CN106410133A - Ball-milling preparation method for attapulgite-based porous silicon nanowire material - Google Patents

Ball-milling preparation method for attapulgite-based porous silicon nanowire material Download PDF

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CN106410133A
CN106410133A CN201610807467.6A CN201610807467A CN106410133A CN 106410133 A CN106410133 A CN 106410133A CN 201610807467 A CN201610807467 A CN 201610807467A CN 106410133 A CN106410133 A CN 106410133A
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attapulgite
ball
milling
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侯建华
蒋欣
戴翔
窦倩
王雪
鄢碧鹏
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Yangzhou University
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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
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    • B82—NANOTECHNOLOGY
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    • C01B33/00—Silicon; Compounds thereof
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    • C01B33/023—Preparation by reduction of silica or free silica-containing material
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    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • 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
    • H01M4/386—Silicon or alloys based on silicon
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/10—Energy storage using batteries

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Abstract

The invention relates to a ball-milling preparation method for an attapulgite-based porous silicon nanowire material, belonging to the technical field of preparation of nanoelectrode materials. The ball-milling preparation method comprises the following steps of: filtering or centrifuging solution containing attapulgite after performing ultrasonic processing, then, drying to obtain dry attapulgite, and mixing attapulgite with aluminium trichloride and aluminium powder or a mixture of aluminium powder or magnesium powder to obtain a mixture containing attapulgite; and, putting the mixture containing attapulgite in a ball mill, milling and cooling to room temperature under the condition of argon gas, collecting a product, washing the product by using distilled water after immersing the product by using diluted hydrochloric acid, and then, preparing the attapulgite-based porous silicon nanowire. The ball-milling preparation method disclosed by the invention is simple in technological process, cheap in raw material and high in productivity; furthermore, preparation is carried out through solid-phase reaction, so that industrial production can be facilitated; and the electrochemical performance is excellent.

Description

A kind of ball-milling preparation method of attapulgite Quito hole silicon nanowire material
Technical field
The invention belongs to the preparing technical field of nano-electrode material.
Background technology
With social fast development, the mankind grow with each passing day to the demand of the energy.Change based on coal, oil, natural gas The stone energy and other non-renewable energy resources gradually use up, and so that environmental quality is declined to a great extent, ecological environment problem is also increasingly serious, this It is all a difficult problem urgently to be resolved hurrily now.Therefore, how to improve efficiency of energy utilization and develop reproducible cleaning new energy（As pure Electric automobile）Problem become the focus of people's growing interest.In this context, new chemical energy storage device is (as secondary cell Deng) gain great popularity.By comparison, the lithium ion battery work in secondary cell has voltage height, discharge capacity height, cycle life The advantages of grow and have a safety feature.
Silicon/carbon/graphite in lithium ion batteries carbon negative pole material theoretical specific capacity only has 372 mAh/g, and high rate performance is poor, vibration density Degree little it is impossible to meet the demand of energy-density lithium ion battery.Thus, the negative material finding height ratio capacity is substituting graphite gesture Must go.Silicon has the theoretical specific capacity of up to 4200 mAh/g and moderate voltage platform, is to be hopeful most to substitute graphite One of lithium ion battery negative material.However, silicon does not only exist serious bulk effect in cyclic process（Reach more than 300%）, Also it is easily caused silicon grain to pulverize, force electrode structure avalanche, and the poorly conductive of silicon, these shortcomings make silicon based anode material in reality It is subject to very big obstruction in the application of border.Preparation nanometer materials, can significantly improve the chemical property of silicon based anode material, but The preparation cost of this kind of nano-structure porous silicon is high at present, and complex process is it is difficult to large-scale production.In addition, preparing nano-structure porous silicon material Material typically requires higher temperature, even if being also required to higher than 550 DEG C using magnesiothermic reduction technology.For example：Zhihao Bao （RSC Adv., 2013, 3(26): 10145-10149）With Yi Cui（Sci.Rep., 2013,3: 1919-1925）Two problems Group, with agricultural product rice husk for porous silicon source, is prepared porous silica material using magnesiothermic reduction technology, and is obtained excellent electrochemistry Energy.In addition, Jaephil Cho (Angew. Chem. Int. Ed., 2008,47 (52):10151-10154) group's knot Close silica and make template and naphthalene sodium reduction SiCl4Preparation 3-D porous silicon, under 1C multiplying power, reversible capacity after 100 circulations Up to 2800 mAh/g.But, the method is not only complicated and relatively costly.For problem above, the present invention is based on environment friend Good type preparation method and selection inexpensive raw material, prepare the side of porous silicon nanowire material especially by easy ball-milling method Method.
Concave convex rod is a kind of natural non-metallic clay mineral, and unique stratiform and chain structure give its special performance, It is made to be widely used in industry-by-industry.The mineral characteristic attapulgite of concave convex rod（Attapulgite）Also known as palygorskite（Paly- gorskite）, it is the porous silicate clay mineral of magnalium containing Shuifu County of a kind of layer of chain structure, be mineralogically under the jurisdiction of Hai Pao Stone race.Be Chinese scholar Xu Jiquan etc. in 1976, Jiangsu Province, China Luhe County bamboo town little winding discovery attapulgite ore deposit, subsequently In succession find this ore deposit on Xuyi Jiangsu, Mingguang, anhui and other places.Its preferable molecular formula is：Mg5(H2O)4[Si4O10]2(OH)2, theoretical Chemical composition mass fraction be：SiO256.96%, (Mg, Al, Fe) O 23.83%, H2O 19.21%.Attapulgite structure In there is crystal lattice, in crystal contain variable amount of Na+、Ca2+、Fe3+、Al3+, crystal is in needle-like, fibrous or fiber collection Shape, and there is certain plasticity and cohesive force.Crystal structure unit layer by 8 Si-O tetrahedrons with 2: 1 type layered arrangement, its In Si4+Can be on a small quantity by Fe3+And Al3+Ion substitution, Mg2+Can be on a small quantity by Fe2+, Fe3+And Al3+Ion substitution. The synthesis result of various ion substitutions be attapulgite usually with a small amount of negative electrical charge, this kind of electric charge belongs to structure charge and has Jie Intermediate structure between chain structure and layer structure.Attapulgite is in earthy, compact massive originates in sedimentary rock and weathering crust In, soil property is fine and smooth, has that oily soapy, light weight, property be crisp, fracture is in conchoidal or irregular shape, and water imbibition is strong, and color is white, ash White, cinerous, celadon or weak silky luster.Attapulgite has many special excellent performances, with adsorbent, bonding The forms such as agent, auxiliary agent, additive, catalyst carrier are widely used in decolouring and water process, building materials, light industry, weaving, geology are surveyed The industries such as spy.
Content of the invention
Present invention aim at providing a kind of ball-milling preparation method of attapulgite Quito hole silicon nanowire material.
The present invention comprises the steps：
1）Filter after will be ultrasonically treated for the solution containing attapulgite or be centrifuged, be then dried and obtain dry attapulgite, then By the mixture of attapulgite and alchlor, aluminium powder or aluminium powder and magnesium powder, obtain the mixture containing attapulgite；
2）Mixture containing attapulgite is placed in ball mill, is ground under the conditions of argon gas；
3）Grinding is cooled to greenhouse after terminating, collect product, after being soaked with watery hydrochloric acid, with distilling water washing, obtains final product attapulgite Quito hole silicon nanowires.
The presoma that the present invention prepares porous silicon nanowires is attapulgite, or contains attapulgite, or concave convex rod Product after soil process.The whole synthesis technique of the present invention has the advantages of process is simple, and the prices of raw materials are cheap, yield is high, and Be conducive to industrialized production using solid phase reaction preparation, and obtain the achievement of excellent chemical property.
The present invention specifically has the beneficial effect that：
1st, simple production process of the present invention, cost are relatively low, and effectively reduce reaction temperature, and the yield of final products is high, Can achieve large-scale production.
2nd, the material prepared by the present invention can be used for high-capacity lithium ion cell, catalyst carrier, ultracapacitor, urges Agent, adsorbent, gas storage, medicament transport, the numerous areas such as bio-imaging and water process.
3rd, lithium ion battery is formed with the material of present invention preparation, after 250 circulations, 0.372 A/g and 3.72A/g electric current Under density, reversible capacity is up to 2258.6 mAh/g and 1086.9 mAh/g respectively.The excellent chemical property of this material is benefited In material, the pattern of porous silicon nanowires alleviates the bulk effect of porous silicon and shortens Li+Diffusion rate.
Further, the mixture of aluminium powder of the present invention or aluminium powder and magnesium powder and the attapulgite being dried, tri-chlorination The mixing quality of aluminium is than for 1～50: 1: 2～50.The consumption of alchlor is for alchlor more than attapulgite purpose High-temperature fusion salt can fully wrap up attapulgite, so can reduce the mixture of expensive aluminium powder or aluminium powder and magnesium powder As the amount of reducing agent, and the length of the porous silicon nanowires prepared is partially long, approximately more than 4 microns.
During described grinding, in ball mill, the mass ratio that feeds intake of mill ball and described compound is 20～1: 1, and rotating speed is 200～1200rpm, milling time is 1～40h.Mill ball and the mass ratio that feeds intake are more than 1, and effect is fully to connect in order that feeding intake Tactile mill ball, reduces milling time.Rotating speed is 200～1200rpm, and milling time is 1～40h, is the rotating speed in this scope Higher with the yield of milling time porous silicon nanometer, and the length of the porous silicon nanowires prepared is partially long, approximately more than 4 microns, such as Fruit rotating speed and milling time are less than this scope, then the yield of porous silicon nanowires is low；If rotating speed and milling time are higher than this Scope is although the yield of porous nano silicon is higher, but corresponding energy consumption is also higher, and porous silicon nanowires also can be ground Disconnected, or even become powder.
Described step 3）In for soak watery hydrochloric acid concentration be 0.1M effect be removal unreacted aluminium powder or （With）Magnesium powder and the impurity such as corresponding aluminum silicide or magnesium silicide.
The attapulgite Quito hole silicon nanowires higher in order to obtain purity, in described step 3）Afterwards, then with hydrofluoric acid or The aqueous slkali of the dense heat of person removes remaining Si oxide, obtains final product refined attapulgite Quito hole silicon nanowires.
Brief description
Fig. 1 is the XRD of prepared attapulgite Quito hole silicon nanowires in embodiment 1.
Fig. 2 is the ESEM of prepared attapulgite Quito hole silicon nanowires in embodiment 1（SEM）Figure.
Fig. 3 is the transmission electron microscope of prepared attapulgite Quito hole silicon nanowires in embodiment 1（TEM）Figure.
Fig. 4 is the lithium ion battery that in embodiment 1 prepared by prepared attapulgite Quito hole silicon nanowires at different times Rate constant current charge-discharge cycle life figure.
Fig. 5 is the ESEM of prepared attapulgite Quito hole silicon nanowires in embodiment 2（SEM）Figure.
Fig. 6 is the transmission electron microscope of prepared attapulgite Quito hole silicon nanowires in embodiment 2（TEM）Figure.
Specific embodiment
Embodiment 1：
Step one：Attapulgite containing 150 g is added to after ultrasonic 1 hour in 300 mL aqueous solvents and filters or be centrifuged After be dried, obtain attapulgite, then with 1: 10: 1 mass ratio by attapulgite and alchlor, aluminium powder mixing, acquirement contains The mixture of attapulgite.
Step 2：Mixture containing attapulgite is placed in full of in the agate pot of argon gas, using planetary ball mill ball milling, Ball material mass ratio is 10: 1, and rotating speed is 500 rpm, and Ball-milling Time is 10 h.
Step 3：After ball milling terminates, naturally cool to greenhouse and collect product, after being soaked with 0.1M watery hydrochloric acid, use distilled water Cyclic washing, finally removes remaining Si oxide with 3% hydrofluoric acid solution, obtains final product attapulgite Quito hole silicon nanowires.
Product and performance test：
The XRD spectrum of prepared attapulgite Quito hole silicon nanowires from Fig. 1 is for embodiment 1, the XRD of the sample obtaining spreads out Penetrate peak as shown in figure 1, only diffraction maximum occurs at 28.6 °, 46.9 °, 56.2 °, 69.4 ° and 76.3 °, these diffraction maximums are brilliant The diffraction maximum of body silicon, corresponds respectively to (111), (220), (311), (400), the interplanar distance of (331) of crystalline silicon.Therefore, Attapulgite, after the technique of embodiment 1, can obtain pure silicon materials.Concrete reaction equation is as follows：
Al+Mg5Si8O20(OH)2(OH2)4+AlCl3→8Si +AlOCl+MgAl2Cl8+5H2O
Accessory substance AlOCl, MgAl in this reaction system2Cl8Easily process.
The ESEM of prepared attapulgite Quito hole silicon nanowires from Fig. 2 is for embodiment 1（SEM）Figure, can see Go out, porous silicon is interconnective nanometer wire shaped and nano particle composition, and the length of the nano wire of some porous silicons is more than 4 Micron, and nano wire is more homogeneous.
The transmission electron microscope of prepared attapulgite Quito hole silicon nanowires from Fig. 3 is for embodiment 1（TEM）In figure observes table Bright：Porous silicon assumes interconnective irregular loose structure, and porous silicon is in polycrystalline structure, and interlamellar spacing is 0. 31 nm, right Should be in (111) interplanar distance of crystalline silicon.
The attapulgite Quito hole silicon nanowires made using the example method makes lithium ion battery, further from Fig. 4's Visible in different multiplying constant current charge-discharge cycle life figure, after 250 circulations, under 0.372 A/g and 3.72 A/g current densities, Reversible capacity is up to 2258.6 mAh/g and 1086.9 mAh/g respectively.The excellent chemical property of this material has benefited from material The pattern of porous silicon nanowires alleviates the bulk effect of porous silicon and shortens Li+Diffusion rate.
Embodiment 2：
Step one：Aluminium powder and magnesium powder are mixed by the ratio with mass ratio for 1: 1 in advance, form the mixture of aluminium powder and magnesium powder.
Attapulgite containing 150g is added to after ultrasonic 1 hour in 300 mL aqueous solvents dry after filtering or being centrifuged Dry, obtain attapulgite.Then again by the mixture of attapulgite and alchlor and aluminium powder and magnesium powder again with mass ratio for 1 : 9: 2 mass ratio mixing, obtain the mixture containing attapulgite.
Step 2：Said mixture is placed in full of in the agate pot of argon gas, using planetary ball mill ball milling, ball material quality For 8: 1, rotating speed is 600 rpm to ratio, and Ball-milling Time is 8 h.
Step 3：After ball milling terminates, naturally cool to greenhouse and collect product, after being soaked with 0.1M watery hydrochloric acid, use distilled water Cyclic washing, finally removes remaining Si oxide with 3% hydrofluoric acid solution, obtains final product attapulgite Quito hole silicon nanowires.
SEM Fig. 5 and TEM Fig. 6 is shown in by prepared material.
The ESEM of prepared attapulgite Quito hole silicon nanowires from Fig. 5 is for embodiment 2（SEM）Figure, can see Go out, porous silicon is interconnective nanometer wire shaped and nano particle composition, and the length of the nano wire of some porous silicons is more than 4 Micron, and nano wire is more homogeneous.
The transmission electron microscope of prepared attapulgite Quito hole silicon nanowires from Fig. 6 is for embodiment 2（TEM）In figure observes table Bright：Porous silicon assumes interconnective irregular loose structure, and porous silicon is in crystal structure, and interlamellar spacing is 0. 30 nm, corresponding (111) interplanar distance in crystalline silicon.
Embodiment 3：
Step one：Attapulgite containing 150g is added to after ultrasonic 1 hour in 300 mL aqueous solvents and filters or be centrifuged After be dried, obtain attapulgite, then again attapulgite and alchlor, aluminium powder mixed with 1: 8: 1 mass ratio, acquirement contains The mixture of attapulgite.
Step 2：Said mixture is placed in full of in the agate pot of argon gas, using planetary ball mill ball milling, ball material quality For 5: 1, rotating speed is 400 rpm to ratio, and Ball-milling Time is 6 h.
Step 3：After ball milling terminates, naturally cool to greenhouse and collect product, after being soaked with 0.1M watery hydrochloric acid, use distilled water Cyclic washing, finally removes remaining Si oxide with 3% hydrofluoric acid solution, obtains final product attapulgite Quito hole silicon nanowires.
Embodiment 4：
Step one：Attapulgite containing 150g is added to ultrasonic 1 hour in 300 mL aqueous solvents and is dried after filtering later, Obtain attapulgite, then again attapulgite and alchlor, aluminium powder are mixed with 1: 6: 1 mass ratio, obtain and contain concave convex rod The mixture of soil.
Step 2：Said mixture is placed in full of in the agate pot of argon gas, using planetary ball mill ball milling, ball material quality For 1: 1, rotating speed is 500 rpm to ratio, and Ball-milling Time is 40 h.
Step 3：After ball milling terminates, naturally cool to greenhouse and collect product, after being soaked with 0.1M watery hydrochloric acid, use distilled water Cyclic washing, finally removes remaining Si oxide with 3% hydrofluoric acid solution, obtains final product attapulgite Quito hole silicon nanowires.
Embodiment 5：
Step one：Attapulgite containing 150 g is added to after ultrasonic 0.5 hour in the hydrochloric acid of 300 mL 0.01M and filters Or it is dried after centrifugation, obtains attapulgite, then attapulgite and alchlor, aluminium powder are mixed with 1: 12: 1 mass ratio again Close, obtain the mixture containing attapulgite.
Step 2：Said mixture is placed in full of in the agate pot of argon gas, using planetary ball mill ball milling, ball material quality For 15: 1, rotating speed is 500 rpm to ratio, and Ball-milling Time is 8 h.
Step 3：After ball milling terminates, naturally cool to greenhouse and collect product, after being soaked with 0.1M watery hydrochloric acid, use distilled water Cyclic washing, finally removes remaining Si oxide with 4% hydrofluoric acid solution, obtains final product attapulgite Quito hole silicon nanowires.
Embodiment 6：
Step one：Attapulgite containing 150g is added to ultrasonic 0.5 hour in the aqueous hydrochloric acid solution of 300 mL 0.01M Filter afterwards or centrifugation after be dried, obtain attapulgite, then again by attapulgite and alchlor, aluminium powder with 1: 20: 20 Mass ratio mixes, and obtains the mixture containing attapulgite.
Step 2：Said mixture is placed in full of in the agate pot of argon gas, using planetary ball mill ball milling, ball material quality For 20: 1, rotating speed is 800 rpm to ratio, and Ball-milling Time is 1h.
Step 3：After ball milling terminates, naturally cool to greenhouse and collect product, after being soaked with 0.1M watery hydrochloric acid, use distilled water Cyclic washing, finally removes remaining Si oxide with 3% hydrofluoric acid solution, obtains final product attapulgite Quito hole silicon nanowires.
Embodiment 7：
Step one：Attapulgite containing 150g is added to after ultrasonic 0.5 hour in the hydrochloric acid of 300 mL 0.01M and filters Or it is dried after centrifugation, obtains attapulgite, then attapulgite and alchlor, aluminium powder are mixed with 1: 8: 1 mass ratio again Close, obtain the mixture containing attapulgite.
Step 2：Said mixture is placed in full of in the agate pot of argon gas, using planetary ball mill ball milling, ball material quality For 7: 1, rotating speed is 300 rpm to ratio, and Ball-milling Time is 16 h.
Step 3：After ball milling terminates, naturally cool to greenhouse and collect product, after being soaked with 0.1M watery hydrochloric acid, use distilled water Cyclic washing, obtains final product attapulgite Quito hole silicon nanowires.
Embodiment 8：
Step one：Aluminium powder and magnesium powder are mixed by the ratio with mass ratio for 2: 1 in advance, form the mixture of aluminium powder and magnesium powder.
By the attapulgite containing 150g be added to after ultrasonic 0.5 hour in the hydrochloric acid of 300 mL 0.01M filter or After centrifugation be dried, obtain attapulgite, then again by the mixture of attapulgite and alchlor and aluminium powder and magnesium powder again with Mass ratio is 1: 14: 1 mass ratio mixing, obtains the mixture containing attapulgite.
Step 2：Said mixture is placed in full of in the agate pot of argon gas, using planetary ball mill ball milling, ball material quality For 8: 1, rotating speed is 800 rpm to ratio, and Ball-milling Time is 15 h.
Step 3：After ball milling terminates, naturally cool to greenhouse and collect product, after being soaked with 0.1M watery hydrochloric acid, use distilled water Cyclic washing, finally removes remaining Si oxide with 3% hydrofluoric acid solution, obtains final product attapulgite Quito hole silicon nanowires.
Embodiment 9：
Step one：Attapulgite containing 150g is added to after ultrasonic 1 hour in 300 mL aqueous solvents and filters or be centrifuged After be dried, obtain attapulgite, then the quality with mass ratio for 1: 26: 15 by attapulgite and alchlor and aluminium powder again Ratio mixing, obtains the mixture containing attapulgite.
Step 2：Said mixture is placed in full of in the agate pot of argon gas, using planetary ball mill ball milling, ball material quality For 9: 1, rotating speed is 600 rpm to ratio, and Ball-milling Time is 18 h.
Step 3：After ball milling terminates, naturally cool to greenhouse and collect product, after being soaked with 0.1M watery hydrochloric acid, use distilled water Cyclic washing, last 70 DEG C of 2M NaOH solution removes remaining Si oxide, you can obtain the porous silicon nanowires of fine work.
Embodiment 10：
Step one：After just the attapulgite containing 150 g is added to ultrasonic 1 hour in 300 mL aqueous solvents filter or from It is dried after the heart, obtains attapulgite, be then 1: 20: 1 by attapulgite and alchlor and magnesium powder and aluminium powder mass ratio again: 1 mass ratio mixing, obtains the mixture containing attapulgite.
Step 2：Above-mentioned mixture is placed in full of in argon gas agate pot, using planetary ball mill ball milling, ball material quality For 15: 1, rotating speed is 400 rpm to ratio, and Ball-milling Time is 5h.
Step 3：After ball milling terminates, naturally cool to greenhouse and collect product, after being soaked with 0.1M watery hydrochloric acid, use distilled water Cyclic washing, last 70 DEG C of 2M NaOH solution removes remaining Si oxide, you can obtain the porous silicon nanowires of fine work.
Embodiment 11：
Step one：Attapulgite containing 150 g is added to after ultrasonic 1 hour in 300 mL aqueous solvents and filters or be centrifuged After be dried, obtain attapulgite, then the quality with mass ratio for 1: 16: 6 by attapulgite and alchlor and aluminium powder again Ratio mixing, obtains the mixture containing attapulgite.
Step 2：Said mixture is placed in full of in the agate pot of argon gas, using planetary ball mill ball milling, ball material quality For 17: 1, rotating speed is 400 rpm to ratio, and Ball-milling Time is 3 h.
Step 3：After ball milling terminates, naturally cool to greenhouse and collect product, after being soaked with 0.1M watery hydrochloric acid, use distilled water Cyclic washing, obtains final product attapulgite Quito hole silicon nanowires.
Embodiment 12：
Step one：Attapulgite containing 150 g is added to after ultrasonic 0.5 hour in the hydrochloric acid of 300 mL 0.01M and filters Or be dried after centrifugation, obtain attapulgite, then again by attapulgite and alchlor and aluminium powder with mass ratio for 1: 24: 12 mass ratio mixing, obtains the mixture containing attapulgite.
Step 2：Said mixture is placed in full of in the agate pot of argon gas, using planetary ball mill ball milling, ball material quality For 18: 1, rotating speed is 500 rpm to ratio, and Ball-milling Time is 4h.
Step 3：After ball milling terminates, naturally cool to greenhouse and collect product, after being soaked with 0.1M watery hydrochloric acid, use distilled water Cyclic washing, obtains final product attapulgite Quito hole silicon nanowires.
Embodiment 13：
Step one：Attapulgite containing 150 g is added to after ultrasonic 0.5 hour in the hydrochloric acid of 300 mL 0.01M and filters Or be dried after centrifugation, obtain attapulgite, then again by attapulgite and alchlor and aluminium powder with mass ratio for 1: 40: 40 mass ratio mixing, obtains the mixture containing attapulgite.
Step 2：Said mixture is placed in full of in the agate pot of argon gas, using planetary ball mill ball milling, ball material quality For 18: 1, rotating speed is 500 rpm to ratio, and Ball-milling Time is 4h；
Step 3：After ball milling terminates, naturally cool to greenhouse and collect product, after being soaked with 0.1M watery hydrochloric acid, with distilled water repeatedly Washing, you can the porous silicon nanowires of doping Si oxide.
Embodiment 14：
Step one：Attapulgite containing 150 g is added to after ultrasonic 0.5 hour in the hydrochloric acid of 300 mL 0.01M and filters Or solution is dried after centrifugation, obtains attapulgite, then again by attapulgite and alchlor and aluminium powder with mass ratio for 1 : 50: 50 mass ratio mixing, obtain the mixture containing attapulgite.
Step 2：Above-mentioned mixture is placed in full of in argon gas agate pot, using planetary ball mill ball milling, ball material quality For 6: 1, rotating speed is 800 rpm to ratio, and Ball-milling Time is 4 h.
Step 3：After ball milling terminates, naturally cool to greenhouse and collect product, after being soaked with 0.1M watery hydrochloric acid, use distilled water Cyclic washing, obtains the porous silicon nanowires of doping Si oxide.
Embodiment 15：
Step one：Attapulgite containing 150 g is added to after ultrasonic 0.5 hour in the hydrochloric acid of 300 mL 0.01M and filters Or be dried after centrifugation, obtain attapulgite, then again by attapulgite and alchlor and aluminium powder with mass ratio for 1: 15: 40 mass ratio mixing, obtains the mixture containing attapulgite.
Step 2：Above-mentioned mixture is placed in full of in argon gas agate pot, using planetary ball mill ball milling, ball material quality For 20: 1, rotating speed is 200 rpm to ratio, and Ball-milling Time is 12h.
Step 3：After ball milling terminates, naturally cool to greenhouse and collect product, after being soaked with 0.1M watery hydrochloric acid, use distilled water Cyclic washing, obtains final product attapulgite Quito hole silicon nanowires.

Claims (5)

1. a kind of ball-milling preparation method of attapulgite Quito hole silicon nanowire material is it is characterised in that comprise the following steps：
1）Filter after will be ultrasonically treated for the solution containing attapulgite or be centrifuged, be then dried and obtain dry attapulgite, then By the mixture of the attapulgite being dried and alchlor, aluminium powder or aluminium powder and magnesium powder, obtain the mixture containing attapulgite；
2）Mixture containing attapulgite is placed in ball mill, is ground under the conditions of argon gas；
3）Grinding is cooled to greenhouse after terminating, collect product, after being soaked with watery hydrochloric acid, with distilling water washing, obtains final product attapulgite Quito hole silicon nanowires.
2. a kind of ball-milling preparation method of attapulgite Quito hole silicon nanowire material according to claim 1, its feature exists In mixture and the attapulgite being dried of described aluminium powder or aluminium powder and magnesium powder, alchlor mixing quality ratio for 1～50: 1: 2～50.
3. a kind of ball-milling preparation method of attapulgite Quito hole silicon nanowire material according to claim 1, its feature exists When described grinding, in ball mill, the mass ratio that feeds intake of mill ball and the described mixture containing attapulgite is 1～20: 1, rotating speed For 200～1200 rpm, milling time is 1～40h.
4. a kind of ball-milling preparation method of attapulgite Quito hole silicon nanowire material according to claim 1, its feature exists In described step 3）In for soak watery hydrochloric acid concentration be 0.1M.
5. according to claim 12 or attapulgite Quito hole silicon nanowire material described in 3 or 5 a kind of ball-milling preparation method, It is characterized in that in described step 3）Afterwards, then with the aqueous slkali of hydrofluoric acid or dense heat remove remaining porous silicon oxide, obtain final product Refined attapulgite Quito hole silicon nanowires.
CN201610807467.6A 2016-09-07 2016-09-07 Ball-milling preparation method for attapulgite-based porous silicon nanowire material Pending CN106410133A (en)

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