CN108172774A - A kind of metastable state kamash alloy material and preparation method thereof - Google Patents

A kind of metastable state kamash alloy material and preparation method thereof Download PDF

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CN108172774A
CN108172774A CN201711182349.1A CN201711182349A CN108172774A CN 108172774 A CN108172774 A CN 108172774A CN 201711182349 A CN201711182349 A CN 201711182349A CN 108172774 A CN108172774 A CN 108172774A
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alloy
preparation
alloy material
tin
sources
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CN108172774B (en
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韩伟强
应杭君
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Zhejiang University ZJU
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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
    • 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
    • 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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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

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Abstract

The invention discloses a kind of metastable state kamash alloy materials and preparation method thereof.The material is mainly made of two kinds of metallic elements of Sn, Ni, it is also possible to containing elements such as Fe, Co, form metastable main phase as MSn5(M=Ni, Fe0.5Ni0.5, Co0.5Ni0.5) kamash alloy material, the present invention by introducing crystal seed in the synthesis process, the kamash alloy cenotype based on tin, nickel that induced synthesis is difficult to synthesize in conventional method, this method provide a kind of new method and thinking for the synthesis of other metastable materials especially metastable state kamash alloy material.The MSn5Alloy material can be used as lithium/sodium-ion battery active cathode material, wherein the presence of inactive M metals can inhibit the reunion of Sn, improve the cyclical stability of material.

Description

A kind of metastable state kamash alloy material and preparation method thereof
Technical field
The present invention relates to the preparation fields of alloy material, and in particular to a kind of novel metastable state kamash alloy material M-Sn The research of preparation and the application of (M=Ni, FeNi or CoNi etc.).
Background technology
Alloy material in industrial production and daily life in have very extensive application.Study alloy phase diagram, pairing The preparation condition of golden material, the understanding of physicochemical property all have very positive meaning, and then the application of alloy material are pushed to open Hair.However, some metastable alloys are mutually not present in traditional alloy phase diagram, supplement is closed in the exploitation of these alloy phases It is significant to improve alloy theory for metallograph.The formation condition of metastable state alloy phase is more harsh, therefore develops metastable phase alloy It needs to select or develops suitable preparation method, and strictly control the conditions such as raw material type, material rate, reaction temperature.
Kamash alloy material has had very extensive application in industrial circle, due to its excellent chemical property, Also become the focus of research in fields such as catalysis, energy storage in recent years.The preparation method of traditional kamash alloy is mainly high temperature melting Refining method, although this method can prepare kamash alloy on a large scale, the control of its pattern to material, size and phase constituent Ability is very limited, it is difficult to applied to fields such as catalysis and energy storage.And the alloy material that traditional high melt method is prepared Material is all steady phase material, is not used to prepare and develops novel metastable phase alloy material.Therefore exploitation one kind can be controlled effectively Pattern, size and the preparation method of phase composition of kamash alloy processed, have the exploitation of research and the application of kamash alloy material Very great meaning.
Since second industrial revolution, energy crisis and environmental pollution become the two big world sex chromosome mosaicisms to become increasingly conspicuous, promote Make energetically exploration of the people to the sustainable novel energy of green.Lithium ion and sodium-ion battery as efficient energy storage device, Compared to conventional batteries, have many advantages, such as that specific capacity is high, monomer voltage is high, self discharge is small, service life is long, it is environmentally protective, The whole world has started research boom.Since tin-based material all has higher theoretical ratio in lithium ion battery and sodium-ion battery Capacity, it is considered to be the contenders of conventional graphite cathode substitute.Alloying is the common modification side of tin base cathode material Method, 2005, Sony was commercialized amorphous Sn-Co-C cathode, has caused researcher and tin base cathode is researched and developed Huge enthusiasm.Novel kamash alloy method is developed, prepares the emphasis that high-performance tin-based material is research.
Invention content
The characteristics of the purpose of the present invention is being directed to metastable phase kamash alloy, provides a kind of kamash alloy material and its preparation side Method, the alloy material are mainly made of Sn, Ni, while also there are the metallic elements such as Fe, Co, Cu.
Its main phase of the kamash alloy material of the present invention is MSn5Alloy, wherein M are Ni, Fe0.5Ni0.5、Co0.5Ni0.5In One kind, material surface have one layer of amorphous metal oxide skin(coating).
One or more in the oxide of metal oxide layer, that is, above-mentioned metal, thickness is often 3-5nm.The tinbase Intermediate alloy MSn5With tetragonal phase, belong to P4/mcc space groups, the pattern of the alloy material is generally spherical or is similar to ball Shape, alloy grain size size range are 10-100nm, preferably 20-70nm, are more preferably 30-50nm.
In above-mentioned technical proposal, further, the MSn5Often there are the M atoms of stoichiometric ratio skies in alloy Position, i.e.,：MaSn5, the ranging from 0 ＜ a ＜ 1 of wherein a.
The MSn5Alloy is NiaSn5Or FebNicSn5Or CodNieSn5, wherein 0.4 ＜ a ＜, 0.8,0 ＜ b, c ＜ 0.5,0 ＜ d, e ＜ 0.5.
Above-mentioned kamash alloy material is prepared, following method can be used：High temperature reduction method, hydrothermal synthesis method, wet chemistry method, High melt method, mechanico-chemical reaction method (such as mechanical attrition method, mechanical alloying method etc.), sol-gal process, magnetron sputtering Method etc., the present invention are included the following steps using wet chemical method：
1) under inert atmosphere conditions, pink salt is added in the organic solvent containing surface stabilizer in 130-170 DEG C Stirring and dissolving is obtained containing solution of tin；
2) reducing agent under inert atmosphere conditions, is added in containing solution of tin, tin ion is reduced to simple substance tin, is obtained single The dispersion liquid of matter tin parent phase；
3) 205 DEG C under inert atmosphere conditions, are warming up to, Fe sources, Co sources, Cu sources are introduced in simple substance tin parent phase dispersion liquid In one kind, be stirred to react to form NSn5Crystal seed, wherein N are Fe, Co or Cu；In order to obtain MSn5Alloy (wherein M for Ni, Fe0.5Ni0.5、Co0.5Ni0.5), the introducing of crystal seed is necessary；
4) after crystal seed is formed, 170 DEG C are cooled to, Ni sources is added in, after being stirred to react, is cooled to room temperature；Centrifugation, washing, It is dry, obtain kamash alloy material.
In above-mentioned technical proposal, further, the pink salt uses tin salt, is selected from：Stannous sulfate, stannous chloride, It is one or more in nitric acid stannous, stannous oxalate；
Further, the organic solvent is ethylene glycol, isopropanol, glycerine, tetraethylene glycol, diethanol amine, oleyl amine, tetrahydrochysene One or more mixing in furans；
Further, the surface stabilizer is polyvinylpyrrolidone (PVP), poly- (- 2 oxazoline of 2- ethyls) (PEtOx), one or more mixing in cetyl trimethylammonium bromide (CTAB), oleyl amine.
Further, the reducing agent is sodium borohydride, sodium hypophosphite, ammonium borohydride, tetrabutyl ammonium borohydride, water Close one or more combinations in hydrazine, active metal.The mode that reducing agent adds in is adds in or divides reducing agent in powder form It dissipates and is added dropwise in a solvent, it is preferable that added in a manner that reducing agent dispersion is added dropwise in a solvent, to control reaction rate.
Further, the Fe sources, Co sources, Cu sources, Ni sources refer respectively to respective metal salt and are scattered in organic solvent The solution formed.Also respective metal simple substance or metal salt can directly be used；Fe salt is preferably Fe2(SO4)3、Fe(NO3)3、 FeCl3Or combination, Co salt are preferably CoBr2、CoCl2、CoSO4、Co(NO3)2Or combination, Cu salt are preferably CuSO4、 CuCl2、Cu(NO3)2Or combination, Ni salt are preferably NiSO4、NiCl2、NiF2、NiBr2Or combination, the organic solvent Corresponding organic solvent i.e. in step 1).
Further, the Fe sources, Co sources, the additive amount in Cu sources are as follows：When the alloy of preparation is NiSn5When, addition Afterwards so that tin and the molar ratio for adding metal are Sn in solution:M ＞ 200, wherein M=Fe/Co/Cu；When the alloy of preparation is Fe0.5Ni0.5Sn5Or Co0.5Ni0.5Sn5When, so that tin and the molar ratio for adding metal are 8 ＜ Sn in solution after addition:M ＜ 20, wherein M=Fe/Co/Cu.
Further, the additive amount in the Ni sources is as follows：When the alloy of preparation is NiSn5When, so that solution after addition The molar ratio of middle tin and Ni are 3 ＜ Sn:Ni ＜ 6；When the alloy of preparation is Fe0.5Ni0.5Sn5And Co0.5Ni0.5Sn5When, after addition So that the molar ratio of tin and Ni are 6 ＜ Sn in solution:Ni ＜ 12.
Kamash alloy material produced by the present invention can be used as lithium ion battery negative material.
Kamash alloy material (Sn simple substance is as a comparison), conductive agent and binding agent are made into negative material, wherein MSn5It closes Golden cenotype or the content of Sn simple substance negative electrode active materials are 40-90wt%, and the content of conductive additive is 5-30wt%, binding agent Content be 5-30wt%.Preferably, MSn5Alloy cenotype or Sn simple substance negative electrode active materials, conductive additive, binding agent Mass ratio is 8:1:1.Preferably, conductive additive is carbon black, and binding agent is the high molecular material containing carboxyl, such as carboxylic first Base sodium cellulosate.
Used diaphragm is arbitrarily common diaphragm material, such as polytetrafluoroethylene film, glass fibre, porous ceramics Deng.
Used electrolyte dissolves the solution obtained in organic solvent for certain density lithium salts or sodium salt.It is selected Lithium salts includes but not limited to following combine：LiPF6、LiClO4, LiCl, LiBr or combination.Selected electrolyte solvent It is including but not limited to following to combine：Dimethyl carbonate, methyl ethyl carbonate, ethylene carbonate, 1,2- dimethoxy-ethanes, carbonic acid two Ethyl ester, propene carbonate, 1,3 dioxolanes, butyrate, acetic acid esters, propionic ester, methyl phenyl ethers anisole, acetonitrile, diethyl ether, propionitrile etc. or A combination thereof.
Used positive electrode is arbitrary common anode material for lithium-ion batteries.It is including but not limited to following to combine： LiCoO2、LiMnO2、LiMn2O4、LiFePO4、LiMn0.33Co0.33Ni0.33O2Deng.
Beneficial effects of the present invention are：
1. MSn has been prepared in the present invention for the first time5(for M based on Ni, especially M is Ni, Fe0.5Ni0.5、Co0.5Ni0.5) tin Alloy cenotype, and structure elucidation has been carried out to it, expand M-Sn alloy phase diagrams.
2. the present invention dexterously introduces crystal seed and (introduces the atoms such as Fe, Co, Cu, form corresponding NSn5Crystal seed), induction is closed The metastable state tinbase interphase synthesized is difficult into using conventional method, this method is applied widely, can develop metastable for other The synthesis of state alloy material.
3. kamash alloy cenotype produced by the present invention and the storage lithium performance comparison of Sn simple substance show that alloying effectively improves The cyclical stability of material.
The alloy phase of meta-stable that the method for the present invention is not easily-synthesized under normal conditions by first introducing crystal seed induction Generation, this method provide a kind of new method and think of for the synthesis of metastable state kamash alloy material and other metastable materials Road.In addition, the alloy material that the present invention is prepared can be used for lithium ion battery active cathode material, the new phase material table of the alloy Reveal higher storage lithium specific capacity, compared to the simple substance Sn cathode of same appearance, cycle performance has obvious improvement.
Description of the drawings
Fig. 1 is Ni prepared in the embodiment of the present invention 20.62Sn5The XRD diagram of the new phase material of alloy.
Fig. 2 is Ni prepared in inventive embodiments 20.62Sn5The structure refinement result of alloy cenotype
Fig. 3 is Ni prepared in inventive embodiments 20.62Sn5The structure cell schematic diagram of alloy cenotype.
Fig. 4 is Ni prepared in the embodiment of the present invention 20.62Sn5The SEM figures of the new phase material of alloy.
Fig. 5 is Ni prepared in the embodiment of the present invention 20.62Sn5The TEM figures of the new phase material of alloy.
Fig. 6 is the XRD diagram of simple substance Sn materials prepared in the embodiment of the present invention 1.
Fig. 7 is the SEM figures of simple substance Sn materials prepared in the embodiment of the present invention 1.
Fig. 8 is the TEM figures of simple substance Sn materials prepared in the embodiment of the present invention 1.
Fig. 9 is Ni prepared in the embodiment of the present invention 20.62Sn5Prepared list in the new phase material of alloy and embodiment 1 Cycle performance comparison when matter Sn materials are as negative electrode of lithium ion battery.
Figure 10 is Fe prepared in the embodiment of the present invention 50.5Ni0.5Sn5The XRD diagram of the new phase material of alloy.
Figure 11 is Co prepared in the embodiment of the present invention 60.5Ni0.5Sn5The XRD diagram of the new phase material of alloy.
Specific embodiment
The present inventor studies by making thorough investigation and study with long-term experiment, develops a kind of method for preparing kamash alloy material, And MSn is prepared for the first time using this method5(M=Ni, Fe0.5Ni0.5, Co0.5Ni0.5) alloy cenotype.The preparation method is set Count it is ingenious, it is applied widely, be expected to urged in the preparation of other alloy materials and the synthesis of alloy cenotype by development and application The fields such as change, energy storage have very extensive application prospect.The preparation method is induced by way of introducing crystal seed in conventional strip The generation of the alloy phase for the meta-stable not being easily-synthesized under part.Further, the alloy material being prepared is used for lithium-ion electric Pond active cathode material, the new phase material of the alloy show higher storage lithium specific capacity, compared to the simple substance Sn cathode of same appearance, Its cycle performance has obvious improvement.
The present invention introduces M atoms in an orderly manner in tin parent phase, forms the MSn that tetragonal crystal system is belonged to parent phase5(M=Ni, Fe0.5Ni0.5, Co0.5Ni0.5) alloy cenotype, using the method for the present invention, when M is Ni, in the material also there are minimal amount of Fe, Co or Cu, but main phase is NiSn5.This method induces the synthesis of the metastable state cenotype, the M atomic energy of introducing by introducing crystal seed The reunion in charge and discharge process of tin is enough effectively inhibited, alleviates the attenuation of effective active matter quality, so as to improve material As the cyclical stability of cathode of lithium battery, and M atoms can also be used as conducting medium.
The MSn5The preparation method of kamash alloy cenotype includes：High temperature reduction method, hydrothermal synthesis method, wet chemistry method, High melt method, mechanico-chemical reaction method (such as mechanical attrition method, mechanical alloying method etc.), sol-gal process, magnetron sputtering Method etc..
In raw material selection, the methods of high temperature reduction method, hydrothermal synthesis method, wet chemistry method, sol-gal process, is preferably corresponding Metal salt material；The methods of mechanico-chemical reaction method (such as mechanical attrition method, mechanical alloying method etc.), magnetron sputtering method, is excellent Select corresponding metal simple-substance material.
The present invention prepares product using wet chemistry method, by introducing crystal seed metastable state MSn5Alloy is more easy to shape Into solving and be difficult to obtain metastable state MSn using conventional method5(especially M is Fe to alloy0.5Ni0.5、Co0.5Ni0.5When) ask Topic.
With reference to specific embodiment, the present invention is further explained.It should be understood that these embodiments are merely to illustrate the present invention Rather than it limits the scope of the invention.Test method without specific conditions in the following example, usually according to conventional strip Part or according to the normal condition proposed by manufacturer.Unless otherwise stated, otherwise percentage and number are calculated by weight.
Embodiment 1
The preparation of simple substance Sn negative materials：
It is 1. 3.6g polyvinylpyrrolidones (PVP, MW=360,000) and 0.6g is poly- (- 2 oxazoline of 2- ethyls) (PEtOx, MW=50,000) is added to specification in 250ml three-necked flasks, 40ml tetraethylene glycols (TEG) to be added in, in high-purity Ar Heat the mixture to 130 DEG C under inert atmosphere, stirring is to being completely dissolved.
2. 0.59g stannous sulfates are distributed at ambient temperature in 16ml tetraethylene glycols, then by SnSO4TEG solution It is added drop-wise in three-necked flask, stirs 15min.1g sodium borohydrides are distributed in 30ml tetraethylene glycols, then by the NaBH of brand-new4's TEG solution is slowly dropped in three-necked flask, obtains black suspension.
3. stirring 1h under an inert atmosphere, centrifuge, washing, 60 DEG C of vacuum drying oven is dried overnight to obtain product.
Crystal Structure and morphology characterization are carried out to the simple substance Sn materials that the present invention is prepared.It is prepared such as Fig. 6 Simple substance Sn XRD spectrum.As can be seen that the pure phase simple substance Sn materials of prepared material from XRD spectrum.Fig. 7 is simple substance The SEM image of Sn, it can be seen from the figure that the pattern of simple substance Sn materials is the nano particle (spherical particle) of 30-50nm.Figure 8 be the TEM image of simple substance Sn materials, and as can be seen from the figure simple substance Sn material surfaces have the amorphous oxide layer of one layer of 3-5nm, Inside is crystalline phase.
The storage lithium performance characterization of simple substance Sn active cathode materials：
The storage lithium performance of Sn simple substance active cathode materials is analyzed using half-cell in the present embodiment.The battery used Type is 2032 type button cells, and it is lithium piece to electrode and reference electrode to use.The lithium hexafluoro phosphate that electrolyte is 1M disperses In ethylene carbonate and dimethyl carbonate (volume ratio EC:DMC=1:1) in mixed liquor.The diaphragm used is polytetrafluoroethylene (PTFE) Film.Charging/discharging voltage ranging from 0.005-2V, charging and discharging currents density are 200mA/g.
The Ni that Fig. 9 is simple substance Sn and prepared by embodiment 20.62Sn5Bianry alloy cenotype is as lithium ion battery negative material Cycle performance compares.It can be seen from the figure that simple substance Sn compares NiSn5With higher initial capacity, but cycle performance is poor.
Embodiment 2
NiSn5The preparation of the new phase material of bianry alloy：
It is 1. 3.6g polyvinylpyrrolidones (PVP, MW=360,000) and 0.6g is poly- (- 2 oxazoline of 2- ethyls) (PEtOx, MW=50,000) is added to specification in 250ml three-necked flasks, 40ml tetraethylene glycols (TEG) to be added in, in high-purity Ar Heat the mixture to 130 DEG C under inert atmosphere, stirring is to being completely dissolved.
2. 0.59g stannous sulfates are distributed at ambient temperature in 16ml tetraethylene glycols, then by SnSO4TEG solution It is added drop-wise in three-necked flask, stirs 15min.1g sodium borohydrides are distributed in 30ml tetraethylene glycols, then by the NaBH of brand-new4's TEG solution is slowly dropped in three-necked flask, obtains black suspension, by temperature rise to 205 DEG C, persistently stirs 15min.
3. 2mg iron chloride is distributed in 5ml tetraethylene glycols, then by FeCl3TEG solution be added drop-wise in three-necked flask, Persistently stir 45min.
4. reaction temperature is dropped to 170 DEG C.64.7mg nickel chlorides are distributed in 30ml tetraethylene glycols, then by NiCl2's TEG solution is added drop-wise in three-necked flask, persistently stirs 60min, is cooled to room temperature.
5. the solution for being dispersed with product is centrifuged, washed with water and ethyl alcohol, repeatedly, done in vacuum drying chamber Dry 12 hours, obtain final product, it is a variety of detect the material is practical for Ni0.62Sn5。
Ni0.62Sn5The characterization of bianry alloy cenotype：
The Ni that the present invention is prepared0.62Sn5Bianry alloy cenotype carries out Crystal Structure and morphology characterization.Such as figure 1, it is prepared Ni0.62Sn5The XRD spectrum of alloy cenotype.As can be seen that not occurring the diffraction of simple substance Sn from XRD spectrum Peak, Sn parent phases are fully converted to Ni0.62Sn5Alloy phase.Fig. 2 is Ni0.62Sn5The structure refinement result of alloy cenotype.Fig. 3 is Ni0.62Sn5The structure cell schematic diagram of alloy cenotype, by schematic diagram it is found that Ni0.62Sn5Alloy cenotype belongs to tetragonal crystal system, structure cell Parameter is as follows：α=β=γ=90 °.Ni0.62Sn5Unit cell volume beTin atom coordinate is Sn1(0,0,0.5), Sn2(0.1945,0.6099,0.5), nickle atom coordinate are Ni (0.5,0.5,0.25).Fig. 4 is Ni0.62Sn5The SEM image of alloy cenotype, it can be seen from the figure that Ni0.62Sn5Alloy cenotype Pattern be 30-50nm nano particle (spherical particle).Fig. 5 is Ni0.62Sn5The TEM image of alloy cenotype, can from figure To find out Ni0.62Sn5Nanometer ball surface has the amorphous oxide layer of one layer of 3-5nm, and inside is crystalline phase.
Ni0.62Sn5The storage lithium performance characterization of bianry alloy cenotype active cathode material：
Using half-cell to Ni in the present embodiment0.62Sn5The storage lithium performance of bianry alloy cenotype is analyzed.The electricity used Pond type is 2032 type button cells, and it is lithium piece to electrode and reference electrode to use.The lithium hexafluoro phosphate point that electrolyte is 1M It dissipates in ethylene carbonate and dimethyl carbonate (volume ratio EC:DMC=1:1) in mixed liquor.The diaphragm used is polytetrafluoroethyl-ne Alkene film.Charging/discharging voltage ranging from 0.005-2V, charging and discharging currents density are 200mA/g.
Fig. 9 is Ni0.62Sn5Alloy cenotype and simple substance Sn are compared as the cycle performance of lithium ion battery negative material.From figure In as can be seen that alloying after, Ni0.62Sn5Cyclical stability have apparent improvement compared with Sn simple substance.
Embodiment 3
Detailed process is as follows：
NiSn5The preparation of the new phase material of bianry alloy：
It is 1. 2.4g polyvinylpyrrolidones (PVP, MW=360,000) and 1.2g is poly- (- 2 oxazoline of 2- ethyls) (PEtOx, MW=50,000) is added to specification in 250ml three-necked flasks, 60ml tetraethylene glycols (TEG) to be added in, in high-purity Ar Heat the mixture to 170 DEG C under inert atmosphere, stirring is to being completely dissolved.
2. 0.52g stannous chlorides are distributed at ambient temperature in 16ml tetraethylene glycols, then by SnCl2TEG solution It is added drop-wise in three-necked flask, stirs 15min.1g sodium borohydrides are distributed in 30ml tetraethylene glycols, then by the NaBH of brand-new4's TEG solution is slowly dropped in three-necked flask, obtains black suspension, by temperature rise to 205 DEG C, persistently stirs 15min.
3. 2.93mg CoCL2 6H2Os are distributed in 5ml tetraethylene glycols, then by CoCl2·6H2The TEG solution of O is added drop-wise to In three-necked flask, 45min is persistently stirred.
4. reaction temperature is dropped to 170 DEG C.64.7mg nickel chlorides are distributed in 30ml tetraethylene glycols, then by NiCl2's TEG solution is added drop-wise in three-necked flask, persistently stirs 60min, is cooled to room temperature.
5. the solution for being dispersed with product is centrifuged, washed with water and ethyl alcohol, repeatedly, done in vacuum drying chamber Dry 12 hours, obtain final product.
Embodiment 4
NiSn5The preparation of the new phase material of bianry alloy：
It is 1. 2.4g polyvinylpyrrolidones (PVP, MW=360,000) and 1.2g is poly- (- 2 oxazoline of 2- ethyls) (PEtOx, MW=50,000) is added to specification in 250ml three-necked flasks, 60ml tetraethylene glycols (TEG) to be added in, in high-purity Ar Heat the mixture to 170 DEG C under inert atmosphere, stirring is to being completely dissolved.
2. 0.52g stannous chlorides are distributed at ambient temperature in 16ml tetraethylene glycols, then by SnCl2TEG solution It is added drop-wise in three-necked flask, stirs 15min.1g sodium borohydrides are distributed in 30ml tetraethylene glycols, then by the NaBH of brand-new4's TEG solution is slowly dropped in three-necked flask, obtains black suspension, by temperature rise to 205 DEG C, persistently stirs 15min.
3. 1mg iron chloride and 1.47mg CoCL2 6H2Os are distributed in 5ml tetraethylene glycols, then by FeCl3And CoCl2· 6H2The TEG solution of O is added drop-wise in three-necked flask, persistently stirs 45min.
4. reaction temperature is dropped to 170 DEG C.64.7mg nickel chlorides are distributed in 30ml tetraethylene glycols, then by NiCl2's TEG solution is added drop-wise in three-necked flask, persistently stirs 60min, is cooled to room temperature.
5. the solution for being dispersed with product is centrifuged, washed with water and ethyl alcohol, repeatedly, done in vacuum drying chamber Dry 12 hours, obtain final product.
Embodiment 5
Fe0.5Ni0.5Sn5The preparation of the new phase material of alloy：
It is 1. 2.4g polyvinylpyrrolidones (PVP, MW=360,000) and 1.2g is poly- (- 2 oxazoline of 2- ethyls) (PEtOx, MW=50,000) is added to specification in 250ml three-necked flasks, 60ml tetraethylene glycols (TEG) to be added in, in high-purity Ar Heat the mixture to 170 DEG C under inert atmosphere, stirring is to being completely dissolved.
2. 0.52g stannous chlorides are distributed at ambient temperature in 16ml tetraethylene glycols, then by SnCl2TEG solution It is added drop-wise in three-necked flask, stirs 15min.1g sodium borohydrides are distributed in 30ml tetraethylene glycols, then by the NaBH of brand-new4's TEG solution is slowly dropped in three-necked flask, obtains black suspension, by temperature rise to 205 DEG C, persistently stirs 15min.
3. 28mg iron chloride is distributed in 5ml tetraethylene glycols, then by FeCl3TEG solution be added drop-wise in three-necked flask, Persistently stir 45min.
4. reaction temperature is dropped to 170 DEG C.32.35mg nickel chlorides are distributed in 30ml tetraethylene glycols, then by NiCl2's TEG solution is added drop-wise in three-necked flask, persistently stirs 60min, is cooled to room temperature.
5. the solution for being dispersed with product is centrifuged, washed with water and ethyl alcohol, repeatedly, done in vacuum drying chamber Dry 12 hours, obtain final product.Figure 10 is prepared Fe0.5Ni0.5Sn5The XRD spectrum of ternary alloy three-partalloy cenotype.
Embodiment 6
Co0.5Ni0.5Sn5The preparation of the new phase material of alloy：
It is 1. 2.4g polyvinylpyrrolidones (PVP, MW=360,000) and 1.2g is poly- (- 2 oxazoline of 2- ethyls) (PEtOx, MW=50,000) is added to specification in 250ml three-necked flasks, 60ml tetraethylene glycols (TEG) to be added in, in high-purity Ar Heat the mixture to 170 DEG C under inert atmosphere, stirring is to being completely dissolved.
2. 0.52g stannous chlorides are distributed at ambient temperature in 16ml tetraethylene glycols, then by SnCl2TEG solution It is added drop-wise in three-necked flask, stirs 15min.1g sodium borohydrides are distributed in 30ml tetraethylene glycols, then by the NaBH of brand-new4's TEG solution is slowly dropped in three-necked flask, obtains black suspension, by temperature rise to 205 DEG C, persistently stirs 15min.
3. 41.2mg cobalt chloride hexahydrates are distributed in 5ml tetraethylene glycols, then by CoCl2·6H2The TEG solution of O is added dropwise Into three-necked flask, 45min is persistently stirred.
4. reaction temperature is dropped to 170 DEG C.32.35mg nickel chlorides are distributed in 30ml tetraethylene glycols, then by NiCl2's TEG solution is added drop-wise in three-necked flask, persistently stirs 60min, is cooled to room temperature.
5. the solution for being dispersed with product is centrifuged, washed with water and ethyl alcohol, repeatedly, done in vacuum drying chamber Dry 12 hours, obtain final product.Figure 11 is prepared Co0.5Ni0.5Sn5The XRD spectrum of ternary alloy three-partalloy cenotype.

Claims (10)

1. a kind of kamash alloy material, which is characterized in that the material main phase is MSn5Alloy belongs to tetragonal crystal system, P4/mcc spaces Group, wherein M are Ni, Fe0.5Ni0.5、Co0.5Ni0.5In one kind, material surface have one layer of amorphous metal oxide skin(coating).
2. kamash alloy material as described in claim 1, which is characterized in that the MSn5There are stoichiometric ratios in alloy M atom vacancies, i.e.,：MaSn5, the ranging from 0 ＜ a ＜ 1 of wherein a.
3. kamash alloy material as described in claim 1, which is characterized in that the MSn5Alloy is NiaSn5Or FebNicSn5Or CodNieSn5, wherein 0.4 ＜ a ＜, 0.8,0 ＜ b, c ＜, 0.5,0 ＜ d, e ＜ 0.5.
4. kamash alloy material as described in claim 1, which is characterized in that the amorphous metal oxide layer thicknesses are 3-5nm。
5. a kind of preparation method of kamash alloy material, which is characterized in that using wet chemical method, include the following steps：
1) under inert atmosphere conditions, pink salt is added in the organic solvent containing surface stabilizer in 130-170 DEG C of stirring Dissolving is obtained containing solution of tin；
2) reducing agent under inert atmosphere conditions, is added in containing solution of tin, tin ion is reduced to simple substance tin, obtains simple substance tin The dispersion liquid of parent phase；
3) 205 DEG C under inert atmosphere conditions, are warming up to, is introduced into Fe sources, Co sources, Cu sources in simple substance tin parent phase dispersion liquid One kind is stirred to react to form NSn5Crystal seed, wherein N are Fe, Co or Cu；
4) after crystal seed is formed, 170 DEG C are cooled to, Ni sources is added in, after being stirred to react, is cooled to room temperature；Centrifugation, washing, it is dry, Obtain kamash alloy material.
6. the preparation method of kamash alloy material according to claim 5, which is characterized in that the pink salt uses stannous Salt is selected from：It is one or more in stannous sulfate, stannous chloride, nitric acid stannous, stannous oxalate；The organic solvent is second One or more mixing in glycol, isopropanol, glycerine, tetraethylene glycol, diethanol amine, oleyl amine, tetrahydrofuran；The surface Stabilizer is polyvinylpyrrolidone (PVP), poly- (- 2 oxazoline of 2- ethyls) (PEtOx), cetyl trimethylammonium bromide (CTAB), one or more mixing in oleyl amine.
7. the preparation method of kamash alloy material according to claim 5, which is characterized in that the reducing agent is boron hydrogen Change one or more combinations in sodium, sodium hypophosphite, ammonium borohydride, tetrabutyl ammonium borohydride, hydrazine hydrate, active metal.
8. the preparation method of kamash alloy material according to claim 5, which is characterized in that the Fe sources, Co sources, Cu Source, Ni sources refer respectively to respective metal salt and are scattered in solution formed in organic solvent.
9. the preparation method of kamash alloy material according to claim 5, which is characterized in that the Fe sources, Co sources, Cu The additive amount in source is as follows：When the alloy of preparation is NiSn5When, molar ratio of the tin with adding metal in solution is caused after addition For：Sn:M ＞ 200, wherein M=Fe/Co/Cu；When the alloy of preparation is Fe0.5Ni0.5Sn5Or Co0.5Ni0.5Sn5When, make after addition In solution the molar ratio of tin and added metal be：8 ＜ Sn:M ＜ 20, wherein M=Fe/Co/Cu.
10. the preparation method of kamash alloy material according to claim 5, which is characterized in that the addition in the Ni sources Amount is as follows：When the alloy of preparation is NiSn5When, the 3 ＜ Sn of molar ratio of tin and Ni in solution are caused after addition:Ni ＜ 6；Work as preparation Alloy be：Fe0.5Ni0.5Sn5Or Co0.5Ni0.5Sn5When, so that the molar ratio of tin and Ni are in solution after addition：6 ＜ Sn:Ni ＜ 12.
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