CN105967740A - Method for preparing micro-nano structured block silicon material through compounding laser cladding and chemical dealloying - Google Patents
Method for preparing micro-nano structured block silicon material through compounding laser cladding and chemical dealloying Download PDFInfo
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Abstract
The invention discloses a method for preparing a micro-nano structured block silicon material through compounding laser cladding and chemical dealloying. The method comprises the following steps: preparing an aluminum-magnesium alloy cladding layer on a matrix through adopting a laser cladding technology, separating the cladding layer from the matrix to obtain a precursor alloy material, carrying out chemical dealloying treatment on the precursor alloy material obtained after the cladding treatment by adopting a corrosive, and removing the element aluminum to finally obtain the micro-nano structured block silicon material. The method has the advantages of simple operation, short preparation period and high efficiency, and the prepared micro-nano structured block silicon material can be applied to the fields of solar batteries, lithium ion batteries and biology.
Description
Technical field
The invention belongs to technical field of material, relate to a kind of with alusil alloy as raw material, use laser melting and coating technique to be combined
The method that the de-alloy technology of chemistry prepares micro nano structure buik silicon material.
Background technology
When silicon face has micro/nano structure, thus it is possible to vary the performances such as the optics of material, electricity.These performances are to realizing too
Efficient utilization, the absorption of characteristic frequency ripple, the raising of chemical property of lithium ion battery negative material, the biology etc. of sun energy
The application of numerous areas has huge potentiality.Therefore, silicon face micro/nano structure technology of preparing and the tune of practicality and high efficiency are explored
Controlling its shape characteristic is very important work.The method preparing micro nanometer silicon at present mainly has template (magnesium reduction process
Sedimentation) and non-template method (electrochemical erosion method chemical corrosion method).(1) electrochemical erosion method, this method is
With p-type Si or N-shaped Si as material, in the electrolyte based on HF, platinum (Pt) or graphite are placed in negative electrode, monocrystal silicon
It is placed in anode, in addition suitable constant current or constant voltage, monocrystal silicon is carried out electrochemical corrosion, can be raw at monocrystalline silicon surface
Become one layer of porous silicon.But the method efficiency is low.(2) chemical corrosion method, is that silicon immerses the corrosive liquid that HF acid is master
In carry out the method that porous silicon is prepared in corrosion.Method is simple, and the cycle is short, but the micro nanometer silicon scantling of preparation is big, knot
Structure lack of homogeneity.(3) de-alloyage, refers to a kind of method of one or more the constituent element selective removals in alloy,
Have simple to operate, by regulating the preparation of presoma, the preparation of different pore size porous silicon can be realized.(4) magnesiothermic reduction
Method, this method is under the high temperature conditions, utilizes magnesium metal that reducing silica becomes silicon, and prepared by this method micro-nano
Silicon material structure not easy-regulating, and reaction condition requirement height, need the most just can carry out.(5) sedimentation, should
Method, with silicon or silane as raw material, by sputtering deposited onto on matrix, prepares micro nanometer silicon material, usual this method system
The thickness of standby micro-nano silicon materials is thin, and the time is long.
Wenchao Zhou etc. as raw material, utilize HCL to erode aluminum unit with alusil alloy powder (Al:Si=88:12wt.%)
Element, prepares spherical porous silicon granule (1-10um), and is applied to lithium ion battery negative.Electric current density is 200mA/g,
After 60 circulations, capacity is left 1150mAh/g.(The nanostructure of the Si–Al eutectic and its use in
lithium batteries.Wenchao Zhou et al.MRS Communications(2013),3,119–121)
Zhiyu Jiang etc. utilizes aluminum silicon mixed-powder (Al:Si=80:20wt.%), erodes aluminium element by HCL, then uses
HF dissolves the oxide that surface exists, and prepares porous silicon powder.For lithium ion battery negative material, electric current density
For 100mA g-1Time, after 258 circulations, capacity remains 1368mAh g-1。(An easy way for preparing
high performance porous silicon powder by acid etching Al–Si alloy powder for lithium ion
battery.Z.Jiang et al.Electrochimica Acta 115(2014)393–398)
Above technical method utilizes alusil alloy powder for raw material, takes off alloyage by chemistry and takes off aluminium element, prepares multi-pore micron silicon grain.And
With aluminum Si powder as raw material, utilize laser melting and coating technique to prepare presoma alloy, then take off aluminium element by the de-alloyage of chemistry, prepare micro-nano
Structural mass silicon materials, do not relate to so far.Compared with multi-pore micron silicon grain, micro nano structure buik silicon material can keep overall structure,
Need not additionally be coated on material surface, it is possible to achieve material function is with structure-integrated.
Summary of the invention
The limitation of multi-pore micron silicon grain can only be prepared for existing de-alloy approach, the invention provides one and utilize laser to melt
Cover and take off alloy with chemistry and be combined the method preparing micro nano structure buik silicon material.
Laser melting and coating technique is used to prepare alusil alloy cladding layer on matrix, then by cladding layer from matrix before isolated
Drive body alloy material, finally use caustic that cladding processes the presoma alloy material obtained and carry out the de-alloy treatment of chemistry,
Remove element aluminum, final acquisition micro nano structure buik silicon material.
Further, laser melting coating matrix material is aluminum or aluminum alloy.
Further, laser melting coating raw material is dusty material, silk material or powder cored filament material, and its total chemical analysis mass percent is:
Al:50～95%, Si:5～50%.
Further, Laser Cladding Treatment power density is 1.5 × 104～2.5 × 105W/cm2, scanning speed is 2～30mm/s.
Further, the de-alloy caustic of chemistry is sodium hydroxide, potassium hydroxide, hydrochloric acid, sulphuric acid, nitric acid or Fluohydric acid..
Further, the de-alloy sodium hydroxide of chemistry, potassium hydroxide, hydrochloric acid, sulphuric acid, nitric acid, the concentration of Fluohydric acid. be 1～
5mol/L, etching time is 2～12 hours.
When silicone content is less than 5%, it is impossible to form silicon skeleton, when silicone content is more than 50%, form thick primary silicon, it is impossible to
Form loose structure.
The present invention uses laser melting and coating technique and chemistry to take off alloy and is combined the method preparing micro nano structure buik silicon material, and it is excellent
Point is as follows:
1) using alusil alloy cladding layer prepared by laser melting coating, fine microstructures composition is uniform, it is ensured that the de-alloy of chemistry
After obtain micro nano structure uniform buik silicon material；
2) preparation method is simple, and the cycle is short, and condition requires simple, can carry out under room temperature.
Accompanying drawing explanation
Fig. 1 is raw material aluminum Si powder SEM of the present invention figure,
Fig. 2 is laser melting coating presoma alloy microstructure figure of the present invention,
Fig. 3 is that the SEM of the micro nano structure buik silicon material after the present invention takes off alloy schemes,
Fig. 4 is that the SEM of the micro nano structure buik silicon material after the present invention takes off alloy schemes,
Fig. 5 is the XRD diffraction spectrogram of micro nano structure silicon materials of the present invention.
Fig. 6 is the macro morphology figure of micro nanometer silicon material of the present invention.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in further detail, but is not limited to following example.
Embodiment 1
1. raw material:
(1) aluminum Si powder (-325 mesh, 99%), Al:Si=95:5wt.%, granularity about 80 μm.
(2) aluminium sheet, purity: 99.0%, size: 100mm × 50mm × 5mm.
(3) the HCL solution of corrosive liquid: 3mol/L.
2. preparation method
Step one, the preparation of presoma alloy material:
Aluminum Si powder being placed on matrix material aluminium sheet (100mm × 50mm × 5mm), pre-set thickness is about 1mm, uses
YLS-6000 optical fiber laser carries out cladding, laser power: 5kW, spot diameter: 5mm, and scanning speed is: 4mm/s,
Argon shield throughput: 15L/min.Then use line cutting to be separated from matrix by cladding layer, obtain presoma alloy material.
The de-alloy treatment of step 2, chemistry:
Presoma alloy material cladding prepared is immersed in the HCL solution of 3mol/L corrosion 2 hours, until anti-
Till should stopping, then using the deionized water micro nano structure intermediate to obtaining after corrosion to wash 3 times, be subsequently placed at
2%HF ethanol solution stirs 2 hours, dissolves surface SiO that may be present2, then with deionized water, dehydrated alcohol
Wash respectively, finally given micro nano structure buik silicon material.
Embodiment 2
1. raw material:
(1) aluminum Si powder (-325 mesh, 99%), Al:Si=88:12wt.%, granularity about 80 μm.
(2) aluminium sheet, purity: 99.0%, size: 100mm × 50mm × 5mm.
(3) the HCL solution of corrosive liquid: 3mol/L.
2. preparation method
The preparation of step one presoma alloy material:
Aluminum Si powder being placed on matrix material aluminium sheet (100mm × 50mm × 5mm), pre-set thickness is about 2mm, uses
YLS-6000 optical fiber laser carries out cladding, laser power: 5.5kW, spot diameter: 5mm, and scanning speed is: 8mm/s,
Argon shield throughput: 15L/min.Then use line cutting to be separated from matrix by cladding layer, obtain presoma alloy material.
The de-alloy treatment of step 2, chemistry:
Presoma alloy material cladding prepared is immersed in the HCL solution of 3mol/L corrosion 8 hours, until anti-
Till should stopping, then using the deionized water micro nano structure intermediate to obtaining after corrosion to wash 3 times, be subsequently placed at
2%HF ethanol solution stirs 2 hours, dissolves surface SiO that may be present2, then with deionized water, dehydrated alcohol
Wash respectively, finally given micro nano structure buik silicon material.
Embodiment 3
1. raw material:
(1) aluminum Si powder (-325 mesh, 99%), Al:Si=50:50wt.%, granularity about 80 μm.
(2) aluminium sheet, purity: 99.0%, size: 100mm × 50mm × 5mm.
(3) the HCL solution of corrosive liquid: 3mol/L.
2. preparation method
The preparation of step one presoma alloy material:
Aluminum Si powder being placed on matrix material aluminium sheet (100mm × 50mm × 5mm), pre-set thickness is about 2mm, uses
YLS-6000 optical fiber laser carries out cladding, laser power: 5.5kW, spot diameter: 5mm, and scanning speed is: 10mm/s,
Argon shield throughput: 15L/min.Then use line cutting to be separated from matrix by cladding layer, obtain presoma alloy material.
The de-alloy treatment of step 2, chemistry:
Presoma alloy material cladding prepared is immersed in the HCL solution of 3mol/L corrosion 12 hours, until anti-
Till should stopping, then using the deionized water micro nano structure intermediate to obtaining after corrosion to wash 3 times, be subsequently placed at
2%HF ethanol solution stirs 2 hours, dissolves surface SiO that may be present2, then with deionized water, dehydrated alcohol
Wash respectively, finally given micro nano structure buik silicon material.
Fig. 2 Fig. 3 is aluminum silicon precursor alloy microstructure figure and the micro nano structure block that finally gives in embodiment 1 respectively
Body silicon materials SEM schemes.
Fig. 4 is the SEM figure of the micro nano structure buik silicon material finally given in embodiment 2.
Fig. 5 is the XRD diffraction spectrogram of the micro nano structure buik silicon material finally given in embodiment 2.
Fig. 6 is the macro morphology figure of the final micro nano structure buik silicon material obtained in embodiment 2.
Claims (6)
1. laser melting coating and chemistry take off alloy and are combined the method preparing micro nano structure buik silicon material, its feature
It is: use laser melting and coating technique to prepare alusil alloy cladding layer on matrix, then cladding layer is separated from matrix
To presoma alloy material, finally use caustic that cladding processes the presoma alloy material obtained and carry out the de-conjunction of chemistry
Gold processes, and removes element aluminum, final acquisition micro nano structure buik silicon material.
A kind of laser melting coating the most according to claim 1 and chemistry take off that alloy is compound prepares micro nano structure block
The method of silicon materials, is characterized in that: laser melting coating matrix material is aluminum or aluminum alloy.
A kind of laser melting coating the most according to claim 1 and chemistry take off that alloy is compound prepares micro nano structure block
The method of silicon materials, is characterized in that: laser melting coating raw material is dusty material, silk material or powder cored filament material, and it is the most chemical
Composition mass percent is: Al:50～95%, Si:5～50%.
A kind of laser melting coating the most according to claim 1 and chemistry take off that alloy is compound prepares micro nano structure block
The method of silicon materials, is characterized in that: Laser Cladding Treatment power density is 1.5 × 104～2.5 × 105W/cm2, scanning
Speed is 2～30mm/s.
A kind of laser melting coating the most according to claim 1 and chemistry take off that alloy is compound prepares micro nano structure block
The method of silicon materials, is characterized in that: the de-alloy caustic of chemistry be sodium hydroxide, potassium hydroxide, hydrochloric acid, sulphuric acid,
Nitric acid or Fluohydric acid..
A kind of laser melting coating the most according to claim 1 and chemistry take off that alloy is compound prepares micro nano structure block
The method of silicon materials, is characterized in that: the de-alloy sodium hydroxide of chemistry, potassium hydroxide, hydrochloric acid, sulphuric acid, nitric acid,
The concentration of Fluohydric acid. is 1～5mol/L, and etching time is 2～12 hours.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108511693A (en) * | 2018-03-01 | 2018-09-07 | 北京工业大学 | A method of note technology is melted based on laser and manufactures lithium ion battery silicium cathode |
| CN108866545A (en) * | 2018-07-25 | 2018-11-23 | 合肥工业大学 | A method of carrying material is got rid of by laser melting coating and prepares gradient aluminium silicon electronic package material |
| CN110775978A (en) * | 2019-11-01 | 2020-02-11 | 山东建筑大学 | Preparation method and application of three-dimensional dendritic crystal porous silicon |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103938130A (en) * | 2014-05-09 | 2014-07-23 | 河北工业大学 | Preparation method of nanometer porous nickel block |
| CN103985848A (en) * | 2014-06-03 | 2014-08-13 | 盐城工学院 | Method for preparing nano porous silicon by utilizing doped silicon particles |
| CN105063400A (en) * | 2015-09-16 | 2015-11-18 | 哈尔滨工业大学 | Preparation method for nanometer porous titanium |
-
2016
- 2016-05-02 CN CN201610285747.5A patent/CN105967740B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103938130A (en) * | 2014-05-09 | 2014-07-23 | 河北工业大学 | Preparation method of nanometer porous nickel block |
| CN103985848A (en) * | 2014-06-03 | 2014-08-13 | 盐城工学院 | Method for preparing nano porous silicon by utilizing doped silicon particles |
| CN105063400A (en) * | 2015-09-16 | 2015-11-18 | 哈尔滨工业大学 | Preparation method for nanometer porous titanium |
Non-Patent Citations (2)
| Title |
|---|
| G.P. DINDA ET AL.: ""Evolution of microstructure in laser deposited Al-11.28% Si alloy"", 《SURFACE & COATINGS TECHNOLOGY》 * |
| HUAJUN TIAN ET AL.: ""Micro-sized nano-porous Si/C anodes for lithium ion batteries"", 《NANO ENERGY》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108511693A (en) * | 2018-03-01 | 2018-09-07 | 北京工业大学 | A method of note technology is melted based on laser and manufactures lithium ion battery silicium cathode |
| CN108511693B (en) * | 2018-03-01 | 2021-04-13 | 北京工业大学 | Method for manufacturing silicon cathode of lithium ion battery based on laser melt injection technology |
| CN108866545A (en) * | 2018-07-25 | 2018-11-23 | 合肥工业大学 | A method of carrying material is got rid of by laser melting coating and prepares gradient aluminium silicon electronic package material |
| CN108866545B (en) * | 2018-07-25 | 2020-01-03 | 合肥工业大学 | Method for preparing gradient aluminum-silicon electronic packaging material by laser cladding melt-spun material |
| CN110775978A (en) * | 2019-11-01 | 2020-02-11 | 山东建筑大学 | Preparation method and application of three-dimensional dendritic crystal porous silicon |
| CN110775978B (en) * | 2019-11-01 | 2023-08-04 | 山东建筑大学 | Preparation method and application of three-dimensional dendrite porous silicon |
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