CN107572531A - A kind of porous silicon preparation method - Google Patents
A kind of porous silicon preparation method Download PDFInfo
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- CN107572531A CN107572531A CN201710977841.1A CN201710977841A CN107572531A CN 107572531 A CN107572531 A CN 107572531A CN 201710977841 A CN201710977841 A CN 201710977841A CN 107572531 A CN107572531 A CN 107572531A
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- porous silicon
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Abstract
The invention discloses a kind of preparation method of porous silicon, this method comprises the following steps：(a) eccentric cleaning is carried out to polycrystalline silica flour with hydrofluoric acid, sulfuric acid, ethanol, ultra-pure water successively；(b) polycrystalline silica flour is put into stirring reaction in the mixed solution of silver nitrate, ice cube and hydrofluoric acid；(c) eccentric cleaning；(d) it is put into ice bath stirring corrosion in the mixed solution of hydrofluoric acid, hydrogen peroxide, ethanol；(e) boric acid is added dropwise and nitric acid continues ice bath stirring corrosion；(f) eccentric cleaning is carried out to D product with ultra-pure water, obtains porous silicon.The present invention preparation method is simple, cost is relatively low, prepared porous silicon have particle aperture it is larger, it is porous be evenly distributed, the advantages of pore size is uniform, and porous silicon adsorbs without metallic, can improve the using effect of porous silicon.
Description
Technical field
The present invention relates to a kind of silicon processing method, particularly a kind of porous silicon preparation method.
Background technology
Porous silicon（porous Si）It is a kind of new 1-dimention nano photon crystal material, is with nano-silicon cluster
" quantum sponge " shape micro-structural of skeleton, porous silicon is due to special surface texture and huge specific surface area, in many fields
There is utilization.Porous silicon can by metal aid in corrosion hair be made, and existing metal auxiliary etch be difficult to prepare aperture compared with
Greatly, it is porous be evenly distributed, the porous silicon grain that pore size is similar, and to prepare porous silicon past for existing metal auxiliary etch
A large amount of metallics are adsorbed toward in porous silicon surface, influence the use of porous silicon, while prepared by existing metal auxiliary etch
The preparation cost of porous silicon is higher.
Therefore, exist at present in the preparation process of porous silicon the porous silicon grain aperture prepared is smaller, more pore size distributions not
Uniformly, pore size differs greatly and prepared the shortcomings that cost is higher, and the easy adsorbing metal particles of porous silicon surface, influences
The using effect of porous silicon.
The content of the invention
It is an object of the present invention to provide a kind of porous silicon preparation method.The preparation method of the present invention is simple, cost compared with
It is low, prepared porous silicon have particle aperture it is larger, it is porous be evenly distributed, the advantages of pore size is uniform, and porous silicon
The silver metal particle overall adsorption that is evenly distributed is less, can improve the using effect of porous silicon.
Technical scheme：A kind of porous silicon preparation method, comprises the following steps：
(a) the polycrystalline silica flour of 3-5 parts is measured, successively with hydrofluoric acid, sulfuric acid, ethanol, ultra-pure water eccentric cleaning.
(b) 0.01mol/L-O.O5mol/L silver nitrates, 20-50 parts rubble ice, 4mol/L-6mol/L hydrofluoric acid and water are taken
50 ~ 300 parts of mixed solution A is mixed and made into, polycrystalline silica flour is put into stirring reaction 2-5 minutes in mixed solution A, obtains A product.
(c) eccentric cleaning is carried out to A product, obtains B product.
(d) 3-6mol/L hydrofluoric acid, 0.5%-3% hydrogen peroxide, 8-15 part second alcohol and waters is taken to be mixed and made into 50 ~ 300 parts of mixing
Solution B, B product are put into ice bath stirring corrosion 0.5h-1.5h in mixed solution B, obtain C product.
(e) 0.3mol/L-1.2mol/L boric acid is added dropwise into C product and 0.5%-1.5% nitric acid continues ice bath stirring corrosion
0.5h-1.5h, obtain D product.
(f) eccentric cleaning is carried out to D product with ultra-pure water, obtains porous silicon.
In a kind of foregoing porous silicon preparation method, the particle diameter of the polycrystalline silica flour in the step (a) is 4-15 μm.
In a kind of foregoing porous silicon preparation method, step (b) medium floe is made up of ultra-pure water.
In a kind of foregoing porous silicon preparation method, ice bath temperature is -10 DEG C -10 DEG C in the step (d), (e).
In a kind of foregoing porous silicon preparation method, the step (a), (c) and the centrifugal rotational speed of eccentric cleaning in (f) are
3000-6000 revs/min.
Compared with prior art, the present invention is by step（b）It is middle that ice cube prepared by ultra-pure water is added into solution, and lead to
Cross in step（d）And step（e）It is middle effectively to reduce porous silicon surface adsorbing metal particles, a small amount of gold of attachment using ice bath
Category particle can increase the electric conductivity of silicon；
The present invention passes through step（d）And step（e）Substep corrosion is carried out, uniform pore diameter is obtained, the larger porous silicon in aperture, can have
The active material cracking even avalanche caused by aperture is uneven when effect is avoided as lithium ion battery negative material；
The present invention passes through step（d）And step（e）Substep addition low-concentration-corrosion agent can effectively prevent porous silicon to be oxidized and produce
Rate is more than 30%.
In summary, preparation method of the invention is simple, cost is relatively low, prepared porous silicon have particle aperture compared with
Greatly, it is porous be evenly distributed, the advantages of pore size is uniform, and porous silicon adsorbing metal particles are uniform and adsorbance is less, can
Improve the using effect of porous silicon.
（b）Silicon under the polarization of fluorine the silver particles in solution can adsorb higher in energy in step（Containing scarce
At sunken surface）And crystallize, reducing solution system temperature with ice cube reduces Ag+As Ag conversion ratio, Ag crystallinity is reduced, is made
The absorption of silver particles evenly is on silicon grain surface.
（d）Due to H in step2O2/H2O is to Si/ [SiF6]-It is poor to there is oxidation-reduction potential, forms galvanic cell, Ag particles
For catalyst, pore-forming can be corroded in the place for having Ag to adsorb.
（e）In have different with the additional difference pressure at non-porous place at hole due to silicon, be more easy to be oxidized by nitric acid at bore edges
Incorporate in solution, hole is further expanded.
Brief description of the drawings
Fig. 1 is ESEM (SEM) the figure A for the porous silicon that the present invention is prepared；
Fig. 2 is ESEM (SEM) the figure B for the porous silicon that the present invention is prepared.
Embodiment
With reference to embodiment, the present invention is further illustrated, but is not intended as the foundation limited the present invention.
Embodiment 1
A kind of preparation method of porous silicon, comprises the following steps：
(a) it is 10 μm of polycrystalline silica flours to take 3g average diameter of particles, successively with hydrofluoric acid, sulfuric acid, ethanol, ultra-pure water eccentric cleaning from
Heart rotating speed is 5000 revs/min.
(b) take 0.03mol/L silver nitrates, 30g ultra-pure waters that ice cube, 5mol/L hydrofluoric acid and water is made and be mixed and made into 150ml
Mixed solution A, polycrystalline silica flour is put into stirring reaction 5 minutes in mixed solution A, obtains A product.
(c) A product are carried out with eccentric cleaning, centrifugal rotational speed is 5000 revs/min, obtains B product.
(d) it is molten that it is 1% hydrogen peroxide to take 5mol/L hydrofluoric acid, mass fraction, 10ml second alcohol and waters are mixed and made into 150ml mixing
Liquid B, B product are put into mixed solution B, stirring corrosion 1.5h, obtains C product under conditions of being -5 DEG C in ice bath temperature.
(e) 0.5mol/L boric acid and 1% nitric acid are added dropwise into C product, continues to stir under conditions of being -5 DEG C in ice bath temperature
Corrode 1.5h, obtain D product.
(f) D product are carried out with eccentric cleaning with ultra-pure water, centrifugal rotational speed is 5000 revs/min, obtains porous silicon.
Embodiment 2
A kind of preparation method of porous silicon, comprises the following steps：
(a) it is 6 μm of polycrystalline silica flours to take 4g average diameter of particles, successively with hydrofluoric acid, sulfuric acid, ethanol, ultra-pure water eccentric cleaning from
Heart rotating speed is 3000 revs/min.
(b) take 0.01mol/L silver nitrates, 20g ultra-pure waters that ice cube, 4mol/L hydrofluoric acid and water is made and be mixed and made into 80ml
Mixed solution A, polycrystalline silica flour is put into stirring reaction 2 minutes in mixed solution A, obtains A product.
(c) A product are carried out with eccentric cleaning, centrifugal rotational speed is 3000 revs/min, obtains B product.
(d) it is molten that it is 0.6% hydrogen peroxide to take 3mol/L hydrofluoric acid, mass fraction, 8ml second alcohol and waters are mixed and made into 80ml mixing
Liquid B, B product are put into mixed solution B, stirring corrosion 0.8h, obtains C product under conditions of being -8 DEG C in ice bath temperature.
(e) 0.3mol/L boric acid and 0.8% nitric acid are added dropwise into C product, continues to stir under conditions of being -8 DEG C in ice bath temperature
Corrosion 0.8h is mixed, obtains D product.
(f) D product are carried out with eccentric cleaning with ultra-pure water, centrifugal rotational speed is 3000 revs/min, obtains porous silicon.
Embodiment 3
A kind of preparation method of porous silicon, comprises the following steps：
(a) it is 8 μm of polycrystalline silica flours to take 5g average diameter of particles, successively with hydrofluoric acid, sulfuric acid, ethanol, ultra-pure water eccentric cleaning from
Heart rotating speed is 4500 revs/min.
(b) take 0.01mol/L silver nitrates, 40g ultra-pure waters that ice cube, 5mol/L hydrofluoric acid and water is made and be mixed and made into 260ml
Mixed solution A, polycrystalline silica flour is put into stirring reaction 3 minutes in mixed solution A, obtains A product.
(c) A product are carried out with eccentric cleaning, centrifugal rotational speed is 4500 revs/min, obtains B product.
(d) it is that 1.5% hydrogen peroxide, 15ml second alcohol and waters are mixed and made into 260ml mixing to take 5mol/L hydrofluoric acid, mass fraction
Solution B, B product are put into mixed solution B, stirring corrosion 0.5h, obtains C product under conditions of being -6 DEG C in ice bath temperature.
(e) 1mol/L boric acid and 1% nitric acid are added dropwise into C product, it is rotten to continue stirring under conditions of being -7 DEG C in ice bath temperature
1.5h is lost, obtains D product.
(f) D product are carried out with eccentric cleaning with ultra-pure water, centrifugal rotational speed is 5000 revs/min, obtains porous silicon.
Claims (5)
1. a kind of porous silicon preparation method, it is characterised in that comprise the following steps：
(a) the polycrystalline silica flour of 3-5 parts is measured, successively with hydrofluoric acid, sulfuric acid, ethanol, ultra-pure water eccentric cleaning；
(b) 0.01mol/L-O.O5mol/L silver nitrates, 20-50 parts rubble ice, 4mol/L-6mol/L hydrofluoric acid and water mixing are taken
50 ~ 300 parts of mixed solution A is made, polycrystalline silica flour is put into stirring reaction 2-5 minutes in mixed solution A, obtains A product；
(c) eccentric cleaning is carried out to A product, obtains B product；
(d) 3-6mol/L hydrofluoric acid, 0.5%-3% hydrogen peroxide, 8-15 part second alcohol and waters is taken to be mixed and made into 50 ~ 300 parts of mixed solutions
B, B product are put into ice bath stirring corrosion 0.5h-1.5h in mixed solution B, obtain C product；
(e) 0.3mol/L-1.2mol/L boric acid is added dropwise into C product and 0.5%-1.5% nitric acid continues ice bath stirring corrosion 0.5h-
1.5h, obtain D product；
(f) eccentric cleaning is carried out to D product with ultra-pure water, obtains porous silicon.
A kind of 2. porous silicon preparation method according to claim 1, it is characterised in that：Polysilicon in the step (a)
The particle diameter of powder is 4-15 μm.
A kind of 3. porous silicon preparation method according to claim 1, it is characterised in that：Step (b) medium floe is by surpassing
Pure water is made.
A kind of 4. porous silicon preparation method according to claim 1, it is characterised in that:Ice bath in the step (d), (e)
Temperature is -10 DEG C -10 DEG C.
A kind of 5. porous silicon preparation method according to claim 1, it is characterised in that：In the step (a), (c) and (f)
The centrifugal rotational speed of eccentric cleaning is 3000-6000 revs/min.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108483448A (en) * | 2018-06-20 | 2018-09-04 | 贵州大学 | A kind of porous silicon preparation method |
| CN109763134A (en) * | 2018-12-27 | 2019-05-17 | 国联汽车动力电池研究院有限责任公司 | The preparation method of porous silicon |
| CN109920990A (en) * | 2019-03-01 | 2019-06-21 | 贵州大学 | A kind of microwave prepares silicon-metal-carbon composite preparation method |
| CN110371984A (en) * | 2019-08-29 | 2019-10-25 | 贵州大学 | A method of impurity B in silicon is absorbed using oxygen-containing porous layer |
| CN110467184A (en) * | 2019-08-30 | 2019-11-19 | 贵州大学 | A kind of method of impurity P in hydro-thermal erosion removal metallurgical grade silicon |
| CN114639807A (en) * | 2022-03-04 | 2022-06-17 | 东华大学 | Porous silicon nanoparticle/porous carbon nanofiber composite electrode material and preparation method and application thereof |
| CN117117159A (en) * | 2023-10-24 | 2023-11-24 | 琥崧智能装备(太仓)有限公司 | Silicon-carbon negative electrode material and preparation method and application thereof |
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| CN103979487A (en) * | 2014-06-03 | 2014-08-13 | 盐城工学院 | Method for preparing doping porous silicon ball |
| CN105680008A (en) * | 2016-01-18 | 2016-06-15 | 南昌大学 | Preparation method and application for metal modified porous silicon powder |
| CN106025196A (en) * | 2016-05-17 | 2016-10-12 | 河南田园新能源科技有限公司 | Preparation method of silicon-carbon negative electrode composite material with high specific surface area |
| CN106784613A (en) * | 2017-02-23 | 2017-05-31 | 华南理工大学 | A kind of porous silicon copper-plating electrode for lithium ion battery and preparation method thereof |
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| CN103979487A (en) * | 2014-06-03 | 2014-08-13 | 盐城工学院 | Method for preparing doping porous silicon ball |
| CN105680008A (en) * | 2016-01-18 | 2016-06-15 | 南昌大学 | Preparation method and application for metal modified porous silicon powder |
| CN106025196A (en) * | 2016-05-17 | 2016-10-12 | 河南田园新能源科技有限公司 | Preparation method of silicon-carbon negative electrode composite material with high specific surface area |
| CN106784613A (en) * | 2017-02-23 | 2017-05-31 | 华南理工大学 | A kind of porous silicon copper-plating electrode for lithium ion battery and preparation method thereof |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108483448A (en) * | 2018-06-20 | 2018-09-04 | 贵州大学 | A kind of porous silicon preparation method |
| CN109763134A (en) * | 2018-12-27 | 2019-05-17 | 国联汽车动力电池研究院有限责任公司 | The preparation method of porous silicon |
| CN109920990A (en) * | 2019-03-01 | 2019-06-21 | 贵州大学 | A kind of microwave prepares silicon-metal-carbon composite preparation method |
| CN109920990B (en) * | 2019-03-01 | 2022-02-11 | 贵州大学 | Preparation method for preparing silicon-metal-carbon composite material by microwave |
| CN110371984A (en) * | 2019-08-29 | 2019-10-25 | 贵州大学 | A method of impurity B in silicon is absorbed using oxygen-containing porous layer |
| CN110467184A (en) * | 2019-08-30 | 2019-11-19 | 贵州大学 | A kind of method of impurity P in hydro-thermal erosion removal metallurgical grade silicon |
| CN114639807A (en) * | 2022-03-04 | 2022-06-17 | 东华大学 | Porous silicon nanoparticle/porous carbon nanofiber composite electrode material and preparation method and application thereof |
| CN117117159A (en) * | 2023-10-24 | 2023-11-24 | 琥崧智能装备(太仓)有限公司 | Silicon-carbon negative electrode material and preparation method and application thereof |
| CN117117159B (en) * | 2023-10-24 | 2023-12-26 | 琥崧智能装备(太仓)有限公司 | Silicon-carbon negative electrode material and preparation method and application thereof |
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Application publication date: 20180112 |