CN102765721B - Method for preparing spongy porous silicon material - Google Patents
Method for preparing spongy porous silicon material Download PDFInfo
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- CN102765721B CN102765721B CN201210295831.7A CN201210295831A CN102765721B CN 102765721 B CN102765721 B CN 102765721B CN 201210295831 A CN201210295831 A CN 201210295831A CN 102765721 B CN102765721 B CN 102765721B
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Abstract
The invention discloses a method for preparing a spongy porous silicon material. The procedure for purifying kieselguhr includes: fully soaking the kieselguhr through acid to remove water-soluble impurities in the kieselguhr, fully mixing the acidified kieselguhr and ammonium sulfate, fully calcining the mixture in the air, filtering the calcined kieselguhr through deionized water to remove impurities, and obtaining the purified deionized water after drying. The reduction process of the deionized water includes: enabling the purified kieselguhr and alkali family metals or alkali earth family metals to fully react under the environment of inert gases, fully soaking the reacted products through hydrochloric acid, and filtering, washing through water and drying to obtain the spongy porous silicon material with high purity. The obtained spongy porous silicon material with high purity can be applied to the industries of energy, semi-conductors, sensors and the like, is regular in pore shape, even in distribution and capable of reducing stress remarkably in application, and improves performance of the spongy porous silicon material.
Description
technical field
The present invention relates to the preparation method for field materials such as chemical cell, sensor, catalyst, relate in particular to a kind of method of preparing spongy porous silica material.
Background technology
Element silicon is the principal element of earth's crust constituent, and a large amount of and widely distributed is present in the Nature, is a kind of and eco-friendly element.Due to the chemical property of silicon, occurring in nature does not exist with elementary state and is blended in rock with silicate form miscellaneous.The oxide compound of industrial silicon is widely used in building materials, pottery, glass and appliance and electronic, and the Reduction of Oxide of silicon is become to polysilicon, and the high purity polycrystalline silicon after purification is the most important raw material of photovoltaic and semiconductor industry.
Chemistry and characteristic electron due to silicon, the silicon of take is example as secondary cell anode, it can have high theoretical energy density (4000 mAh/g), but during as lithium ion battery anode, while inserting due to ion, can produce great volume change, as shown in Figure 1, easily destroy electrode structure and lower circulating density and electrode life.If silicon can be manufactured to spongy porous silicon, its porousness has absorbed the stress of volume change, can solve electrode structure instability problem.But the mode of production that not yet occurs spongy porous silica material in prior art.
Spongy porous silica material is except having as lithium ion battery sun potentiality, porous silica material is by its unique substance characteristics of what, also possess the potentiality as special sensor or catalyst material, therefore, prior art needs further improve and develop for the mode of production and the application of spongy porous silica material.
Summary of the invention
In view of above-mentioned the deficiencies in the prior art, the object of the present invention is to provide a kind of method of preparing spongy porous silica material, be intended to prepare spongy porous silica material, for the energy, semi-conductor, sensor industry provide good base mateiral.
Technical scheme of the present invention is as follows:
A method of preparing spongy porous silica material, it comprises the following steps:
A, purified silicious earth step: diatomite is fully soaked and removes water-soluble impurity wherein with acid, it is fully calcined in air after diatomite after acidifying is fully mixed with ammonium sulfate, diatomite after calcining, through deionized water filtering and impurity removing, is obtained to purified silicious earth after oven dry;
B, diatomite reduction step: described purified silicious earth is fully reacted under inert gas environment with alkali family metal or alkaline earth metal, reacted product is fully soaked with hydrochloric acid, then filter, wash post-drying and obtain highly purified spongy porous silica material.
Described preparation method, wherein, what described steps A was concrete comprises: by described for diatomite sulfuric acid, nitric acid or hydrochloric acid fully soak and remove water-soluble impurity wherein in 5-10 hour, the mass ratio of described diatomite and sulfuric acid, nitric acid or hydrochloric acid is between 1:10-1:50.
Described preparation method, wherein, what described steps A was concrete comprises: the diatomite after described acidifying and ammonium sulfate are calcined 2-4 hours 400 ℃ of-600 ℃ of conditions, diatomite after calcining, through deionized water filtering and impurity removing, is obtained to described purified silicious earth after drying under 80 ℃ of-120 ℃ of conditions; Diatomaceous mass ratio after described ammonium sulfate and described acidifying is at 1:10-1:50.
Described preparation method, wherein, what described step B was concrete comprises: described purified silicious earth and described alkali family metal or described alkaline earth metal are fully reflected 4 hours-6 hours under argon shield condition and under 600 ℃ of-800 ℃ of conditions; The mass ratio of described purified silicious earth and alkali family metal or alkaline earth metal is between 60:48-60:130.
Described preparation method, wherein, described alkali family metal is sodium or potassium, described alkaline earth metal is magnesium or calcium.
Described preparation method, wherein, the mass ratio of described purified silicious earth and sodium is between 60:90-60:100, or the mass ratio of described purified silicious earth and potassium is between 60:110-60:130, or the mass ratio of described purified silicious earth and magnesium is between 60:48-60:80, or the mass ratio of described purified silicious earth and calcium is between 60:80-60:100.
Described preparation method, wherein, what described step B was concrete comprises: described reacted product is fully soaked with described hydrochloric acid, after then filtering, washing, 80 ℃ of-120 ℃ of oven dry, obtain highly purified described spongy porous silica material.
A kind of method of preparing spongy porous silica material provided by the invention, the mode that adopts purified silicious earth step to combine with diatomite reduction step, thereby obtain highly purified spongy porous silica material, because spongy porous silica material has special structure and characteristic of semiconductor, by different elements, mix and can obtain electricity widely, magnetic and chemical affinity, can be applied to the energy, semi-conductor, sensor industry, the hole shape rule of spongy porous silica material, arrange evenly, when application, can significantly reduce its stress, improve the performance of spongy porous silica material.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of lithium cell silicon anode discharge in prior art;
Fig. 2 is spongy porous silicon at the phasor of 650 ℃;
Fig. 3 is 5000 times of electron microscope structural representations of spongy porous silicon;
Fig. 4 is spongy porous silicon XRD spectrum schematic diagram;
Fig. 5 is 50000 times of electron microscope structural representations of spongy porous silicon;
Fig. 6 is spongy porous silicon high power electron microscope structural representation;
Fig. 7 is preparation method's of the present invention schematic flow sheet.
Embodiment
The invention provides a kind of method of preparing spongy porous silica material, for making object of the present invention, technical scheme and effect clearer, clear and definite, below the present invention is described in more detail.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
The invention provides a kind of method of preparing spongy porous silica material, as shown in Figure 7, what it was concrete comprises the following steps:
Step 101: diatomite is fully soaked and removes water-soluble impurity wherein with acid, it is fully calcined in air after diatomite after acidifying is fully mixed with ammonium sulfate, diatomite after calcining, through deionized water filtering and impurity removing, is obtained to purified silicious earth after oven dry;
Step 102: described purified silicious earth is fully reacted under inert gas environment with alkali family metal or alkaline earth metal, reacted product is fully soaked with hydrochloric acid, then filter, wash post-drying and obtain highly purified spongy porous silica material.By technique of the present invention, obtain spongy porous silica material, its hole shape rule, arranges evenly, when application, can significantly reduce its stress, can be applied to the energy, semi-conductor, sensor industry, has expanded its application space.
In another preferred embodiment of the present invention, what described step 101 was concrete also comprises: by described for diatomite sulfuric acid, nitric acid or hydrochloric acid fully soak and remove water-soluble impurity wherein in 5-10 hour, the mass ratio of described diatomite and sulfuric acid, nitric acid or hydrochloric acid is between 1:10-1:50.
Further, what described step 101 was concrete also comprises: the diatomite after described acidifying and ammonium sulfate are calcined 2-4 hours 400 ℃ of-600 ℃ of conditions, diatomite after calcining, through deionized water filtering and impurity removing, is obtained to described purified silicious earth after drying under 80 ℃ of-120 ℃ of conditions; Diatomaceous mass ratio after described ammonium sulfate and described acidifying is at 1:10-1:50.
In another preferred embodiment of the present invention, what described step 102 was concrete also comprises: described purified silicious earth and described alkali family metal or described alkaline earth metal are fully reflected 4 hours-6 hours under argon shield condition and under 600 ℃ of-800 ℃ of conditions; The mass ratio of described purified silicious earth and alkali family metal or alkaline earth metal is between 60:48-60:130.And described alkali family metal is sodium or potassium, described alkaline earth metal is magnesium or calcium.
Further, the mass ratio of described purified silicious earth and sodium is between 60:90-60:100, or the mass ratio of described purified silicious earth and potassium is between 60:110-60:130, or the mass ratio of described purified silicious earth and magnesium is between 60:48-60:80, or the mass ratio of described purified silicious earth and calcium is between 60:80-60:100.
In another preferred embodiment of the present invention, what described step 102 was concrete also comprises: described reacted product is fully soaked with described hydrochloric acid, after then filtering, washing, 80 ℃ of-120 ℃ of oven dry, obtain highly purified described spongy porous silica material.
Embodiment 1
Purified silicious earth: utilize sulfuric acid, nitric acid or salt acid soak to filter for 5-10 hours in diatomite (dioxide-containing silica is between 80-90%) and remove water-soluble impurity, after mixing than the weight ratio of 5%-2% with 95-98% with ammonium sulfate again under 400 ℃ of-600 ℃ of conditions, in air, calcine 2 hours-4 hours, cooling rear and deionized water and stirring filtration removal water-soluble impurity is dried and is obtained purified silicious earth under 80 ℃ of-120 ℃ of conditions.
Diatomite reduction: by purified silicious earth and sodium, potassium, magnesium or calcium with chemical equivalent or higher than the ratio of chemical equivalent 25% directly in protective gas argon gas; at 600 ℃-800 ℃, high temperature reduction reaction is 4 hours-6 hours; reaction after product utilize aqueous hydrochloric acid neutralization, soak the muriate except sodium, potassium, magnesium or calcium; filter, washing, under 80 ℃ of-120 ℃ of conditions, after oven dry, obtain highly purified spongy porous silicon.As shown in Fig. 3, Fig. 5 and Fig. 6, the concrete structure of highly purified spongy porous silica material under different multiples microscope, its hole shape rule, arranges evenly, when application, can significantly reduce its stress.As shown in Figure 4, be the XRD spectrum figure of highly purified spongy porous silica material, can further show, the spongy porous silica material that the present invention obtains has good character.
The magnesium of take describes as example as reductive agent, and the principal reaction that the silicon-dioxide in diatomite and magnesium carry out is as follows:
SiO2(s) + 2Mg(s)
?Si(s) + 2MgO(s)
Its reaction conditions is that its reaction is thermopositive reaction at 650 ℃, reaction heat is DH (650 ℃)=-312 KJ, free energy is DG ° of (650 ℃)=-261KJ, as shown in Figure 2, owing to reacting diffusibleness and chemical ratio, likely form the dephasigns such as Mg2Si, Mg2SiO4, but can recently control product by controlling chemical equivalent.
Purified silicious earth: utilize sulfuric acid, nitric acid or salt acid soak to filter removal water-soluble impurity for 5-10 hours with 12000 grams in 600 grams of diatomite (dioxide-containing silica is between 80-90%), its mix with 60 grams of ammonium sulfate again after under 400 ℃ of-600 ℃ of conditions, in air, calcine 2 hours-4 hours, cooling rear and deionized water and stirring filtration removal water-soluble impurity is dried and is obtained purified silicious earth under 80 ℃ of-120 ℃ of conditions.
Diatomite reduction: by purified silicious earth and 900 grams of calcium directly in protective gas argon gas; at 600 ℃-800 ℃, high temperature reduction reaction is 4 hours-6 hours; reaction after product utilize aqueous hydrochloric acid neutralization, soak the muriate except sodium, potassium, magnesium or calcium; filter, washing, under 80 ℃ of-120 ℃ of conditions, after oven dry, obtain highly purified spongy porous silicon.
The calcium of take describes as example as reductive agent, and the principal reaction that the silicon-dioxide in diatomite and calcium carry out is as follows:
SiO2(s) + 2Ca(s)
Si(s) + 2CaO(s)
Its reaction conditions is that its reaction is thermopositive reaction at 650 ℃, owing to reacting diffusibleness and chemical ratio, likely forms Ca
2the dephasign such as Si, Ca2SiO4, but can recently control product by controlling chemical equivalent.
Because manufacturing processed of the present invention is similar, its difference is only that the ratio between each material is different, therefore about each reaction example, at this, do not enumerating, its concrete ratio is respectively: diatomite and sour ratio are at 1:10-1:50, and its optimum proportion is 1:20; Diatomaceous mass ratio after described ammonium sulfate and described acidifying is at 1:10-1:50, and its optimum proportion is 1:20; The mass ratio of described purified silicious earth and alkali family metal or alkaline earth metal between 60:48-60:130, its be more specifically the mass ratio of described purified silicious earth and sodium between 60:90-60:100, its optimum proportion is 60:92 or 60:98; The mass ratio of described purified silicious earth and potassium is between 60:110-60:130, and its optimum proportion is 60:120 or 60:127.5; The mass ratio of described purified silicious earth and magnesium is between 60:48-60:80, and its optimum proportion is 60:48.6 or 60:54.7; The mass ratio of described purified silicious earth and calcium is between 60:80-60:100, and its optimum proportion is 60:80 or 60:90.In order to obtain the spongy porous silica material of better performances, can within the scope of aforementioned proportion, adjust.
Should be understood that, application of the present invention is not limited to above-mentioned giving an example, and for those of ordinary skills, can be improved according to the above description or convert, and all these improvement and conversion all should belong to the protection domain of claims of the present invention.
Claims (1)
1. a method of preparing spongy porous silica material, it comprises the following steps:
A, purified silicious earth step: diatomite is fully soaked and removes water-soluble impurity wherein with acid, it is fully calcined in air after diatomite after acidifying is fully mixed with ammonium sulfate, diatomite after calcining, through deionized water filtering and impurity removing, is obtained to purified silicious earth after oven dry;
B, diatomite reduction step: described purified silicious earth is fully reacted under inert gas environment with alkali family metal or alkaline earth metal, reacted product is fully soaked with hydrochloric acid, then filter, wash post-drying and obtain highly purified spongy porous silica material;
What described steps A was concrete comprises: by described for diatomite sulfuric acid, nitric acid or hydrochloric acid fully soak and remove water-soluble impurity wherein in 5-10 hour, the mass ratio of described diatomite and sulfuric acid, nitric acid or hydrochloric acid is between 1:10-1:50;
What described steps A was concrete comprises: the diatomite after described acidifying and ammonium sulfate are calcined 2-4 hours 400 ℃ of-600 ℃ of conditions, diatomite after calcining, through deionized water filtering and impurity removing, is obtained to described purified silicious earth after drying under 80 ℃ of-120 ℃ of conditions; Diatomaceous mass ratio after described ammonium sulfate and described acidifying is at 1:10-1:50;
What described step B was concrete comprises: described purified silicious earth is fully reacted 4 hours-6 hours under argon shield condition and under 600 ℃ of-800 ℃ of conditions with described alkali family metal or described alkaline earth metal; The mass ratio of described purified silicious earth and alkali family metal or alkaline earth metal is between 60:48-60:130;
Described alkali family metal is sodium or potassium, and described alkaline earth metal is magnesium or calcium;
The mass ratio of described purified silicious earth and sodium is between 60:90-60:100, or the mass ratio of described purified silicious earth and potassium is between 60:110-60:130, or the mass ratio of described purified silicious earth and magnesium is between 60:48-60:80, or the mass ratio of described purified silicious earth and calcium is between 60:80-60:100;
What described step B was concrete comprises: described reacted product is fully soaked with described hydrochloric acid, after then filtering, washing, 80 ℃ of-120 ℃ of oven dry, obtain highly purified described spongy porous silica material.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1322673A (en) * | 2001-06-26 | 2001-11-21 | 中国科学院长春应用化学研究所 | Diatomite purifying treatment method |
| CN102249240A (en) * | 2011-06-08 | 2011-11-23 | 浙江大学 | Preparation method for using diatomite to prepare high-purity simple substance silicon |
| CN102259858A (en) * | 2011-06-07 | 2011-11-30 | 同济大学 | Method for preparing porous silicon by magnesiothermic reduction |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1322673A (en) * | 2001-06-26 | 2001-11-21 | 中国科学院长春应用化学研究所 | Diatomite purifying treatment method |
| CN102259858A (en) * | 2011-06-07 | 2011-11-30 | 同济大学 | Method for preparing porous silicon by magnesiothermic reduction |
| CN102249240A (en) * | 2011-06-08 | 2011-11-23 | 浙江大学 | Preparation method for using diatomite to prepare high-purity simple substance silicon |
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