CN107324347B - A kind of method and product preparing nano silicon material using waste cement - Google Patents
A kind of method and product preparing nano silicon material using waste cement Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2006/12—Surface area
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- C01P2006/14—Pore volume
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
Abstract
The present invention provides a kind of methods and product that nano silicon material is prepared using waste cement.Waste cement is the hydrated product of cement, method includes the following steps: waste cement powder is carried out calcination and cooling, then the waste cement powder after calcination is mixed with the solid ammonium salt that can be used as water absorbing agent, heating after concentrated acid mixes then is added and is evaporated and washs to prepare nano silica.Preparation gained nano silicon material has big specific surface area, hierarchical porous structure, is expected to apply in the fields such as environment remediation and energy storage.This method is simple, efficient, at low cost, short preparation period, is conducive to the prepare with scale of nano-silicon.The present invention provides new method for the resource utilization of waste cement, and provides new approaches for the preparation of nano silicon material.
Description
Technical field
The present invention relates to the preparation of inorganic nano silicon materials and solid waste comprehensive utilization of resources field, and in particular to a kind of utilizations
Waste cement prepares the method and product of nano silicon material.
Background technique
Cement is widely used in building, bridge, road as production and most commonly used engineering material in mankind's activity
Etc., tremendous contribution is made that for the development and welfare of human society.Meanwhile being widely used for cement also produces largely
Waste cement.It data show, it is contemplated that the waste cement amount generated to the year two thousand twenty China is up to 2,000,000,000 tons.If to waste water
Mud is mishandling, can not only impact to environment, but also is the waste to resource.Currently, master is disposed in the processing of waste cement
If landfill or recycling and reusing.For example, using waste cement be raw material, prepared using certain technique regenerated aggregate or
Recycled cement, but the regeneration rate of current waste cement is lower.Waste cement processing method of disposal is less at present, existing method
The derived material added value of preparation is not high, and therefore, the resource utilization method for further developing waste cement is still very necessary.
Summary of the invention
The purpose of the present invention is to provide a kind of methods and product that nano silicon material is prepared using waste cement, to solve
Utilize the not high problem of the derived material added value of waste cement preparation.
The present invention solves its technical problem and adopts the following technical solutions to realize.
The present invention provides a kind of method for preparing nano silicon material using waste cement, waste cement is the aquation of cement
Product, comprising the following steps: waste cement powder is subjected to calcination and cooling, then by after calcination waste cement powder with can
Solid ammonium salt as water absorbing agent mixes, and heating after concentrated acid mixes then is added and is evaporated and washs to prepare nano silica.
The present invention also provides the products that the above method is prepared.
The embodiment of the present invention prepare the method for nano silicon material using waste cement and the beneficial effect of product is: with useless
Abandoning cement is raw material, and first calcination, then selective pickling, dehydration obtain nano silica, then by metallothermic reduction and
Pickling again can prepare nano silicon material.Preparation gained nano silicon material has big specific surface area, hierarchical porous structure, is expected to answer
Used in the fields such as environment remediation and energy storage.This method is simple, efficient, at low cost, short preparation period, raw material range of choice
Greatly, be conducive to the prepare with scale of nano-silicon, it is easy to realize industrialization promotion and application.
There is the nano silicon material of method preparation of the invention big specific surface area (to reach as high as about 110m2/ g) and hole body
Product (reaches as high as about 0.64cm3/ g), hierarchical porous structure (mesoporous and macropore), be expected to apply in environment remediation and energy storage etc.
Field.
Method of the invention can turn waste into wealth, and provide new method for the resource utilization of waste cement, and be nanometer
The preparation of silicon materials provides new approaches.
Detailed description of the invention
Fig. 1 is the X-ray diffractogram for the nano silica that embodiment 1 is prepared.
Fig. 2 is the scanning electron microscope diagram for the nano silica that embodiment 1 is prepared.
Fig. 3 is the X-ray diffractogram for the nano silicon material that embodiment 1 is prepared.
Fig. 4 is the Si 2p high-resolution X-ray fluorescence spectra figure for the nano silicon material that embodiment 1 is prepared.
Fig. 5 is the scanning electron microscope diagram for the nano silicon material that embodiment 1 is prepared.
Fig. 6 is the nitrogen adsorption desorption curve for the nano silicon material that embodiment 1 is prepared.
Fig. 7 is the graph of pore diameter distribution for the nano silicon material that embodiment 1 is prepared.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
Inventor's discovery: nano-silicon causes everybody concern, including Energy Section due to unique property in numerous areas
Learn (battery electrode material and catalyst for preparing hydrogen), environment remediation (chemical sensor and different-phase catalyst), biological medicine (biology at
Picture and pharmaceutical carrier).Compared with buik silicon, nano-silicon can provide bigger ratio table for the load of goal response or active material
Face accelerates interfacial mass transfer process, shortens diffusion length.In addition, for some specific reaction (embedding lithiums in such as charge and discharge/de-
Lithium process), the vesicular structure of nano-silicon can effectively adapt to the volume expansion of silicon in reaction process, enhance its stability.
It is mainly nano silica, silane, siliceous organic matter etc. in terms of silicon precursor selection.These presomas are practical
On both be from quartzite, be quartzite is prepared by complicated physical and chemical process.High cost and complicated preparation process limit
The large-scale production of nano-silicon is made, it is difficult to realize industrial applications.
Below specifically to the method for preparing nano silicon material using waste cement of the embodiment of the present invention and product progress
It is bright.
Present embodiments provide for a kind of method for preparing nano silicon material using waste cement, waste cement is cement
Hydrated product, comprising the following steps:
S1.1: by the waste cement of solid-like is broken and grind into powder, can be carried out using existing means it is broken and
Grinding, details are not described herein.Cement be it is a kind of with tricalcium silicate, dicalcium silicate, tricalcium aluminate and tetra calcium aluminoferrite be mainly at
The powdery hydraulicity inorganic coagulation material divided, hydration reaction can be occurred by meeting water.Waste cement is then the hydrated product of cement, mainly
By CaO-SiO2-H2O gel, calcium hydroxide, entringite etc. are constituted.Waste cement is usually at bulk, if directly purchase has added
Work crosses into powdered waste cement, then can omit step S1.1.
S1.2: waste cement powder is subjected to calcination and cooling.
The temperature of calcination waste cement can be 300~800 DEG C, and corresponding calcination time can be 0.5~3 hour.It can
Choosing, the temperature of calcination waste cement is 400~800 DEG C.Optionally, the temperature of calcination waste cement is 500~800 DEG C.Item
The case where part allows calcination temperature can be above 800 DEG C, but the temperature of calcination waste cement is unsuitable excessively high, otherwise will form
It is difficult to the high-temperature-phase being acid washed, is impacted to subsequent step.
The type of cooling can use natural cooling or other conventional chilling modes.It can be cooled to room temperature or approach
Room temperature.
S1.3: by calcination and waste cement powder after cooling is mixed with the solid ammonium salt that can be used as water absorbing agent.
First waste cement powder and solid ammonium salt are mixed before adding concentrated acid, the waste cement powder after can avoid calcination
It grabs moisture in concentrated acid and generates gel.The main function that can be used as the solid ammonium salt of water absorbing agent is: using solid ammonium salt and cement
Powder mixes, and when adding concentrated acid, using the strong absorptive of solid ammonium salt, waste cement powder is made not will form gel.In turn
So that metal ion is not easy to be mixed into gel, metal ion removal rate is higher.
It is possible to further adjust waste cement powder and solid ammonium salt to suitable ratio.Such as solid ammonium salt with
The mass ratio of waste cement is more than or equal to 3:1.It is further alternative, the mass ratio of solid ammonium salt and waste cement is 5~
10:1。
Optionally, the solid ammonium salt that can be used as water absorbing agent includes at least one of ammonium chloride and ammonium nitrate.It is preferred that using
Ammonium chloride, ammonium chloride is at low cost, and easily recycles.
S1.4: addition concentrated acid is heated after mixing and is evaporated to prepare nano silica.Energy after waste cement and concentrated acid effect
Silicic acid and soluble chloride are generated, wherein silicic acid (SiO2·H2O it) is easy to exist in colloidal form in aqueous solution, by adding
Solid ammonium salt and heating, which are evaporated, can be such that its overwhelming majority dehydration is precipitated, to separate with components other in solution.
The dosage of concentrated acid be it is a small amount of, optionally, the volume mass ratio of concentrated acid and waste cement is 4~10mL/g.Concentrated acid
Mass concentration can be 36%-38%.Optionally, concentrated acid is any one of the concentrated sulfuric acid, concentrated nitric acid and concentrated hydrochloric acid or dense sulphur
At least two mixture in acid, concentrated nitric acid and concentrated hydrochloric acid.
Contain Fe in the product wherein obtained after S1.33+、Al3+Plasma.Due to Fe3+、Al3+Plasma is excessively high in temperature
Shi Rongyi hydrolysis generates slightly solubility basic salt, is mixed into and is difficult to separate in silicic acid gel, therefore, strict control temperature is wanted during being evaporated
Degree.Optionally, temperature when heating is evaporated is 80-100 DEG C.
S1.5: it can will then be evaporated product and be washed to neutral, drying to get more pure nano silica.In order to
Moisture removal is removed in quickening, is dried again after being first centrifuged after washing.
The available nano silica after above-mentioned steps, if it is desired to further obtain nano-silicon, can carry out
Following step.
S2.1: further including sealing the mixture that nano silica, metallic reducing agent and salt are formed under protective atmosphere
It heats and keeps the temperature.
Mixture can be nano silica, metallic reducing agent and salt and mix according to molar ratio 1:0.2~3:3~12
It is made.
Above-mentioned heating temperature can be 300~900 DEG C, and soaking time can be 1~20h.Optionally, heating temperature is
650~800 DEG C, soaking time is 4~5h.
Above-mentioned salt forms fused salt after heatingization is molten, fused salt as heat absorbent, can be absorbed released in reduction process it is more
Excess heat, be effectively prevented temperature it is excessively high caused by high temperature miscellaneous phase generation and nano silicon particles melting aggregation.
Above-mentioned salt can select the salt of alkali metal or the salt of alkaline-earth metal.It is possible to further select potassium chloride, sodium chloride,
One of aluminium chloride, zinc chloride, lithium chloride and magnesium chloride or a variety of combinations.
In addition, metallic reducing agent is also possible to prevent the generation of high temperature miscellaneous phase and the oxidation of silicon.The selection of metallic reducing agent is former
It is then 50 DEG C of fusing point or more that its fusing point is lower than selected salt, and guarantees that there is reproducibility at the heating temperature.Metallic reducing agent can
To select the group of one or more of magnesium metal, metallic sodium, metallic zinc, metallic aluminium, metallic potassium, calcium metal or metallic iron
It closes.Optionally, metallic reducing agent is selected from magnesium metal and metallic aluminium.
Optionally, diluted acid includes one of hydrochloric acid, nitric acid, sulfuric acid or phosphoric acid or a variety of, and volumetric concentration used is 5~
20%.Optionally, the volumetric concentration of diluted acid is 8-20%.Optionally, the volumetric concentration of diluted acid is 15-20%.Optionally, diluted acid
Volumetric concentration be 8-15%.
Optionally, protective gas is the combination of one or more of nitrogen and rare gas.
Closed environment can be provided by closed container, further, can choose stainless steel reactor.
S2.2: dilute acid wash again is first washed with water after object to be mixed is cooling.
The salt that generation is heated in step S2.1 can be recycled by way of evaporative crystallization.
S2.3 mixture washs immersion 2 minutes or more after weak acid scrubbing, then with diluted hydrofluoric acid or ammonium hydrogen fluoride solution,
Then it is washed with water to neutral and dry.
Inventors have found that being impregnated after weak acid scrubbing, then with diluted hydrofluoric acid or ammonium hydrogen fluoride solution in mixture
The product quality obtained afterwards is preferable.The possible reason is there may be silicon oxide compounds for silicon face in the product obtained after S2.2
And/or the SiO not reacted away completely2.And after diluted hydrofluoric acid or ammonium hydrogen fluoride solution impregnate, it can remove the silicon oxygen of silicon face
Compound and/or the SiO not reacted away completely2, it is further reduced impurity.
Further, the volumetric concentration of hydrofluoric acid can be 1%~5%.When using ammonium hydrogen fluoride solution, can using and
The equivalent amount of hydrofluoric acid.Such as the mass fraction of ammonium hydrogen fluoride solution is 1%~20%.
Embodiments of the present invention also provide a kind of product that the above method is prepared.
Feature and performance of the invention are described in further detail with reference to embodiments.
Embodiment 1
A method of nano silicon material is prepared using waste cement, comprising the following steps:
The first broken, grind into powder by waste water clod, is placed in Muffle furnace calcination 1h, natural cooling at 500 DEG C；Then
Waste cement powder and 30g solid ammonium chloride after taking 5g calcination are uniformly mixed, and add 25mL concentrated hydrochloric acid, after mixing evenly, 105 DEG C
Heating water bath is evaporated, and with milli-Q water to neutrality, centrifugation, drying obtain nano silica.
It takes 1g nano silica obtained above, 0.8g metal magnesium powder and 5g sodium chloride to be uniformly mixed, is transferred to stainless
Steel reactor, and it is closed, then the stainless steel reactor for filling mixture is placed in tube furnace, 700 DEG C under protection of argon gas
Heating keeps the temperature 4h, after cooling, first uses milli-Q water, is then washed with volumetric concentration for 8% dilute hydrochloric acid, then with 1% dilute hydrogen fluorine
Acid soak 10min, finally with milli-Q water to neutrality, centrifugation, drying are to get nano silicon material.
Embodiment 2
A method of nano silicon material is prepared using waste cement, comprising the following steps:
The first broken, grind into powder by waste water clod, is placed in Muffle furnace calcination 0.5h, natural cooling at 800 DEG C；So
Waste cement powder and 25g solid ammonium chloride after taking 4g calcination afterwards are uniformly mixed, and add 20mL concentrated hydrochloric acid, after mixing evenly, 100
DEG C heating water bath is evaporated, centrifugation, dry with milli-Q water to neutrality, obtains nano silica.
It takes 1g nano silica obtained above, 1g metallic aluminium powder and 3g sodium chloride to be uniformly mixed, is transferred to stainless steel
Reactor, and it is closed, then the stainless steel reactor for filling mixture is placed in tube furnace, is added for 800 DEG C under protection of argon gas
Heat keeps the temperature 5h, after cooling, first uses milli-Q water, is then washed with volumetric concentration for 15% dilute hydrochloric acid, then with 2% dilute hydrogen fluorine
Acid soak 5min, finally with milli-Q water to neutrality, centrifugation, drying are to get nano silicon material.
Gained nano silicon material has preferable crystal form, has hierarchical porous structure, BET specific surface area 105m2/ g, total hole body
Product is 0.61cm3/g。
Embodiment 3
A method of nano silicon material is prepared using waste cement, comprising the following steps:
The first broken, grind into powder by waste water clod, is placed in Muffle furnace calcination 3h, natural cooling at 400 DEG C；Then
Waste cement powder and 50g solid ammonium chloride after taking 10g calcination are uniformly mixed, and add 50mL concentrated hydrochloric acid, after mixing evenly, 102
DEG C heating water bath is evaporated, centrifugation, dry with milli-Q water to neutrality, obtains nano silica.
It takes 2g nano silica obtained above, 2g metal magnesium powder and 12g sodium chloride to be uniformly mixed, is transferred to stainless steel
Reactor, and it is closed, then the stainless steel reactor for filling mixture is placed in tube furnace, is added for 650 DEG C under protection of argon gas
Heat keeps the temperature 5h, after cooling, first uses milli-Q water, is then washed with volumetric concentration for 20% dilute hydrochloric acid, then with 1.5% dilute hydrogen
Fluoric acid impregnates 8min, and finally with milli-Q water to neutrality, centrifugation, drying are to get nano silicon material.
Gained nano silicon material has preferable crystal form, has hierarchical porous structure, BET specific surface area 98m2/ g, total hole body
Product is 0.54cm3/g。
Embodiment 4
A method of nano silicon material is prepared using waste cement, comprising the following steps:
The first broken, grind into powder by waste water clod, is placed in Muffle furnace calcination 3h, natural cooling at 400 DEG C；Then
Waste cement powder and 30g solid ammonium nitrate after taking 10g calcination are uniformly mixed, and add the 50mL concentrated sulfuric acid, after mixing evenly, 102
DEG C heating water bath is evaporated, centrifugation, dry with milli-Q water to neutrality, obtains nano silica.
It takes 2g nano silica obtained above, 2g metallic aluminium powder and 12g potassium chloride to be uniformly mixed, is transferred to stainless steel
Reactor, and it is closed, then the stainless steel reactor for filling mixture is placed in tube furnace, is added for 750 DEG C under nitrogen protection
Heat keeps the temperature 5h, after cooling, first uses milli-Q water, is then washed with volumetric concentration for 20% dilute hydrochloric acid, then with 1.5% dilute hydrogen
Fluoric acid impregnates 8min, and finally with milli-Q water to neutrality, centrifugation, drying are to get nano silicon material.
Embodiment 5
A method of nano silicon material is prepared using waste cement, comprising the following steps:
The first broken, grind into powder by waste water clod, is placed in Muffle furnace calcination 3h, natural cooling at 400 DEG C；Then
Waste cement powder and 50g solid ammonium chloride after taking 10g calcination are uniformly mixed, and add 50mL concentrated hydrochloric acid, after mixing evenly, 100
DEG C heating water bath is evaporated, centrifugation, dry with milli-Q water to neutrality, obtains nano silica.
It takes 2g nano silica obtained above, 2g metal magnesium powder and 9g sodium chloride to be uniformly mixed, is transferred to stainless steel
Reactor, and it is closed, then the stainless steel reactor for filling mixture is placed in tube furnace, is added for 650 DEG C under protection of argon gas
Heat keeps the temperature 3h, after cooling, first uses milli-Q water, is then washed with volumetric concentration for 20% dilute hydrochloric acid, then with 5% dilute hydrogen fluorine
Acid soak 5min, finally with milli-Q water to neutrality, centrifugation, drying are to get nano silicon material.
Test example 1
The nano silica being prepared using embodiment 1 obtains the X-ray diffractogram of the nano silica as sample
The scanning electron microscope diagram (as shown in Figure 2) of (as shown in Figure 1) and the nano silica.
X-ray diffraction spectra (XRD) as the result is shown (Fig. 1), in one obvious Bao Feng of~24 ° (2 θ) appearance, illustrates by giving up
The nano silica for abandoning cement preparation is mainly amorphous silica.
In addition, having also appeared the characteristic peak of nano silica in picture, illustrate that there are also least a portion of crystal two in product
Silica.Scanning electron microscope diagram spectrum (SEM) shows (Fig. 2), and nanoparticle aggregate pattern is presented in gained silica.
Test example 2
The nano-silicon obtained after metallothermic reduction and pickling using embodiment 1 obtains the X of the nano silicon material as sample
X ray diffration pattern x (as shown in Figure 3)；The Si 2p high-resolution X-ray fluorescence spectra figure (as shown in Figure 4) of the nano silicon material；It should
The scanning electron microscope diagram (as shown in Figure 5) of nano silicon material；The nitrogen adsorption desorption curve of the nano silicon material is (such as Fig. 6 institute
Show)；The graph of pore diameter distribution (as shown in Figure 7) of the nano silicon material.
As the result is shown (Fig. 3), apparent elemental silicon characteristic diffraction peak is presented in products therefrom to XRD, correspond to (111),
(220), (311), (400), (331) crystal face.
High-resolution X-ray fluorescence spectra figure (XPS) show (Fig. 4), the peak Si 2p mainly by be located at~99.1 and~
Two peaks of 103.50eV are constituted, and are respectively belonging to simple substance Si and SiOx, and simple substance Si accounts for major part.
SEM as the result is shown (Fig. 5), prepares products therefrom and loose porous nanotopography is presented.Nitrogen adsorption desorption curve is shown
(Fig. 6), preparation gained nano silicon material belong to IV type thermoisopleth, have H3 type hysteresis loop.When relative pressure is higher, nitrogen is inhaled
Attached amount quicklys increase, and shows that the material has macroporous structure.It is according to the specific surface area that the material is calculated in BET formula
110m2/ g, total pore volume 0.64cm3/g。
Graph of pore diameter distribution (Fig. 7) further demonstrates that the material has hierarchical porous structure, predominantly mesoporous and macropore.
To sum up, verification result shows that this method is successfully prepared using waste cement and has both bigger serface and multi-stage porous
The nano silicon material of structure.Raw material range of choice of the present invention is wide, at low cost, and preparation method is simple and efficient, energy consumption
Low, short preparation period is suitable for prepare with scale, and prospects for commercial application is wide.It is provided newly for the resource utilization of waste cement
Method, and new approaches are provided for the preparation of nano silicon material.
Embodiments described above is a part of the embodiment of the present invention, instead of all the embodiments.Reality of the invention
The detailed description for applying example is not intended to limit the range of claimed invention, but is merely representative of selected implementation of the invention
Example.Based on the embodiments of the present invention, obtained by those of ordinary skill in the art without making creative efforts
Every other embodiment, shall fall within the protection scope of the present invention.
Claims (22)
1. a kind of method for preparing nano silicon material using waste cement, the waste cement is the hydrated product of cement, special
Sign is, comprising the following steps:
Waste cement powder is subjected to calcination and cooling, then by the waste cement powder after calcination and can be used as water absorbing agent
Solid ammonium salt mix, then be added concentrated acid mix after heating be evaporated and wash to prepare nano silica；
The mixture that the nano silica, metallic reducing agent and salt are formed heated sealed and is kept the temperature under protective atmosphere,
Dilute acid wash again is first washed with water after the mixture is cooling.
2. the method according to claim 1, wherein the volume mass of the concentrated acid and waste cement ratio be 4~
10mL/g。
3. the method according to claim 1, wherein the mass concentration of the concentrated acid is 36%-38%.
4. according to the method described in claim 3, it is characterized in that, the concentrated acid is in the concentrated sulfuric acid, concentrated nitric acid and concentrated hydrochloric acid
It is any.
5. the method according to claim 1, wherein the mass ratio of the solid ammonium salt and the waste cement is big
In or equal to 3:1.
6. according to the method described in claim 5, it is characterized in that, the mass ratio of the solid ammonium salt and the waste cement is
5~10:1.
7. according to the method described in claim 6, it is characterized in that, the solid ammonium salt include in ammonium chloride and ammonium nitrate extremely
Few one kind.
8. the method according to claim 1, wherein the temperature of waste cement described in calcination be 300~800 DEG C,
Calcination time is 0.5~3 hour.
9. according to the method described in claim 8, it is characterized in that, the temperature of waste cement described in calcination is 400~800 DEG C.
10. according to the method described in claim 8, it is characterized in that, the temperature of waste cement described in calcination is 500~800 DEG C.
11. according to the method described in claim 8, it is characterized in that, temperature when heating is evaporated is 80-100 DEG C.
12. the method according to claim 1, wherein further including the drying steps carried out after a wash step.
13. -12 described in any item methods according to claim 1, which is characterized in that the mixture is by the nano-silica
SiClx, the metallic reducing agent and the salt are mixed according to molar ratio 1:0.2~3:3~12 and are made.
14. according to the method for claim 13, which is characterized in that the mixture is after weak acid scrubbing, then with dilute hydrogen fluorine
Acid or ammonium hydrogen fluoride solution wash immersion 2 minutes or more, are then washed with water to neutral and dry.
15. the method according to claim 1, wherein the metallic reducing agent includes magnesium metal, metallic sodium, gold
Belong at least one of zinc, metallic aluminium, metallic potassium, calcium metal or metallic iron.
16. according to the method for claim 15, which is characterized in that the metallic reducing agent is selected from magnesium metal and metallic aluminium；
The salt is the salt of alkali metal or the salt of alkaline-earth metal.
17. according to the method for claim 16, which is characterized in that the salt includes potassium chloride, sodium chloride, aluminium chloride, chlorine
Change at least one of zinc, lithium chloride or magnesium chloride.
18. according to the method for claim 15, which is characterized in that the diluted acid includes in hydrochloric acid, nitric acid, sulfuric acid or phosphoric acid
It is one or more, volumetric concentration used be 5~20%.
19. according to the method for claim 15, which is characterized in that the gas of the protective atmosphere is nitrogen and rare gas
At least one of body.
20. according to the method for claim 14, which is characterized in that the volumetric concentration of the hydrofluoric acid is 1%~5%, institute
The mass fraction for stating ammonium hydrogen fluoride solution is 1%~20%.
21. the method according to claim 1, wherein heating temperature be 300~900 DEG C, soaking time be 1~
20h。
22. according to the method for claim 21, which is characterized in that heating temperature be 650~800 DEG C, soaking time be 4~
5h。
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| CN104577082A (en) * | 2015-01-09 | 2015-04-29 | 南京大学 | Nano-silicon material and application thereof |
| CN104591191A (en) * | 2013-11-01 | 2015-05-06 | 无锡华臻新能源科技有限公司 | Preparation method for regular-morphology mesoporous silicon nanometer material for optical devices |
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| CN104591191A (en) * | 2013-11-01 | 2015-05-06 | 无锡华臻新能源科技有限公司 | Preparation method for regular-morphology mesoporous silicon nanometer material for optical devices |
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