium hydride, lithium hydride or borine.
In some variants of this illustrative methods, hydride can be mixed with the preparation be made up of zero-valent metal with the stoichiometric proportion of metallic atom 1:1 with hydride molecule.In other variant, this stoichiometric proportion can be 2:1,3:1,4:1 or higher.In some variants, hydride molecule with also can comprise mark quantity by the stoichiometric proportion of the metallic atom in the preparation that zero-valent metal is formed, such as 2.5:1.Should be appreciated that when utilizing this illustrative methods to prepare reagent complex wherein, the stoichiometry of the mixture in this illustrative methods will be tended to control the stoichiometry of complex compound pointed by y value according to formula I.
Be contemplated that the ball mill used in this illustrative methods can be any type.Such as adopted ball mill can be tub ball mill, aeropulverizer, sand mill, horizontally rotates ball mill, vibrator or planetary ball mill.In some instances, the ball mill adopted in this illustrative methods will be planetary ball mill.
Be contemplated that the ball-milling medium used in this illustrative methods can be any composition.Such as, the ball-milling medium adopted can be made up of metal such as stainless steel, brass or antimonial lead (hardened lead), or they can be made up of pottery such as aluminium oxide or silica.In some variants, the ball-milling medium in this illustrative methods will be stainless steel.Be to be understood that ball-milling medium can be various shape, such as they can be column or spherical.In some variants, ball-milling medium will for spherical.
Optionally, various analytical technology can be adopted to monitor this illustrative methods and to determine that it successfully completes.Discuss the technology that some are so below, such as x-ray photoelectron power spectrum (XPS) and X-ray diffraction (XRD), but can optionally adopt known in the art is useful any analysis means.
Respectively illustrate in Figures 2 A and 2 B for simple substance tin powder with for reagent complex Sn (LiBH 4) 2tin region in XPS scanning.In Figures 2 A and 2 B, heavy line shows original XPS data, and fine line display is through the data of adjustment.The peak of the single deconvolution (deconvoluted) of dotted line and/or chain-dotted line display spectrum.The central point of the electron-volt number of the peak maximum of deconvolution is pointed out by arrow.
Fig. 2 C shows from the spectrum (chain-dotted line) of tin through adjustment of the non-complexing of Fig. 2 A and the Sn (LiBH from Fig. 2 B 4) 2complex compound is through spectrum (solid line) overlapping of adjustment.As appreciable from Fig. 2 C, the complexing between zeroth order tin and lithium borohydride forms the lower electron energy overall offset causing new peak occurs and spectrum is observed towards zero-valent metal electronics.Prepared the certain situation of reagent complex wherein by this illustrative methods under, compared with the spectrum of the zero-valent metal of non-complexing, the x-ray photoelectron power spectrum including the zero-valent metal in this reagent complex in by entirety to more low-yield skew.In some cases, wherein M is identified by center in the existence at the x-ray photoelectron power spectrum peak at about 484eV place 0for tin and X is the reagent complex of lithium borohydride.
In some variants, this illustrative methods can be carried out under water-less environment, oxygen-free environment or anhydrous and oxygen-free environment.Such as, this illustrative methods can be carried out under argon gas or under vacuo.Such as when the hydride used in this illustrative methods is the hydride for molecular oxygen, water or both sensitivities, the feature that this is optional can be comprised.
Disclose the battery terminal comprising the core-shell structure copolymer metal nanoparticle synthesized by said method.As mentioned, the Mg ion accumulator of tinbase anode is adopted to show hope (people such as N.Singh, Chem.Commun., 2013,49,149-151 of the high-energy-density substitute as conventional Li ion accumulator; Include in full herein with it by reference).Especially, based on ~ 100nm Sn 0the tin anode of powder shows impressive capacity and insertion/extraction voltage in such system.Sharply the reducing of tin nanostructure of such anode can improve the rate capability of such system and ability capable of circulation, but needs the tin nanoparticles of oxide-free.Tin nanoparticles is such as open herein and the tin nanoparticles of the 11nm oxide-free represented in FIG can be the useful anode material in such storage battery system.In addition, by forming the bismuth shell around tin core, can by utilizing the superconducting property of the bismuth of magnesium to reduce the defect caused by the ion diffusion rates of difference in tin.
Electrode can comprise active material, and this active material comprises the core-shell nanoparticles by the method synthesis of disclosed synthesis core-shell nanoparticles above.The method comprises the step to adding surfactant according to the reagent complex of formula I:
Wherein be zero-valent metal, wherein X is hydride molecule, and wherein y be greater than zero value.In some cases, y can be greater than zero and be less than or equal to four value.This value represented by y can be integer value or fractional value, and such as 2.5.The product of this step can be called " core nano particle ".
The synthesis forming the core-shell structure copolymer metal nanoparticle of this electrode can be included in the additional step adding surfactant under the existence of core nano particle to shell reagent complex, and this shell reagent complex is described by formula II,
Wherein that atomic number is different from zero-valent metal, wherein X ' is hydride molecule, and it can be identical or different with X, and wherein y be greater than zero value.In many cases, y can be greater than zero and be less than or equal to four value.The value represented by y can be integer value or fractional value, and such as 2.5.The surfactant used in above-mentioned two steps can be identical or different.In some cases, with sn and Bi can be respectively.In other cases, with bi and Sn can be respectively.
By any this electrode of suitable fabrication techniques, such as pressed powder embrane method, and this electrode can comprise non-active material (such as carbon black) and adhesive.In some cases, this electrode can comprise the metal nanoparticle with the average out to out being less than 50nm.In some cases, this electrode can comprise the metal nanoparticle with the average out to out being less than 20nm.In some cases, this electrode can comprise the metal nanoparticle of the average out to out with about 10nm.In some cases, this electrode can comprise the metal nanoparticle with the average out to out being less than 10nm.
This electrode can comprise the nano particle of transition metal or post transition metals.In some variants, this electrode can comprise tin nanoparticles.In some special variants, this electrode can comprise the tin nanoparticles of the average out to out with about 10nm.
In addition, also disclose have above the electrochemical cell of electrode of disclosed type.As mentioned, synthesized by a kind of method the core-shell nanoparticles forming this electrode, the method comprises the step to adding surfactant according to the reagent complex of formula I:
Wherein be zero-valent metal, wherein X is hydride molecule, and wherein y be greater than zero value.In many cases, y can be greater than zero and be less than or equal to four value.This value represented by y can be integer value or fractional value, and such as 2.5.The product of this step can be called " core nano particle ".
The synthesis forming the core-shell structure copolymer metal nanoparticle of electrode included in this electrochemical cell can be included in the additional step adding surfactant under the existence of core nano particle to shell reagent complex, and this shell reagent complex is described by formula II,
Wherein that atomic number is different from zero-valent metal, wherein X ' is hydride molecule, and it can be identical or different with X, and wherein y be greater than zero value.In many cases, y can be greater than zero and be less than or equal to four value.The value represented by y can be integer value or fractional value, and such as 2.5.The surfactant used in above-mentioned two steps can be identical or different.In some cases, with sn and Bi can be respectively.In other cases, with bi and Sn can be respectively.
The electrode of electrochemical cell above-mentioned can be male or female, but can be anode in some special situations.Under the particular case that some are such, this electrode can be insert type anode.This electrochemical cell can adopt any electrochemical reaction and can be the type being applicable to storage battery, such as available in lithium-ions battery lithium battery, or can be the type being applicable to fuel cell, such as hydrogen fuel cell.
In some cases, this electrochemical cell can be magnesium electrochemical cell or the Mg ion electrochemical cell of the general half-cell reaction with the type described by reaction I part:
In some special situations, this electrochemical cell can be the insert type anode and the Mg ion electrochemical cell comprised according to the work half-cell reaction of reacting II that have and comprise according to the nano particle of present disclosure synthesis:
Wherein M 0represent and include according to the zero-valent metal in the shell of the core-shell structure copolymer metal nanoparticle of present disclosure, wherein χ is stoichiometry, and it can be the integer value being greater than zero, and wherein ω is stoichiometry, and it can be the integer value being greater than zero.Under the particular case that some are such, χ can be any one in, two and three, and ω can be any one in, two and three.
In other more particularly situation; this electrochemical cell can be Mg ion electrochemical cell; it has the insert type anode of Sn-Bi core-shell nanoparticles or the bismuth-Xi core-shell nanoparticles comprised according to present disclosure synthesis, and comprises according to the work half-cell reaction of at least one in reaction III and reaction IV:
With regard to following examples, further illustrate the various aspects of present disclosure.Should be understood that the particular providing these embodiments to carry out present disclosure, and these embodiments should not be regarded as any special in limit the scope of the disclosure or the scope of present disclosure be limited to any special in.
The synthesis of embodiment 1. tin core nano particle
0.503g tin metal powder and 0.187g lithium borohydride are merged in planetary ball mill.By consolidated material in planetary ball mill (use Fritsch pulervisette 7 planetary ball mill) with 400rpm in the airtight ball grinder of 250mL stainless steel ball milling 4 hours to prepare Sn (LiBH 4) 2reagent complex, this ball grinder has 1 3/ 4inch, 3 1/ 2inch and 5 1/ 4inch 316 stainless steel ball bearings.The ball milling complex compound of gained is suspended in THF.With 0.443g octylame this suspended substance of solution titration in 10mL THF.Consequential reaction proceeded at internal environment temperature at about 3 hours, caused having the zeroth order tin nanoparticles of the average grain size of about 11nm, as shown in the X-ray diffraction spectrum of Fig. 1.The spectrum of Fig. 1 points out the pure tin metal of oxide-free material.Whole synthesis procedure is carried out under inert conditions to avoid oxidation in glove box.
The synthesis of embodiment 2.Sn-Bi core-shell nanoparticles
By bismuth meal end and lithium borohydride merging and with 400rpm ball milling 4 hours to prepare Bi (LiBH in planetary ball mill 4) 2reagent complex.By Bi (LiBH 4) 2the tin nanoparticles of reagent complex and embodiment 1 suspends altogether and with the octylame of 2:1 molar excess in THF: Bi (LiBH 4) 2reagent complex titration is to prepare Sn-Bi core shell nanoparticles.Whole synthesis procedure is carried out under inert conditions to avoid oxidation in glove box.
The synthesis of embodiment 3.Bi-Sn core-shell nanoparticles
By the Bi (LiBH of embodiment 2 4) 2reagent complex to be suspended in THF and with the octylame of 2:1 molar excess: Bi (LiBH 4) 2reagent complex titration is to prepare Bi core nano particle.By the Sn (LiBH of embodiment 1 4) 2reagent complex and Bi core nano particle suspend altogether and with the octylame of 2:1 molar excess in THF: Sn (LiBH 4) 2reagent complex titration is to prepare Bi-Sn core-shell nanoparticles.Whole synthesis procedure is carried out under inert conditions to avoid oxidation in glove box.
Embodiment 4. electrode fabrication
Electrode is formed by the Sn-Bi nano particle of the type of synthesis in embodiment 2 by pressed powder embrane method.In brief, by compressed together with 70% active material, 20% carbon black and 10% adhesive (all percentage (w/w)) to the Sn-Bi nano particle (herein also referred to as " active material ") according to embodiment 2, carbon black and Kynoar (herein also referred to as " adhesive ").The method has prepared Sn-Bi electrode.
Similarly, electrode is formed by pressed powder embrane method by the Bi-Sn nano particle of the type of synthesis in embodiment 3.In brief, by compressed together with 70% active material, 20% carbon black and 10% adhesive (all percentage (w/w)) to the Bi-Sn nano particle (herein also referred to as " active material ") according to embodiment 3, carbon black and Kynoar (herein also referred to as " adhesive ").The method has prepared Bi-Sn electrode.All electrode fabrication operations are carried out under inert conditions to avoid material oxidation in glove box.
Embodiment 5. electrochemical cell structure and test
Construct two electrochemical cells, the Sn-Bi electrode of an employing embodiment 4, another adopts the Bi-Sn electrode of embodiment 4 as its electrode.Each electrochemical cell uses Tomcell structure.In brief, the electrode (Sn-Bi or Bi-Sn) of embodiment 4 is relative with the Mg foil electrode with glass fibre spacer body.Electrolyte solution is the LiBH of the 3:1 in 1,2-dimethoxy-ethane 4: Mg (BH 4) 2.
The anode magnesium circulated is tested at 50 DEG C and with the C multiplying power of C/200.Show the first circulation magnesium curve of Sn-Bi electrode in figure 3, and show the first circulation magnesium curve of Bi-Sn electrode in the diagram.It should be noted that for bismuth or tin anode active material, voltage does not obviously reach stable at the theoretical voltage place of battery, and for often kind of two kinds of anode type, in nucleocapsid interface, alloy is to a certain degree formed this hint.
Aforementioned description relates to and is considered to most realistic embodiment at present.But be to be understood that, present disclosure is not limited to these embodiments, and on the contrary, it is intended to be encompassed in the interior included various change of spirit and scope and the equivalent arrangements of claims, should give this scope the most wide in range explanation, thus all such changes comprising that law allows and equivalent construction.

Claims (17)

1. the method for synthetic metals nano particle, the method comprises:
Add surfactant to prepare core nano particle to core reagent complex, this core reagent complex is described by formula I,
Wherein be zero-valent metal, wherein X is hydride molecule, and wherein y be greater than zero value; With
Under the existence of core nano particle, add surfactant to shell reagent complex, this shell reagent complex is described by formula I I:
Wherein that atomic number is different from zero-valent metal, wherein X ' is hydride molecule, and it can be identical or different with X, and wherein y be greater than zero value.
2. the process of claim 1 wherein with eachly be selected from the group comprising metal after Zero-valence transition metal and zero valent transition.
3. the method for claim 2, wherein with eachly be selected from the group comprising tin and bismuth.
4. the method for claim 3, wherein for tin and for bismuth.
5. comprise the electrode of core-shell nanoparticles, synthesize this core-shell nanoparticles by following method, the method comprises:
Add surfactant to prepare core nano particle to core reagent complex, this core reagent complex is described by formula I,
Wherein be zero-valent metal, wherein X is hydride molecule, and wherein y be greater than zero value; With
Under the existence of core nano particle, add surfactant to shell reagent complex, this shell reagent complex is described by formula II:
Wherein that atomic number is different from zero-valent metal, wherein X ' is hydride molecule, and it can be identical or different with X, and wherein y be greater than zero value.
6. the electrode of claim 5, wherein with eachly be selected from the group comprising metal after Zero-valence transition metal and zero valent transition.
7. the electrode of claim 6, wherein with eachly be selected from the group comprising tin and bismuth.
8. the method for claim 7, wherein for tin and for bismuth.
9. have the electrochemical cell of electrode, this electrode comprises core-shell nanoparticles, and synthesize this core-shell nanoparticles by following method, the method comprises:
Add surfactant to prepare core nano particle to core reagent complex, this core reagent complex is described by formula I,
Wherein be zero-valent metal, wherein X is hydride molecule, and wherein y be greater than zero value; With
Under the existence of core nano particle, add surfactant to shell reagent complex, this shell reagent complex is described by formula II:
Wherein that atomic number is different from zero-valent metal, wherein X ' is hydride molecule, and it can be identical or different with X, and wherein y be greater than zero value.
10. the electrochemical cell of claim 9, wherein this electrode is anode.
The electrochemical cell of 11. claims 9, wherein this electrode is insert type anode.
The electrochemical cell of 12. claims 9, it is Mg ion electrochemical cell.
The electrochemical cell of 13. claims 9, it is Mg ion electrochemical cell, and wherein this electrode is insert type anode, and wherein with eachly be selected from the group comprising metal after Zero-valence transition metal and zero valent transition.
The electrochemical cell of 14. claims 13, wherein with eachly be selected from the group comprising tin and bismuth.
The electrochemical cell of 15. claims 14, wherein for tin and for bismuth.
The electrochemical cell of 16. claims 14, wherein for bismuth and for tin.
The electrochemical cell of 17. claims 14, it comprises the work electrochemical reaction according at least one in reaction III and reaction IV:
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