CN106299283A - The ball-milling preparation method of hole, rice husk Quito silicon nano material - Google Patents
The ball-milling preparation method of hole, rice husk Quito silicon nano material Download PDFInfo
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- CN106299283A CN106299283A CN201610807180.3A CN201610807180A CN106299283A CN 106299283 A CN106299283 A CN 106299283A CN 201610807180 A CN201610807180 A CN 201610807180A CN 106299283 A CN106299283 A CN 106299283A
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- H—ELECTRICITY
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- 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
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- H—ELECTRICITY
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- 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
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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
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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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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The ball-milling preparation method of hole, rice husk Quito silicon nano material, belong to nano-electrode material preparing technical field, in atmosphere will after washing and drying rice husk heated oxide or incomplete oxidation, obtain rice hull ash, then after soaking with dilute hydrochloric acid, it is dried with after distilled water wash, obtains dried rice hull ash；Compound is obtained after dried rice hull ash and aluminium powder or aluminium powder and magnesium powder and the mixing of corresponding chloride, then it is ground in compound is placed in ball mill, is cooled to greenhouse, collect product, after soaking with dilute hydrochloric acid, with distilled water wash, obtain hole, rice husk Quito silicon nano material.Process of the present invention is simple, and the prices of raw materials are cheap, productivity is high, and utilizes solid state reaction preparation to be conducive to industrialized production, and obtains the achievement of the chemical property of excellence.
Description
Technical field
The invention belongs to nano-electrode material preparing technical field, particularly to the preparation of hole, rice husk Quito silicon nano material
Technology.
Background technology
Along with exhaustion and the aggravation of environmental problem of fossil resource, the mankind are in the urgent need to cleaning, energy efficient, continuable
Source, and associated energy is changed and storage new technique.Energy storage device is the indispensable crucial device of modern society
One of part.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, tap density
Little, it is impossible to meet the demand of energy-density lithium ion battery.Thus, the negative material of searching height ratio capacity substitutes graphite gesture and exists
Must go.Silicon has the theoretical specific capacity of up to 4200 mAh/g and moderate voltage platform, is the lithium being hopeful most to substitute graphite
One of ion battery cathode material.But, silicon does not only exist serious bulk effect (reaching more than 300%) in cyclic process, and
And it is easily caused silicon grain pulverizing, and forcing electrode structure avalanche, and the poorly conductive of silicon, these shortcomings make silicon based anode material exist
By the biggest obstruction in actual application.In order to reduce the change in volume of silicon, generally use its nanorize (dimensional effect) or
Prepare loose structure (porous effect) and carry out being coated with the method for (depression effect) on its surface to improve its cyclicity
Energy.Wen(Electrochemistry Communi-cations, 2013,29:67-70) et al. first synthesize SiO2Nanotube,
Then preparing nano-tube with magnesiothermic reduction, nano-tube has good cycle performance；Yao (Nano Lett., 2011,
11 (7): 2949-2954) et al. then with SiO2Nanosphere is template, in its surface high-temp (485 DEG C) silane cracking cladding
Silicon, obtains Si hollow nano-sphere, and after 700 charge and discharges circulation, capacity still has about 1500 mAh/g, and capability retention is up to 55%.
Lee(Angew.Chem.Int.Ed., 2012,51 (11): 2767-2771) et al. utilize metallic catalyst etch block SiO
Material, obtains 3D porous SiO, then high temperature (> 800 DEG C) under by chemistry auxiliary Heat disproportionation reaction obtain 3D porous silicon material
Material, material capacity is up to 1600 mAh/g, and after circulating 100 times, capability retention is 91.3%；Chen
(Angew.Chem.Int.Ed.
, 2012,51 (10): 2409-2413) et al. at room temperature synthesize hollow porous SiO2, high-temperature calcination remove template and
Surfactant, then obtains hollow porous silicon with magnesiothermic reduction, and nano silicon particles size reaches 3762 at 100 nm, reversible capacity
MAh/g, cycle performance is excellent.As fully visible, by the careful design of material structure, obtain the silicon materials with loose structure,
The bulk effect of silicon can be obviously reduced, improve the chemical property (especially multiplying power and cycle performance) of silicon.While it is true,
In the preparation process of above-mentioned porous silica material, more expensive raw material and complicated preparation technology, cause material preparation cost higher, and
Typically require high temperature, seriously constrain the application of silicon based anode material.Nearest research shows, prepares silicon materials and typically requires relatively
High temperature, even if using magnesiothermic reduction technology to be also required to higher than 550 DEG C.Such as: Zhi hao Bao (RSC Adv.,
2013,3 (26): 10145-10149) and Yi Cui(Sci.Rep., 2013,3:1919-1925) Liang Ge seminar is with agriculture
Product rice husk is silicon source, uses magnesiothermic reduction technology to prepare porous silica material, and obtains the chemical property of excellence.It addition,
Jaephil Cho (Angew. Chem. Int. Ed, 2008,47 (52): 10151-10154) group combines silicon dioxide
Make template and naphthalene sodium reduction SiCl4Preparation 3-D porous silicon, under 1C multiplying power, after 100 circulations, reversible capacity is up to 2800
mAh/g.But, these methods are the most complicated and relatively costly.
Rice husk is cheap and easy to get as one, the waste material of sustainable use.Rice husk mainly by lignin, cellulose,
Hemicellulose, SiO2Form with a small amount of metal-oxide etc..Rice husk is of many uses, SiO therein2It is cheap silicon source, conventional
In preparing the materials such as concrete filter aid and silicide.Organic matter fractions in rice husk is then used for preparing activated carbon, as useless
The adsorbing material of water process and catalyst carrier etc..While it is true, rice husk is as the agricultural wastes of a kind of rich reserves, seek
The high value added utilization of rice husk is significant.
In recent years, the energy storage device such as lithium ion battery obtains more coming along with the raising of the market demand, high-performance energy storage material
The favor of the most researcheres and attention.But higher cost of material and complicated preparation technology are unfavorable for market development, therefore,
Seeking cheap raw material and easy syntheti c route, the development for energy storage industry is significant.
Summary of the invention
Present invention aim at proposing hole, the rice husk Quito silicon nano material that a kind of syntheti c route is simple, cost of manufacture is cheap
Ball-milling preparation method.
The present invention comprises the steps:
1) in atmosphere will after washing and drying rice husk heated oxide or incomplete oxidation, obtain rice hull ash, then use dilute salt
After acid soak, it is dried with after distilled water wash, obtains dried rice hull ash；
2) after dried rice hull ash and aluminium powder or aluminium powder and magnesium powder and the mixing of corresponding chloride, compound is obtained, so
After compound is placed in ball mill in be ground；
3) grinding is cooled to greenhouse after terminating, and collects product, after soaking with dilute hydrochloric acid, with distilled water wash, obtains rice husk Quito
Hole silicon nano material.
The present invention, with cheap rice husk as raw material, utilizes the silicon in rice husk, oxygen element, rice husk oxidation can be obtained nanometer
The SiO of porous2Then restore, prepare the high power capacity silicium cathode material of lithium ion battery.It addition, utilize in rice husk simultaneously
Carbon and element silicon, i.e. obtain Nano-meter SiO_2 in rice husk2/ C composite, Nano-meter SiO_2 therein2Be reduced to silicon, simultaneously with
Carbon, as conductive agent, active substance and the volumetric expansion of alleviation porous silicon, has the electrochemical lithium storage content higher than graphite.In view of
Rice husk can be as lithium ion battery active substance silicon and the common denominator of carbon, and the present invention is with the Nano-meter SiO_2 in rice husk2Pass through ball
Mill method is reduced into porous silicon nano material under conditions of reducing agent exists, simultaneously can also be by the air oxidation journey to rice husk
Degree regulates wherein carbon content, it is thus achieved that lithium ion battery silicon (carbon) composite negative pole material.
It is simple that the whole synthesis technique of the present invention has process, and the prices of raw materials are cheap, productivity advantages of higher, and utilize solid phase
Reaction preparation is conducive to industrialized production, and obtains the achievement of the chemical property of excellence.
Specifically have the beneficial effect that:
1. the present invention uses the method that ball mill grinding prepares hole, rice husk Quito silicon nano material, simple to operate, cost is relatively low, and
It is substantially reduced reaction temperature, and the productivity of final products is high, can realize large-scale production.
2. the material prepared by the present invention can be used for high-capacity lithium ion cell, catalyst carrier, ultracapacitor,
The numerous areas such as catalyst, adsorbent and gas storage.
3., after 250 circulations, under 0.372 A/g and 1.86A/g electric current density, reversible capacity is up to respectively
1469.9mAh/g and 757.9mAh/g.The chemical property of this material excellence has benefited from the pattern of silicon porous in material and alleviates
The bulk effect of silicon and shorten Li+Diffusion rate.
4. use the material made of the inventive method can be used for the high-quality lithium ion battery porous silicon negative material of practicality with
And high-capacity lithium ion cell, ultracapacitor, catalyst carrier, lithium-sulfur cell, medicament transport, bio-imaging, water process etc.
Multiple fields.
Further, dried rice hull ash of the present invention and aluminium powder or magnesium powder and corresponding muriatic mixing
Mass ratio is 1: 1～25: 2～45.Aluminum chloride with denier more than attapulgite purpose be the high-temperature fusion for aluminum chloride
Salt can fully wrap up attapulgite, so can reduce the mixture of expensive aluminium powder or aluminium powder and magnesium powder as reduction
Between the amount of agent, and the interconnective porous silicon nano material of preparation, there is well balanced mesoporous and macropore.
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
100～3000 rpm, milling time is 2～40 h.Mill ball and the mass ratio that feeds intake are more than 1, and effect is to make to feed intake fully
Contact mill ball, reduces milling time.Rotating speed is 200～3000 rpm, and milling time is 2～40 h, in this scope
The productivity of rotating speed and milling time porous silicon nanometer is higher, and has good between the interconnective porous silicon nano material of preparation
Mesoporous and the macropore of good balance, if rotating speed and milling time are less than this scope, then the productivity of porous silicon nano material is on the low side；As
Really rotating speed and milling time are higher than this scope, although the productivity of porous nano silicon is higher, but corresponding energy consumption is the highest, and
Macropore in porous silicon nano material is as ball milling excessively disappears.
Corresponding chloride of the present invention is AlCl3Or AlCl3And MgCl2In mixture at least any one.Necessary
Containing chloride AlCl3Effect be: because during ball milling, AlCl3Fuse salt can be become owing to frictionally heating, its
Liquid phase behavior is as reaction medium, it is ensured that reactant is in close contact each other.Second, it is because aluminum chloride and can participate in instead
Should, the oxygen element in Si oxide is removed with the formation generating AlOCl compound, it is to avoid form stable aluminium oxide passivation
Layer, thus may advantageously facilitate persistently carrying out of reaction, and AlOCl removes with dilute hydrochloric acid easily.3rd, due to melted three
Aluminum chloride is at the existence Al=Al of ionization process3++ 3e, produces the electronics of substantial amounts of high activity, produces ion and solvation
Electronics has the strongest reducing power, so that being smoothed out under the relatively low temperature conditions that produces in ball milling of reduction reaction.
In described step 3) the concentration of dilute hydrochloric acid for soaking be 0.1M effect be remove unreacted aluminium powder or
(with) magnesium powder and the corresponding impurity such as aluminum silicide or magnesium silicide.
In order to obtain hole, purity higher attapulgite Quito silicon nanowires, after described step 3), then with Fluohydric acid. or
The aqueous slkali of the dense heat of person removes remaining Si oxide, obtains refined hole, rice husk Quito silicon nano material.
Accompanying drawing explanation
Fig. 1 is the XRD figure of hole, rice husk Quito silicon nano material prepared by embodiment 1.
Fig. 2 is scanning electron microscope (SEM) figure of hole, rice husk Quito silicon nano material prepared by embodiment 1.
Fig. 3 is transmission electron microscope (TEM) figure of hole, rice husk Quito silicon nano material prepared by embodiment 1.
Fig. 4 is high power transmission electron microscope (HR-TEM) figure of hole, rice husk Quito silicon nano material prepared by embodiment 1.
Fig. 5 is the permanent in different multiplying of the lithium ion battery prepared of hole, rice husk Quito silicon nano material prepared by embodiment 1
Stream charge and discharge circulation life figure.
Fig. 6 is scanning electron microscope (SEM) figure of prepared hole, rice husk Quito silicon nano material in embodiment 2.
Fig. 7 is transmission electron microscope (TEM) figure of prepared hole, rice husk Quito silicon nano material in embodiment 2.
Detailed description of the invention
Embodiment 1
Step one: with rice husk after washing and drying as raw material, with microwave device 1000 W microwave heated oxygen in air atmosphere
Change and obtain rice hull ash in 30 minutes, after then soaking with dilute hydrochloric acid, be finally dried with after distilled water cyclic washing, obtain dried
Rice hull ash.
Step 2: by dried rice hull ash and aluminium powder and AlCl3Mass ratio with 1: 1: 10 mixes, and obtains mixture.
Step 3: be placed in by mixture in the Achates tank of full noble gas, uses planetary ball mill ball milling, ball material quality
Ratio is 5: 1, and rotating speed is 400 rpm, and Ball-milling Time is 20 h.
Step 4: after ball milling terminates, naturally cools to greenhouse and collects product, after soaking with 0.1 M dilute hydrochloric acid, use distilled water
Cyclic washing, finally removes remaining Si oxide with the hydrofluoric acid solution that mass percent is 3%, obtains rice husk Ji Duokongguina
Rice material.
Product and performance test:
From the XRD figure of hole, rice husk Quito silicon nano material, the XRD diffraction maximum of the sample obtained prepared by this example of Fig. 1
As it is shown in figure 1, only there is diffraction maximum at 28.6 °, 46.9 °, 56.2 °, 69.4 °, 76.3 ° and 88.0 °, these diffraction maximums are
The diffraction maximum of crystalline silicon, corresponds respectively to (111), (220), (311), (400), (331) and the interplanar of (006) of crystalline silicon
Away from.Therefore, rice husk, after the technique of embodiment 1, can obtain pure silicon materials.Concrete reaction equation is as follows: 4Al+
3SiO2 +2AlCl3By-product AlOCl in → 3Si+6AlOCl, and this reaction system easily processes.
Fig. 2 is scanning electron microscope (SEM) figure of hole, rice husk Quito silicon nano material prepared by embodiment 1, can from figure
Going out, hole, rice husk Quito silicon nano material is made up of tiny nano-particle, and nano-particle is the most homogeneous.
Fig. 3 is transmission electron microscope (TEM) figure of hole, rice husk Quito silicon nano material prepared by embodiment 1, observes from figure
Hole, rice husk Quito silicon nano material is made up of the homogeneous nano-particle that is connected with each other, and constitutes good big between nano-particle
Hole.
Fig. 4 is high power transmission electron microscope (HR-TEM) figure of hole, rice husk Quito silicon nano material prepared by embodiment 1, from Fig. 4
Can be seen that porous silicon presents irregular loose structure, porous silicon is crystal structure, and interlamellar spacing is 0. 31 nm, corresponding to crystal
(111) interplanar distance of silicon.
Hole, the rice husk Quito silicon nano material preparation further using the example method to make obtains lithium ion battery, in difference
Multiplying power constant current charge-discharge cycle life figure, as it is shown in figure 5, after 250 circulations, under 0.372 A/g and 1.86A/g electric current density,
Reversible capacity is up to 1469.9 mAh/g and 757.9 mAh/g respectively.The chemical property of this material excellence has benefited from material
The structure of short grained nano-silicon pattern and porous alleviates the bulk effect of silicon and shortens Li+Diffusion rate.
Embodiment 2
Step one: with rice husk after washing and drying as raw material, with microwave device 1000 W microwave heated oxygen in air atmosphere
Change and obtain rice hull ash in 30 minutes, after then soaking with dilute hydrochloric acid, be finally dried with after distilled water cyclic washing, obtain dried
Rice hull ash.
Step 2: by dried rice hull ash and aluminium powder, magnesium powder, AlCl3Mass ratio with 1: 1: 1: 9 mixes, and obtains mixed
Compound.
Step 3: be placed in by said mixture in full noble gas Achates tank, uses planetary ball mill ball milling, ball material matter
Amount ratio is 5: 1, and rotating speed is 800 rpm, and Ball-milling Time is 16 h.
Step 4: after ball milling terminates, naturally cools to greenhouse and collects product, after soaking with 0.1M dilute hydrochloric acid, use distilled water
Cyclic washing, finally removes remaining Si oxide with 3% hydrofluoric acid solution, i.e. can get hole, rice husk Quito silicon nano material.
Product is identified:
Fig. 6 is scanning electron microscope (SEM) figure of hole, rice husk Quito silicon nano material prepared by embodiment 2, it can be seen that rice
Hole, shell Quito silicon nano material is made up of tiny nano-particle, and nano-particle is the most homogeneous.
Fig. 7 is transmission electron microscope (TEM) figure of hole, rice husk Quito silicon nano material prepared by embodiment 2, observes from figure
Hole, rice husk Quito silicon nano material is made up of the homogeneous nano-particle that is connected with each other, and constitutes good big between nano-particle
Hole.
Embodiment 3
Step one: with rice husk after washing and drying as raw material, aoxidizes with microwave device 800 W microwave heating in air atmosphere
Within 15 minutes, obtain rice hull ash, after then soaking with dilute hydrochloric acid, be finally dried with after distilled water cyclic washing, obtain dried rice
Shell ash.
Step 2: by dried rice hull ash and aluminium powder, magnesium powder, AlCl3Mass ratio with 1: 0.5: 0.5: 12 mixes, and takes
Obtain mixture.
Step 3: be placed in by above-mentioned mixture in full noble gas Achates tank, uses planetary ball mill ball milling, ball material
Mass ratio is 4: 1, and rotating speed is 600 rpm, and Ball-milling Time is 16 h.
Step 4: after ball milling terminates, naturally cools to greenhouse and collects product, after soaking with 0.1M dilute hydrochloric acid, use distilled water
Cyclic washing, the remaining Si oxide of 2M NaOH solution removal of last 70 DEG C, the porous silicon that i.e. can get rice husk base carbon doping is received
Rice material.
Embodiment 4
Step one: with rice husk after washing and drying as raw material, aoxidizes with microwave device 700 W microwave heating in air atmosphere
Within 18 minutes, obtain rice hull ash, after then soaking with dilute hydrochloric acid, be finally dried with after distilled water cyclic washing, obtain dried rice
Shell ash.
Step 2: by dried rice hull ash and aluminium powder, magnesium powder, AlCl3And MgCl2With 1: 0.5: 0.5: the mass ratio of 4: 4
Mixing, obtains mixture.
Step 3: be placed in by above-mentioned mixture in full noble gas Achates tank, uses planetary ball mill ball milling, ball material
Mass ratio is 5: 1, and rotating speed is 500 rpm, and Ball-milling Time is 14 h.
Step 4: after ball milling terminates, naturally cools to greenhouse and collects product, after soaking with 0.1M dilute hydrochloric acid, use distilled water
Cyclic washing, the remaining Si oxide of 2M NaOH solution removal of last 70 DEG C, the porous silicon that i.e. can get rice husk base carbon doping is received
Rice material.
Embodiment 5
Step one: with rice husk after washing and drying as raw material, with microwave device 1000 W microwave heated oxygen in air atmosphere
Change and obtain rice hull ash in 30 minutes, after then soaking with dilute hydrochloric acid, be finally dried with after distilled water cyclic washing, obtain dried
Rice hull ash.
Step 2: by dried rice hull ash and aluminium powder, AlCl3Mass ratio with 1: 1: 9 mixes, and obtains mixture.
Step 3: be placed in by above-mentioned mixture in full noble gas Achates tank, uses planetary ball mill ball milling, ball material
Mass ratio is 5: 1, and rotating speed is 600 rpm, and Ball-milling Time is 10 h；
Step 4: after ball milling terminates, naturally cools to greenhouse and collects product, after soaking with 0.1 M dilute hydrochloric acid, with distilled water repeatedly
Washing, finally removes remaining Si oxide with 3% hydrofluoric acid solution, i.e. can get hole, rice husk Quito silicon nano material.
Embodiment 6
Step one: with rice husk after washing and drying as raw material, aoxidizes with microwave device 900 W microwave heating in air atmosphere
Within 40 minutes, obtain rice hull ash, after then soaking with dilute hydrochloric acid, be finally dried with after distilled water cyclic washing, obtain dried rice
Shell ash.
Step 2: by dried rice hull ash and aluminium powder, magnesium powder, AlCl3Mass ratio with 1: 0.75: 0.75: 8 mixes,
Obtain mixture.
Step 3: be placed in by above-mentioned mixture in full noble gas Achates tank, uses planetary ball mill ball milling, ball material
Mass ratio is 5: 1, and rotating speed is 800 rpm, and Ball-milling Time is 16 h.
Step 4: after ball milling terminates, naturally cools to greenhouse and collects product, after soaking with 0.1M dilute hydrochloric acid, use distilled water
Cyclic washing, finally removes remaining Si oxide with 3% hydrofluoric acid solution, i.e. can get hole, rice husk Quito silicon nano material.
Embodiment 7
Step one: with rice husk after washing and drying as raw material, aoxidizes with microwave device 700 W microwave heating in air atmosphere
Within 15 minutes, obtain rice hull ash, after then soaking with dilute hydrochloric acid, be finally dried with after distilled water cyclic washing, obtain dried rice
Shell ash.
Step 2: by dried rice hull ash and aluminium powder, magnesium powder, AlCl3Mass ratio with 1: 0.5: 0.5: 8 mixes, and takes
Obtain mixture.
Step 3: be placed in by above-mentioned mixture in full noble gas Achates tank, uses planetary ball mill ball milling, ball material
Mass ratio is 4: 1, and rotating speed is 400 rpm, and Ball-milling Time is 16 h.
Step 4: after ball milling terminates, naturally cools to greenhouse and collects product, after soaking with 0.1M dilute hydrochloric acid, use distilled water
Cyclic washing, is eventually adding 3% hydrofluoric acid solution and removes remaining Si oxide, and the porous silicon that i.e. can get rice husk base carbon doping is received
Rice material.
Embodiment 8
Step one: with rice husk after washing and drying as raw material, aoxidizes with microwave device 700 W microwave heating in air atmosphere
Within 16 minutes, obtain rice hull ash, after then soaking with dilute hydrochloric acid, be finally dried with after distilled water cyclic washing, obtain dried rice
Shell ash.
Step 2: by dried rice hull ash and aluminium powder, magnesium powder, AlCl3、MgCl2With 1: 0.5: 0.5: the mass ratio of 5: 5
Mixing, obtains mixture.
Step 3: after ball milling terminates, is placed in above-mentioned mixture in full noble gas Achates tank, uses planetary ball mill
Machine ball milling, ball material mass ratio is 5: 1, and rotating speed is 500 rpm, and Ball-milling Time is 14 h.
Step 4: after ball milling terminates, naturally cools to greenhouse and collects product, after soaking with 0.1M dilute hydrochloric acid, use distilled water
Cyclic washing, is eventually adding 3% hydrofluoric acid solution reaction and removes remaining Si oxide, i.e. can get the porous of rice husk base carbon doping
Silicon nano material.
Embodiment 9
Step one: with rice husk after washing and drying as raw material, with microwave device 1000 W microwave heated oxygen in air atmosphere
Change and obtain rice hull ash in 30 minutes, after then soaking with dilute hydrochloric acid, be finally dried with after distilled water cyclic washing, obtain dried
Rice hull ash.
Step 2: by dried rice hull ash and aluminium powder, AlCl3Mass ratio with 1: 1: 10 mixes, and obtains mixture.
Step 3: be placed in by above-mentioned mixture in full noble gas Achates tank, uses planetary ball mill ball milling, ball material
Mass ratio is 5: 1, and rotating speed is 600 rpm, and Ball-milling Time is 10 h.
Step 4: after ball milling terminates, naturally cools to greenhouse and collects product, after soaking with 0.1M dilute hydrochloric acid, use distilled water
It is dried after cyclic washing, i.e. can get rice husk base Si oxide doping porous silicon nano material.
Embodiment 10
Step one: with rice husk after washing and drying as raw material, aoxidizes with microwave device 900 W microwave heating in air atmosphere
Within 50 minutes, obtain rice hull ash, after then soaking with dilute hydrochloric acid, be finally dried with after distilled water cyclic washing, obtain dried rice
Shell ash.
Step 2: by dried rice hull ash and aluminium powder, magnesium powder, AlCl3Mass ratio with 1: 1: 0.5: 8 mixes, and obtains
Mixture.
Step 3: be placed in by above-mentioned mixture in full noble gas Achates tank, uses planetary ball mill ball milling, ball material
Mass ratio is 5: 1, and rotating speed is 800 rpm, and Ball-milling Time is 16 h.
Step 4: after ball milling terminates, naturally cools to greenhouse and collects product, after soaking with 0.1 M dilute hydrochloric acid, use distilled water
It is dried after cyclic washing, i.e. can get rice husk base Si oxide doping porous silicon nano material.
Embodiment 11
Step one: with rice husk after washing and drying as raw material, aoxidizes with microwave device 700 W microwave heating in air atmosphere
Within 15 minutes, obtain rice hull ash, after then soaking with dilute hydrochloric acid, be finally dried with after distilled water cyclic washing, obtain dried rice
Shell ash.
Step 2: by dried rice hull ash and aluminium powder, magnesium powder, AlCl3Mass ratio with 1: 0.5: 0.5: 8 mixes, and takes
Obtain mixture.
Step 3: be placed in by above-mentioned mixture in full noble gas Achates tank, uses planetary ball mill ball milling, ball material
Mass ratio is 4: 1, and rotating speed is 400 rpm, and Ball-milling Time is 16 h.
Step 4: after ball milling terminates, naturally cools to greenhouse and collects product, after soaking with 0.1M dilute hydrochloric acid, use distilled water
It is dried after cyclic washing, i.e. can get the porous silicon nano material of rice husk base carbon and Si oxide codope.
Embodiment 12
Step one: with rice husk after washing and drying as raw material, aoxidizes with microwave device 700 W microwave heating in air atmosphere
Within 25 minutes, obtain rice hull ash, after then soaking with dilute hydrochloric acid, be finally dried with after distilled water cyclic washing, obtain dried rice
Shell ash.
Step 2: by dried rice hull ash and aluminium powder, magnesium powder, AlCl3、MgCl2With 1: 0.66: 0.34: 6.5: 3.5
Mass ratio mixes, and obtains mixture.
Step 3: be placed in by above-mentioned mixture in full noble gas Achates tank, uses planetary ball mill ball milling, ball material
Mass ratio is 5: 1, and rotating speed is 500 rpm, and Ball-milling Time is 14 h.
Step 4: after ball milling terminates, naturally cools to greenhouse and collects product, after soaking with 0.1M dilute hydrochloric acid, use distilled water
It is dried after cyclic washing, i.e. can get the porous silicon nano material of rice husk base carbon and Si oxide codope.
Embodiment 13
Step one: will rice husk be raw material after washing and drying, aoxidizes 120 with diamond heating to 660 DEG C in air atmosphere
Minute obtain rice hull ash, after then soaking with dilute hydrochloric acid, be finally dried with after distilled water cyclic washing, obtain dried rice husk
Ash.
Step 2: by dried rice hull ash and aluminium powder, AlCl3Mass ratio with 1: 1: 8 mixes, and obtains mixture.
Step 3: be placed in by above-mentioned mixture in full noble gas Achates tank, uses planetary ball mill ball milling, ball material
Mass ratio is 3: 1, and rotating speed is 500 rpm, and Ball-milling Time is 15 h.
Step 4: after ball milling terminates, naturally cools to greenhouse and collects product, after soaking with 0.1 M dilute hydrochloric acid, use distilled water
Cyclic washing, finally removes remaining Si oxide by the 2M NaOH solution of 70 DEG C, i.e. can get rice husk base porous silicon nanometer material
Material.
Embodiment 14
Step one: will rice husk be raw material after washing and drying, aoxidizes 60 points with diamond heating to 760 DEG C in air atmosphere
Clock obtains rice hull ash, after then soaking with dilute hydrochloric acid, is finally dried with after distilled water cyclic washing, obtains dried rice husk
Ash.
Step 2: by dried rice hull ash and aluminium powder, magnesium powder, AlCl3Mass ratio with 1: 1.125: 0.375: 9 mixes
Close, obtain mixture.
Step 3: be placed in by above-mentioned mixture in full noble gas Achates tank, uses planetary ball mill ball milling, ball material
Mass ratio is 5: 1, and rotating speed is 600 rpm, and Ball-milling Time is 6 h.
Step 4: after ball milling terminates, naturally cools to greenhouse and collects product, after soaking with 0.1M dilute hydrochloric acid, use distilled water
Cyclic washing, finally removes remaining Si oxide with 3% hydrofluoric acid solution, i.e. can get hole, rice husk Quito silicon nano material.
Embodiment 15
Step one: will rice husk be raw material after washing and drying, aoxidizes 80 points with diamond heating to 500 DEG C in air atmosphere
Clock obtains rice hull ash, after then soaking with dilute hydrochloric acid, is finally dried with after distilled water cyclic washing, obtains dried rice husk
Ash.
Step 2: by dried rice hull ash and aluminium powder, magnesium powder, AlCl3Mass ratio with 1: 0.9: 0.9: 8 mixes, and takes
Obtain mixture.
Step 3: be placed in by above-mentioned mixture in full noble gas Achates tank, uses planetary ball mill ball milling, ball material
Mass ratio is 8: 1, and rotating speed is 600 rpm, and Ball-milling Time is 8 h.
Step 4: after ball milling terminates, naturally cools to greenhouse and collects product, after soaking with 0.1 M dilute hydrochloric acid, use distilled water
Cyclic washing, finally removes remaining Si oxide with 3% hydrofluoric acid solution, i.e. can get the porous silicon nanometer of rice husk base carbon doping
Material.
Embodiment 16
Step one: will rice husk be raw material after washing and drying, aoxidizes 30 points with diamond heating to 480 DEG C in air atmosphere
Clock obtains rice hull ash, after then soaking with dilute hydrochloric acid, is finally dried with after distilled water cyclic washing, obtains dried rice husk
Ash.
Step 2: by dried rice hull ash and aluminium powder, magnesium powder (mass ratio is 2:1), AlCl3、MgCl2With 1: 1.05:
The mass ratio mixing of 0.55: 6.65: 3.35, obtains mixture.
Step 3: be placed in by above-mentioned mixture in full noble gas Achates tank, uses planetary ball mill ball milling, ball material
Mass ratio is 4: 1, and rotating speed is 400 rpm, and Ball-milling Time is 18 h.
Step 4: after ball milling terminates, naturally cools to greenhouse and collects product, after soaking with 0.1M dilute hydrochloric acid, use distilled water
Cyclic washing, finally removes remaining Si oxide with 3% hydrofluoric acid solution, i.e. can get the porous silicon nanometer of rice husk base carbon doping
Material.
More than testing proof, in addition to the product of example 1,2 reaches purpose of design of the present invention, the product of example 3 to example 16 is also
Purpose of design of the present invention can be reached.
Claims (6)
1. the ball-milling preparation method of hole, rice husk Quito silicon nano material, it is characterised in that comprise the following steps:
1) in atmosphere will after washing and drying rice husk heated oxide or incomplete oxidation, obtain rice hull ash, then use dilute salt
After acid soak, it is dried with after distilled water wash, obtains dried rice hull ash；
2) after dried rice hull ash and aluminium powder or aluminium powder and magnesium powder and the mixing of corresponding chloride, compound is obtained, so
After compound is placed in ball mill in be ground；
3) grinding is cooled to greenhouse after terminating, and collects product, after soaking with dilute hydrochloric acid, with distilled water wash, obtains rice husk Quito
Hole silicon nano material.
Method the most according to claim 1, it is characterised in that described dried rice hull ash and aluminium powder or magnesium powder and phase
The muriatic mixing quality ratio answered is 1: 1～25: 2～45.
Method the most according to claim 1 or claim 2, it is characterised in that mill ball and described compound in ball mill during described grinding
The mass ratio that feeds intake be 20～1: 1, rotating speed is 200～3000 rpm, and milling time is 1～40 h.
Method the most according to claim 1 or claim 2, it is characterised in that after described step 3), then by Fluohydric acid. or dense heat
Aqueous slkali is removed and is remained in the Si oxide in the silicon nano material of hole, rice husk Quito, obtains refined rice husk base porous silicon nanometer material
Material.
Method the most according to claim 1 or claim 2, it is characterised in that corresponding chloride is AlCl3Or AlCl3With
MgCl2In mixture at least any one.
Method the most according to claim 1, it is characterised in that in described step 3), the concentration for the dilute hydrochloric acid of immersion is
0.1M。
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| CN113594442A (en) * | 2021-07-27 | 2021-11-02 | 北京大学 | Preparation method of boron-doped nano silicon |
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