CN110284037A - A method of it decomposing ternary alloy three-partalloy and prepares silicon or germanium nano material - Google Patents

A method of it decomposing ternary alloy three-partalloy and prepares silicon or germanium nano material Download PDF

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CN110284037A
CN110284037A CN201910667413.8A CN201910667413A CN110284037A CN 110284037 A CN110284037 A CN 110284037A CN 201910667413 A CN201910667413 A CN 201910667413A CN 110284037 A CN110284037 A CN 110284037A
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partalloy
ternary alloy
silicon
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CN110284037B (en
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夏盛清
贺彦清
刘超
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Shandong University
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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Abstract

The present invention provides a kind of method that decomposition ternary alloy three-partalloy prepares silicon or germanium nano material, comprising steps of the synthesis in solid state of Li-Zn-Si or Li-Zn-Ge ternary alloy three-partalloy chemical combination object；Silicon or germanium nano material is prepared through decomposing in Li-Zn-Si or Li-Zn-Ge ternary alloy three-partalloy chemical combination object.The raw material that the present invention uses is cheap, non-toxic and safe；Reaction condition is mild, process stabilizing, and yield is high, at low cost, without complicated cumbersome last handling process, is suitble to the large-scale production of nano-silicon or germanium material, has great market competition advantage.Gained nano-silicon or germanium material are porous structure, and partial size is small (10~100nm), and particle diameter distribution is narrow, particle size uniformity, high-purity low-oxygen, and dispersion performance is good, and application is strong.

Description

A method of it decomposing ternary alloy three-partalloy and prepares silicon or germanium nano material
Technical field
The present invention relates to a kind of methods that decomposition ternary alloy three-partalloy prepares silicon or germanium nano material, belong to nano material preparation skill Art field.
Background technique
Silicon, germanium are important semiconductor material, have been widely used in photoelectric field tool, corresponding nano material is in aviation Space flight, nuclear physics detecting, optical-fibre communications, infrared optics, solar battery, chemical catalyst, biomedicine, lithium ion battery etc. Field has particularly important application.
Current silicon, germanium preparation method of nano material are divided into two class of physical method and chemical method.Physical method is mainly with silicon or germanium Block simple substance is raw material, using means such as heating evaporation, laser ablation, magnetron sputterings, obtains the atomic vapour or height of silicon or germanium Isothermal plasma, then nano particle is obtained by substrate deposition or solution dispersion.Such method is limited to instrument and equipment, is suitable only for The preparation of small lot laboratory, can not be applied to scale industrial production.Another preparation method of physical method is high-energy ball milling, so And the powder body material particle size distribution obtained with silicon or germanium simple substance ball milling merely is wider, can not obtain the nanometer of size uniformity Grain, is unable to satisfy practical application request.Chemical method prepare the most representative method of nano particle be Pintsch process organosilicon or Organic germanium precursor, this is also batch preparation means more mature at present；In addition, passing through active alkali or alkaline earth metal high temperature The oxide precursor for restoring silicon or germanium is also to study more scheme at present.The chemical synthesis process of above-mentioned complexity, often relates to Pyroreaction needs expensive reagent, such as silane, sodium magnesium metal, and these raw materials are vivaciously inflammable, are easy to bring security risk, In addition chemical reduction method is difficult to control reaction process, it is easy to cause silicon oxygen or germanium oxygen impurities and alloy cpd, therefore also Need cumbersome postprocessing working procedures.Above-mentioned reason causes current silicon or the industrial production cost of germanium nano material occupies height not Under, seriously limit the application of material.
Preparation about nano silicon material: as Chinese patent literature CN102616785A discloses a kind of four chlorinations of zinc reduction The method that silicon prepares nano silica fume particle.Metallic zinc granule becomes zinc fume by melting gasifier, does protection gas and load in argon gas Brought into tubular reactor under conditions of gas, silicon tetrachloride be slowly introduced into liquid form in tubular reactor gasify after with Zinc reaction, generates the mixture of silicon powder particle and zinc chloride, obtains nano silica fume through overpickling and vacuum freeze drying processing Particle.But the patent needs to gasify metallic zinc and silicon tetrachloride, and energy consumption is high；And it needs to carry using carrier gas, reaction yield It is lower；It is related to reduction reaction simultaneously, required reaction temperature is up to 1000 DEG C or so, and it is at high cost, and react not easy to control；Gained silicon The mixture separating step of powder particles and zinc chloride is relatively complicated, while gained silicon powder particle partial size is larger, wider distribution；It is above-mentioned So that the application of silicon powder particle is restricted.
Preparation about nanometer germanium material: as Chinese patent literature CN104985177A discloses a kind of one-step synthesis method table The method of the nanometer germanium particle of face passivation；This method enhances chemical gas-phase deposition system using inductively coupled plasma body, uses Liquid germanium and water are as reaction source, the nanometer germanium particle of the direct synthetic surface passivation of a step.Although the invention eliminates reaction source Inflammable and explosive hidden danger, but need to carry ge source and water using carrier gas, reaction yield is lower, required inductively coupled plasma body It is complicated to enhance chemical gas-phase deposition system, is not suitable for prepare with scale；Although also, nano grain surface is passivated the group of avoiding It is poly-, but passivation in substance forms oxide on surface, can not obtain high-purity low-oxygen sample, products application is limited.For another example, Chinese Patent document CN102764896A discloses a kind of germanium nanometer grain preparation method that can stablize nanometer germanium；This method is by GeO2 It is dissolved in lye, obtains germanic acid radical ion precursor liquid, biocompatible natural biological macromolecular is then added, high-speed stirred is mixed Close, obtain after reactant solution under conditions of high-speed stirred with reducing agent hybrid reaction, finally by reduction reaction liquid by saturating Bag dialysis treatment is analysed, centrifugation freeze-drying obtains germanium nano particle.Gained germanium nano particle has preferable dispersed and smaller Granularity, but natural biological macromolecular is not easy to remove from product as stabilizer, equally can greatly limit the reality of product Application power.
Summary of the invention
In view of the deficienciess of the prior art, the present invention provides and a kind of efficiently mildly prepares silicon or germanium nanometer under room temperature The method of material.The method of the present invention both expensive organosilicons or germanium reagent inflammable without using toxicity, also without relying on high activity Inflammable sodium magnesium metal is reducing agent, but uses the metastable Li-Zn-Si and Li-Zn-Ge of chemical property ternary alloying Conjunction object is precursor, by simply aoxidizing, acid processing or low speed ball-milling treatment, can prepare that Domain size is small, granularity is equal in batches One and purity is high silicon or germanium nano material.The raw material that the present invention uses is cheap, non-toxic and safe；Reaction condition is mild, Process stabilizing, yield is high, at low cost, without complicated cumbersome last handling process, is suitble to the scale metaplasia of nano-silicon or germanium material It produces, there is great market competition advantage.
Technical scheme is as follows:
A method of it decomposing ternary alloy three-partalloy and prepares silicon or germanium nano material, comprising steps of
(1) synthesis in solid state of Li-Zn-Si or Li-Zn-Ge ternary alloy three-partalloy chemical combination object；
(2) silicon or germanium nano material is prepared through decomposing in Li-Zn-Si or Li-Zn-Ge ternary alloy three-partalloy chemical combination object.
Preferred according to the present invention, in step (1), the Li-Zn-Si ternary alloy three-partalloy chemical combination object is Li2ZnSi、 Li2ZnSi3Or Li8Zn2Si3；Li-Zn-Ge ternary alloy three-partalloy chemical combination object is LiZnGe, Li2ZnGe、Li2ZnGe3Or Li8Zn2Ge3。
Preferably, in step (1), the method for the synthesis in solid state Li-Zn-Si ternary alloy three-partalloy chemical combination object are as follows: by lithium metal, Zinc, elementary silicon or lithium metal, zinc, the corresponding binary compound of silicon are mixed to get mixture by chemical formula metering ratio；Then Constant temperature solid phase reaction at 500~800 DEG C is warming up under vacuum or inert atmosphere protection, with the heating rate of 150~250 DEG C/h 2~5h, cooling are ground to no metallic luster；Products therefrom under vacuum or inert atmosphere protection, with the liter of 150~250 DEG C/h Warm rate is warming up to 2~7h of constant temperature solid phase reaction at 600~900 DEG C, cooling, be ground to no metallic luster and obtain Li-Zn-Si ternary Alloy cpd.
The corresponding binary compound of the lithium metal, zinc, silicon refers to binary compound, zinc and silicon selected from lithium and zinc composition Two or three in binary compound that binary compound, lithium and the silicon of composition form.
It is further preferred that the inert atmosphere is argon gas.
Preferably, in step (1), the method for the synthesis in solid state Li-Zn-Ge ternary alloy three-partalloy chemical combination object are as follows: by lithium metal, Zinc, germanium simple substance or the corresponding binary compound of lithium metal, zinc, germanium are mixed to get mixture by chemical formula metering ratio；Then Constant temperature solid phase reaction at 300~500 DEG C is warming up under vacuum or inert atmosphere protection, with the heating rate of 60~100 DEG C/h Then 10~15h is warming up to 40~60h of constant temperature solid phase reaction at 700~900 DEG C with the heating rate of 60~100 DEG C/h, through grinding No metallic luster is milled to up to Li-Zn-Ge ternary alloy three-partalloy chemical combination object.
The corresponding binary compound of the lithium metal, zinc, germanium refers to binary compound, zinc and germanium selected from lithium and zinc composition Two or three in binary compound that binary compound, lithium and the germanium of composition form.
It is further preferred that the inert atmosphere is argon gas.
It is preferred according to the present invention, in step (2), the isolation are as follows: slow oxygenolysis, weak acid solution decompose or Mechanical ball mill is decomposed.
Preferably, the slow oxygenolysis step are as follows: be placed in Li-Zn-Si or Li-Zn-Ge ternary alloy three-partalloy chemical combination object In oxygen-containing continuous flow, room temperature is slowly oxidizing to compound and decomposes completely.The slow oxygenolysis can prepare porous structure and receive Rice grain.
It is further preferred that the oxygen-containing continuous flow is air.
It is further preferred that the oxidization time is ten days to 30 days.
Preferably, the weak acid solution decomposition step are as follows: by Li-Zn-Si or Li-Zn-Ge ternary alloy three-partalloy chemical combination object with it is weak Acidic buffer solution mixing, under the conditions of 15~40 DEG C of constant temperature, stirring is decomposed completely to compound, is then filtered, washed, is done Dry obtained silicon or germanium nano material.
It is further preferred that the quality of the ternary alloy three-partalloy chemical combination object and the volume ratio of buffer solution are 0.5-1.5: 500g/ml。
It is further preferred that the weak acid buffer solution is the pH that glacial acetic acid, anhydrous sodium acetate and deionized water are prepared The solution that value is 5~7.
It is further preferred that the mixing time is 15~40h.
Preferably, the mechanical ball mill decomposition step are as follows: be placed in Li-Zn-Si or Li-Zn-Ge ternary alloy three-partalloy chemical combination object In ball grinder, under vacuum or inert gas shielding, room-temperature ball-milling to compound decomposes completely.
It is further preferred that the inert gas is argon gas.
It is further preferred that the revolving speed of the ball milling is 250-350r/min；The Ball-milling Time is 24~48 hours.
It is further preferred that after the mechanical ball mill decomposition step also 4-6h need to be made annealing treatment at 350-450 DEG C.
Preferably, when isolation is slow oxygenolysis or mechanical ball mill decomposition, products therefrom also needs separate pure Silicon or germanium nano material is finally prepared in the step of change.
It is further preferred that described isolate and purify comprising steps of Li-Zn-Si or Li-Zn-Ge ternary alloy three-partalloy chemical combination object passes through After decomposition products therefrom through pickling, be filtered, washed, be dried in vacuo up to silicon or germanium nano material.
It is further preferred that described isolate and purify including one or more in the following conditions:
A, pickling be by Li-Zn-Si or Li-Zn-Ge ternary alloy three-partalloy chemical combination object after decomposing products therefrom in 0.1-2mol/ 30min is stirred to react in the hydrochloric acid of L；
B, the filtering is the mixed ester membranes for the use of aperture being 200nm；
C, the washing is washed with deionized water or dehydrated alcohol；
D, the vacuum drying condition are as follows: be dried in vacuo 1-6h at 60-80 DEG C.
It technical characterstic of the invention and has the beneficial effect that:
1, Li-Zn-Si or Li-Zn-Ge ternary alloy three-partalloy chemical combination object of the present invention only needs simple solid phase reaction that can be prepared into It arrives, it is easily prepared and raw materials used cheap and easy to get.The present invention uses Li-Zn-Si or Li-Zn-Ge ternary alloy three-partalloy chemical combination object for before Body, without using high activity sodium or magnesium as reducing agent, and avoid inflammable and explosive expensive organosilicon or germanium reagent, cost It is more cheap, it produces safer.The preparation of nano-silicon or germanium material of the present invention is closed by Li-Zn-Si or Li-Zn-Ge ternary Gold compound slowly decomposes acquisition in room temperature, avoids the unevenness of particle caused by high temperature secondary reaction process and direct removal alloying One problem；The Nano-Zinc formed in decomposable process can form protection to silicon or germanium nano-crystal, easily obtain receiving for high-purity low-oxygen Rice silicon or germanium material；Present invention process is simple, and reaction and product size pattern are easily controllable.The present invention is without using hydrogen fluorine Acid, surfactant, the post-treatment reagents such as stabilizer, separation and purification of products simple process, no external introducing pollution further mention The high purity of gained nano-silicon or germanium material.
2, the method for the present invention is easily achieved, reaction yield height (> 90%), being capable of large scale preparation；Gained nano-silicon or germanium Material is porous structure, and partial size is small (10~100nm), and particle diameter distribution is narrow, particle size uniformity, high-purity low-oxygen, and dispersion performance is good, Application is strong.
Detailed description of the invention
Fig. 1 is the nano silicon material powder X-ray RD prepared in embodiment 1.
Fig. 2 is the transmission electron microscope picture of the nano silicon material prepared in embodiment 1.
Fig. 3 is the nanometer germanium material powder XRD prepared in embodiment 2.
Fig. 4 is the transmission electron microscope picture of the nanometer germanium material prepared in embodiment 2.
Fig. 5 is the nanometer germanium material powder XRD prepared in embodiment 3.
Fig. 6 is the transmission electron microscope picture of the nanometer germanium material prepared in embodiment 3
Fig. 7 is the nanometer germanium material powder XRD prepared in embodiment 4.
Fig. 8 is the transmission electron microscope picture of the nanometer germanium material prepared in embodiment 4.
Fig. 9 is the alcohol dispersion liquid of the nano silicon material prepared in embodiment 1.
Figure 10 is the amylalcohol dispersion liquid of the nanometer germanium material prepared in embodiment 2.
Figure 11 is the amylalcohol dispersion liquid of the nanometer germanium material prepared in embodiment 3.
Figure 12 is the amylalcohol dispersion liquid of the nanometer germanium material prepared in embodiment 4.
Specific embodiment
The present invention will be further described combined with specific embodiments below, but not limited to this.
Experimental method described in following embodiments is unless otherwise specified conventional method simultaneously；The reagent and material Material, unless otherwise specified, commercially obtains.
Embodiment 1
Mechanical ball mill decomposes Li2The method that ZnSi ternary alloy three-partalloy chemical combination object prepares nano silicon material, comprising steps of
(1) in argon atmospher glove box, simple substance Li, Zn, Si is mixed by the molar ratio of 2:1:1 and are sealed to metal tantalum container In, metal tantalum container is placed in vacuum environment, 600 DEG C of heat preservation 3h are warming up to the heating rate of 190 DEG C/h, it is cold with furnace But, metal tantalum container is opened in argon atmospher glove box, the abrasive lapping that solid phase reaction is obtained to no metallic luster.Then will Metal tantalum is placed in vacuum environment by the material secondary seal after grinding into metal tantalum container, with the heating rate of 210 DEG C/h It is warming up to 770 DEG C of heat preservation 4h.Metal tantalum container is opened in argon atmospher glove box, the Li-Zn-Si tri- that solid phase reaction is obtained First alloy cpd is ground to no metallic luster and obtains Li2ZnSi ternary alloy three-partalloy chemical combination object.
(2) in argon atmospher glove box, by Li2ZnSi ternary alloy three-partalloy chemical combination object powder is fitted into agate jar, agate The sealing of ball grinder external application stainless steel tank body；Ball grinder is placed on planetary ball mill, with 300r/min's under argon atmosphere Rotational velocity room-temperature ball-milling 36h；Ball grinder is opened in argon atmospher glove box after ball milling, the powder in collecting tank.Institute The X ray diffracting spectrum of powder is obtained as shown in Figure 1, resulting nano silicon material is amorphous.By above-mentioned powder in 400 DEG C of vacuum Under carry out pickling after annealing 5h (500ml1.2mol/L dilute hydrochloric acid is added in every 0.5g powder), stir after 30min and be through aperture The mixed ester membranes filtering of 200nm, deionized water are washed, vacuum drying 3h obtains crystal form nano Si material at 70 DEG C.
The X ray diffracting spectrum of nano Si material obtained by the present embodiment is as shown in Figure 1；As seen from the figure, prepared by this method Nano Si is cubic, free from admixture.
The transmission electron microscope picture of nano Si material manufactured in the present embodiment is as shown in Figure 2；As seen from the figure, what prepared by this method receives Rice Si has porous structure, and granularity is in 20-50nm.
Embodiment 2
The method of slow oxygenolysis LiZnGe ternary alloy three-partalloy chemical combination object preparation nanometer germanium material, comprising steps of
(1) in argon atmospher glove box, simple substance Li, Zn, Ge is mixed by the molar ratio of 1:1:1 and are sealed to metal tantalum container In, metal tantalum container is placed in vacuum environment, 400 DEG C of heat preservation 12hr are warming up to the heating rate of 80 DEG C/h, then with The heating rate of 80 DEG C/h is warming up to 850 DEG C of heat preservation 48h.Metal tantalum container is opened in argon atmospher glove box, solid phase is anti- The Li-Zn-Ge ternary alloy three-partalloy chemical combination object that should be obtained is ground to no metallic luster and obtains LiZnGe ternary alloy three-partalloy chemical combination object.
(2) in argon atmospher glove box, LiZnGe ternary alloy three-partalloy chemical combination object powder is packed into glass container, glass is held Device is placed to be decomposed for 30 days to complete in air.It takes 1g powder to be added in the dilute hydrochloric acid of the 1.2mol/L of 500ml, is stirred to react 30min washes away other ingredients, and the mixed ester membranes that via hole diameter is 200nm filter, deionized water is washed, vacuum at 70 DEG C Dry 3h obtains a nanometer Ge material.
The X ray diffracting spectrum of products therefrom and nanometer germanium material after the present embodiment LiZnGe ternary alloy three-partalloy chemical combination object decomposes As shown in Figure 3；From the figure 3, it may be seen that the product that LiZnGe ternary alloy three-partalloy chemical combination object decomposes completely is Ge, Zn and ZnO, the compound of Li It is difficult to demarcate in X ray diffracting spectrum.After dilute hydrochloric acid solution is handled, cubic-phase nano Ge, free from admixture are left behind.
The transmission electron microscope characterization result of nanometer Ge material obtained by the present embodiment is as shown in Figure 4；As shown in Figure 4, gained nanometer Ge has nano-porous structure, and granularity is in 100nm or so.
Embodiment 3
The method that weak acid solution decomposes LiZnGe ternary alloy three-partalloy chemical combination object preparation nanometer germanium material, comprising steps of
(1) LiZnGe ternary alloy three-partalloy chemical combination object prepare it is as described in Example 2.
(2) acidic buffer solution that pH=6 is prepared with glacial acetic acid, anhydrous sodium acetate and deionized water, is computed glacial acetic acid Molar ratio with sodium acetate is 0.056:1；Take LiZnGe ternary alloy three-partalloy chemical combination object powder 1g that the acidic buffer solution of 500ml is added It is fitted into the glass container of argon atmospher with stirring magneton；Glass container is immersed in 30 DEG C of water-baths, and magnetic agitation, which is adjusted to glass, to be held Have vortex generation, after being uninterruptedly stirred to react for 24 hours, open glass container in air in device, by the solution in glass container into Row filtering, gained precipitating obtain a nanometer Ge material through vacuum drying 3h at deionized water washing, 70 DEG C.
The chalk line diffracting spectrum of nanometer Ge material obtained by the present embodiment is as shown in Figure 5；As shown in Figure 5, prepared by this method Cubic-phase nano Ge, free from admixture.
The transmission electron microscope picture of nanometer Ge material manufactured in the present embodiment is as shown in Figure 6；It will be appreciated from fig. 6 that this method preparation Nanometer Ge has porous structure, and granularity is in 10-100nm.
Embodiment 4
The method that mechanical ball mill decomposes LiZnGe ternary alloy three-partalloy chemical combination object preparation nanometer germanium material, comprising steps of
(1) LiZnGe ternary alloy three-partalloy chemical combination object prepare it is as described in Example 2.
(2) in argon atmospher glove box, LiZnGe ternary alloy three-partalloy chemical combination object powder is fitted into agate jar, agate ball The sealing of grinding jar external application stainless steel tank body；Ball grinder is placed on planetary ball mill, in argon atmosphere with 300r/min from Rotary speed ball milling 36h；Ball grinder is opened in argon atmospher glove box after ball milling, the powder in collecting tank；Gained powder X ray diffracting spectrum as shown in fig. 7, there is the Kuan Huafeng of germanium in gained powder, illustrate it with crystalline state, without annealing. It takes 1g powder that the dilute hydrochloric acid of the 1.2mol/L of 500ml is added, is stirred to react 30min and washes away other ingredients, via hole diameter is 200nm's Mixed ester membranes filtering, deionized water are washed, vacuum drying 3h obtains a nanometer Ge material at 60 DEG C.
The X-ray diffraction of products therefrom and nanometer Ge particle after the present embodiment LiZnGe ternary alloy three-partalloy chemical combination object powder ball milling Map is as shown in Figure 7；As seen from the figure, LiZnGe ternary alloy three-partalloy chemical combination object powder is fully converted into a nanometer Ge after ball-milling treatment And Zn, by dilute hydrochloric acid solution pickling after, leave cubic-phase nano Ge, free from admixture.
The transmission electron microscope picture of nanometer Ge particle manufactured in the present embodiment is as shown in Figure 8；As shown in Figure 8, prepared by this method Nanometer Ge has porous structure, and granularity is in 10-50nm.
Test example 1
Dispersion performance test
Test specimen: nanometer germanium obtained by embodiment 1-4 or silicon materials.
Test method: by 0.1g sample dispersion in 500mL amylalcohol or ethanol solution, ultrasonic 0.5h obtains nano-silicon or germanium Amylalcohol or alcohol dispersion liquid.
Fig. 9-12 is successively the nanometer germanium material of the alcohol dispersion liquid of nano silicon material prepared by embodiment 1, the preparation of embodiment 2 Nanometer germanium material prepared by the amylalcohol dispersion liquid and embodiment 4 of nanometer germanium material prepared by the amylalcohol dispersion liquid of material, embodiment 3 The photo of amylalcohol dispersion liquid, as seen from the figure, present invention gained nanometer germanium or silicon materials dispersibility are preferably.At room temperature, gained silicon, Germanium disperses solution and places seven days still without precipitating.

Claims (10)

1. a kind of method decomposed ternary alloy three-partalloy and prepare silicon or germanium nano material, comprising steps of
(1) synthesis in solid state of Li-Zn-Si or Li-Zn-Ge ternary alloy three-partalloy chemical combination object；
(2) silicon or germanium nano material is prepared through decomposing in Li-Zn-Si or Li-Zn-Ge ternary alloy three-partalloy chemical combination object.
2. decomposing the method that ternary alloy three-partalloy prepares silicon or germanium nano material according to claim 1, which is characterized in that step (1) in, the Li-Zn-Si ternary alloy three-partalloy chemical combination object is Li2ZnSi、Li2ZnSi3Or Li8Zn2Si3；Li-Zn-Ge ternary alloy three-partalloy Compound is LiZnGe, Li2ZnGe、Li2ZnGe3Or Li8Zn2Ge3。
3. decomposing the method that ternary alloy three-partalloy prepares silicon or germanium nano material according to claim 2, which is characterized in that described solid The method for being combined to Li-Zn-Si ternary alloy three-partalloy chemical combination object are as follows: lithium metal, zinc, elementary silicon or lithium metal, zinc, silicon is corresponding Binary compound, by chemical formula metering ratio be mixed to get mixture；Then under vacuum or inert atmosphere protection, with 150~ The heating rate of 250 DEG C/h is warming up to 2~5h of constant temperature solid phase reaction at 500~800 DEG C, and cooling is ground to no metallic luster；Institute Product that constant temperature is warming up at 600~900 DEG C under vacuum or inert atmosphere protection, with the heating rate of 150~250 DEG C/h is solid 2~7h of phase reaction, it is cooling, be ground to no metallic luster and obtain Li-Zn-Si ternary alloy three-partalloy chemical combination object.
4. decomposing the method that ternary alloy three-partalloy prepares silicon or germanium nano material according to claim 2, which is characterized in that described solid The method for being combined to Li-Zn-Ge ternary alloy three-partalloy chemical combination object are as follows: lithium metal, zinc, germanium simple substance or lithium metal, zinc, germanium is corresponding Binary compound, by chemical formula metering ratio be mixed to get mixture；Then under vacuum or inert atmosphere protection, with 60~ The heating rate of 100 DEG C/h is warming up to 10~15h of constant temperature solid phase reaction at 300~500 DEG C, then with the liter of 60~100 DEG C/h Warm rate is warming up to 40~60h of constant temperature solid phase reaction at 700~900 DEG C, it is ground to no metallic luster up to Li-Zn-Ge tri- First alloy cpd.
5. decomposing the method that ternary alloy three-partalloy prepares silicon or germanium nano material according to claim 1, which is characterized in that step (2) in, the isolation are as follows: slow oxygenolysis, weak acid solution decompose or mechanical ball mill is decomposed.
6. decomposing the method that ternary alloy three-partalloy prepares silicon or germanium nano material according to claim 5, which is characterized in that described slow Slow oxygenolysis step are as follows: Li-Zn-Si or Li-Zn-Ge ternary alloy three-partalloy chemical combination object is placed in oxygen-containing continuous flow, room temperature is slow Slowly compound is oxidizing to decompose completely；
Preferably, the oxygen-containing continuous flow is air；
Preferably, the oxidization time is ten days to 30 days.
7. decomposing the method that ternary alloy three-partalloy prepares silicon or germanium nano material according to claim 5, which is characterized in that described weak Acid solution decomposition step are as follows: mix Li-Zn-Si or Li-Zn-Ge ternary alloy three-partalloy chemical combination object with weak acid buffer solution, in perseverance Under the conditions of 15~40 DEG C of temperature, stirring is decomposed completely to compound, is then filtered, washed, dries obtained silicon or germanium nano material；
Preferably, the quality of the ternary alloy three-partalloy chemical combination object and the volume ratio of buffer solution are 0.5-1.5:500g/ml；
Preferably, it is 5~7 that the weak acid buffer solution, which is the pH value that glacial acetic acid, anhydrous sodium acetate and deionized water are prepared, Solution；
Preferably, the mixing time is 15~40h.
8. decomposing the method that ternary alloy three-partalloy prepares silicon or germanium nano material according to claim 5, which is characterized in that the machine Tool ball milling decomposition step are as follows: Li-Zn-Si or Li-Zn-Ge ternary alloy three-partalloy chemical combination object is placed in ball grinder, in vacuum or inertia Under gas shield, room-temperature ball-milling to compound decomposes completely；
Preferably, the revolving speed of the ball milling is 250-350r/min；The Ball-milling Time is 24~48 hours；
Preferably, also 4-6h need to be made annealing treatment at 350-450 DEG C after the mechanical ball mill decomposition step.
9. decomposing the method that ternary alloy three-partalloy prepares silicon or germanium nano material according to claim 5, which is characterized in that decomposition side When formula is slow oxygenolysis or mechanical ball mill decomposition, products therefrom also needs the step of being isolated and purified, to be finally prepared Silicon or germanium nano material；It is described to isolate and purify comprising steps of Li-Zn-Si or Li-Zn-Ge ternary alloy three-partalloy chemical combination object is after decomposing Products therefrom through pickling, be filtered, washed, be dried in vacuo up to silicon or germanium nano material.
10. decomposing the method that ternary alloy three-partalloy prepares silicon or germanium nano material according to claim 9, which is characterized in that described It isolates and purifies including one or more in the following conditions:
A, pickling be by Li-Zn-Si or Li-Zn-Ge ternary alloy three-partalloy chemical combination object after decomposing products therefrom in 0.1-2mol/L 30min is stirred to react in hydrochloric acid；
B, the filtering is the mixed ester membranes for the use of aperture being 200nm；
C, the washing is washed with deionized water or dehydrated alcohol；
D, the vacuum drying condition are as follows: be dried in vacuo 1-6h at 60-80 DEG C.
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