CN105529451A - Preparation method for porous monatomic silicon - Google Patents
Preparation method for porous monatomic silicon Download PDFInfo
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- CN105529451A CN105529451A CN201510953072.2A CN201510953072A CN105529451A CN 105529451 A CN105529451 A CN 105529451A CN 201510953072 A CN201510953072 A CN 201510953072A CN 105529451 A CN105529451 A CN 105529451A
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- silicon
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- elemental silicon
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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
- H01M4/00—Electrodes
- 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
-
- 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
- C01B33/02—Silicon
- C01B33/021—Preparation
- C01B33/023—Preparation by reduction of silica or free silica-containing material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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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
- H01M4/00—Electrodes
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method for porous monatomic silicon, relating to the technical field of a battery material. The monatomic silicon is obtained by taking soft silicon as a raw material and magnesium powder as a reducing agent and carrying out reduction in an inert environment, wherein the grain size of the soft silicon is 1 to 10 micrometers, the specific surface area is 180-230m<2>/g, and the porous monatomic silicon has a porous hollow structure. According to the preparation method, the soft silicon is taken as the raw material and has ellipsoidal appearance; compared with solid silicon dioxide sphere used in the method, magnesium can easily enter the interior of porous silicon dioxide when the soft silicon reacts the magnesium; moreover, with the adoption of heating according to temperature regions, more uniform heating is achieved; and compared with aerogel, the porous silicon structure is preserved better and more stably, and the wall thickness of the porous silicon can be maintained over 100 nanometers.
Description
Technical field:
The present invention relates to battery material technical field, be specifically related to a kind of preparation method of porous elemental silicon.
Background technology:
At present, along with mobile electronic equipment to high power capacity, long-life batteries demand growing, the performance of people to lithium ion battery is had higher requirement.Capacity of lithium ion battery is on the low side has become a bottleneck of restriction battery industry development, and the negative material finding more height ratio capacity has become an important development direction in battery material field.Current commercialization negative material is carbon, and since lithium ion battery commercialization, the research of material with carbon element obtains significant progress, close to the theoretical value of 372mAh/g, is difficult to the space having lifting again.Thus find and substitute the negative material of carbon and become an important developing direction.In numerous selectable negative material, silicon has higher specific capacity (theoretical value: 4200mAh/g) and lower removal lithium embedded voltage because of it and gets most of the attention.
But because elemental silicon change in volume higher than 300%, and can produce efflorescence material phenomenon in charge and discharge process, cause capacity to reduce rapidly, the internal resistance of cell increases suddenly, thus limit its application in field of lithium ion battery.Porous elemental silicon inside has pore passage structure, and relative to the solid elemental silicon of same particle diameter, according to there being higher specific area, density is lower.Inner space may be used for alleviating elemental silicon volumetric expansion in charge and discharge process.
Production porous elemental silicon has very important significance for lithium cell cathode material, and the method that tradition prepares porous elemental silicon has anodic attack method, stain etch, spark-discharge method, hydrothermal etching, pulsed etching method etc.The aperture of porous elemental silicon surface corrosion prepared by these methods is less, and between several nanometer to tens nanometers, and longitudinal degree of depth of etch pit is lower, can not meet the requirement of lithium cell negative pole material.Utilize magnesium thermit by reed, straw, the reducing silica in silicon ball algae etc. becomes porous elemental silicon, good effect is achieved on electrochemistry cycle performance, but these discarded object impurities such as reed, straw are more, especially inorganic salts, amorphous carbon etc., during volume production, be difficult to removing.The nano simple substance silicon of the preparation such as aeroge, although have loose structure, wall thickness is limited, easily caves in actual applications.
Summary of the invention:
Technical problem to be solved by this invention is to provide a kind of reduces fully, technical process is simple and have the preparation method of the porous elemental silicon of bending pore passage structure.
Technical problem to be solved by this invention adopts following technical scheme to realize:
A preparation method for porous elemental silicon, with soft silicon for raw material, magnesium powder is reducing agent, and in inert environments, reduction obtains porous elemental silicon;
Described soft silicon particle diameter is 1-10um, and specific area is 180-230m
2/ g and there is porous hollow.
Described porous elemental silicon particle diameter is 1-10um, and wall thickness is 50-150nm.
A kind of preparation method of porous elemental silicon; concrete steps are: first soft silicon and magnesium powder are mixed, then are added by mixture in iron crucible with cover, then crucible are placed in the atmosphere furnace of argon shield; in 600-700 DEG C, step heat preservation 2-7h, namely obtain porous elemental silicon finally by salt acid attack.
Operation principle of the present invention:
With particle diameter at 1-10um, specific area is 180-230m
2/ g and the soft silicon with porous hollow is raw material, adopt a point warm area insulation magnesium reduction process, porous silicon and magnesium powder are mixed, be placed in atmosphere furnace and calcine, regulate calcining heat, heat stepwise, makes the elemental silicon in microballoon fully reduce.This technical process is simple, be easy to operation controls, and prepared elemental silicon has bending pore passage structure.
The invention has the beneficial effects as follows: the present invention is with particle diameter at 1-10um, and specific area is 180-230m
2/ g and the soft silicon with porous hollow is raw material, its profile is elliposoidal, relative to the solid silica spheres of use, when soft silicon and reactive magnesium, magnesium can be easy to the inside entering into porous silica, and adopts a point warm area heating, make reaction more even, relative to aeroge, it is more intact and stable that Porous Silicon structures is preserved, and the wall thickness of porous silicon can remain on more than 100nm.
Accompanying drawing illustrates:
Fig. 1 is the SEM shape appearance figure of the soft silicon of raw material;
Fig. 2 is that at 600 DEG C, be incubated 1h, 620 DEG C of insulation 2h, the samples after 650 DEG C of insulation 2h, through the porous silicon SEM shape appearance figure that overpickling prepares with the soft silicon of 30.48g and 25.46g magnesium powder for raw material;
Fig. 3 is that the sample be incubated 4h at 650 DEG C after, through the porous silicon SEM shape appearance figure that overpickling prepares with the soft silicon of 61.04g and 52.39g for raw material;
Fig. 4 is that at 600 DEG C, be incubated 1h, 620 DEG C of insulation 2h, the samples after 650 DEG C of insulation 3h, through the porous silicon SEM shape appearance figure that overpickling prepares with the soft silicon of 167.82g and 142.56g magnesium powder for raw material;
Fig. 5 is with the soft silicon of 110.39g and 93.77g magnesium powder for raw material, and the samples after 650 DEG C of insulation 6h, through the porous silicon SEM shape appearance figure that overpickling prepares.
Embodiment:
The technological means realized to make the present invention, creation characteristic, reaching object and effect is easy to understand, below in conjunction with specific embodiment, setting forth the present invention further.
Embodiment 1
With the soft silicon of 30.48g and 25.46g magnesium powder for raw material, at 600 DEG C, be incubated 1h, 620 DEG C of insulation 2h, the samples after 650 DEG C of insulation 2h, prepare porous silicon through overpickling.As seen from Figure 2, the porous silicon after reduction maintains the loose structure of raw material well, and compared with raw material, there is the trend of expansion in hole.
Embodiment 2
With the soft silicon of 61.04g and 52.39g for raw material, the sample be incubated 4h at 650 DEG C after, prepares porous silicon through overpickling, and as seen from Figure 3, the Porous Silicon structures part after a step reduction is caved in.
Embodiment 3
With the soft silicon of 167.82g and 142.56g magnesium powder for raw material, at 600 DEG C, be incubated 1h, 620 DEG C of insulation 2h, the samples after 650 DEG C of insulation 3h, prepare porous silicon through overpickling.Find out from accompanying drawing 4, the aperture of gained porous silicon is about 100-200nm, and porosity is very high, and the wall thickness of elemental silicon is less than 100nm, and duct is curve.
From above case study on implementation, the present invention for silicon source, utilizes magnesium thermit to prepare skeleton shape porous elemental silicon with soft silicon; The particle diameter of porous silicon is at 3 microns, and products therefrom maintains the pore passage structure of raw material substantially, and wall thickness, at about 100nm, through removal of impurities process, can obtain porous elemental silicon product.By the porous elemental silicon material regulating temperature processing procedure and material rate can obtain tactical rule.
More than show and describe general principle of the present invention and principal character and advantage of the present invention.The technical staff of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and specification just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.Application claims protection range is defined by appending claims and equivalent thereof.
Claims (3)
1. a preparation method for porous elemental silicon, is characterized in that: with soft silicon for raw material, and magnesium powder is reducing agent, and in inert environments, reduction obtains porous elemental silicon;
Described soft silicon particle diameter is 1-10um, and specific area is 180-230m
2/ g and there is porous hollow.
2. the preparation method of a porous elemental silicon, it is characterized in that, concrete steps are: first soft silicon and magnesium powder are mixed, again mixture is added in iron crucible with cover, then crucible is placed in the atmosphere furnace of argon shield, in 600-700 DEG C, step heat preservation 2-7h, namely obtain porous elemental silicon finally by salt acid attack;
Described soft silicon particle diameter is 1-10um, and specific area is 180-230m
2/ g and there is porous hollow.
3. the preparation method of porous elemental silicon according to claim 1 and 2, is characterized in that: described porous elemental silicon particle diameter is 1-10um, and wall thickness is 50-150nm.
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| CN201510953072.2A CN105529451A (en) | 2016-03-07 | 2016-03-07 | Preparation method for porous monatomic silicon |
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| CN201510953072.2A CN105529451A (en) | 2016-03-07 | 2016-03-07 | Preparation method for porous monatomic silicon |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106684364A (en) * | 2017-01-26 | 2017-05-17 | 南京大学 | Nano porous material and preparation method thereof |
| US11069885B2 (en) | 2017-09-13 | 2021-07-20 | Unifrax I Llc | Silicon-based anode material for lithium ion battery |
| CN114074942A (en) * | 2021-11-17 | 2022-02-22 | 青岛科技大学 | Method for preparing simple substance silicon by using joule heat |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102208634A (en) * | 2011-05-06 | 2011-10-05 | 北京科技大学 | Porous silicon/carbon composite material and preparation method thereof |
| CN102976341A (en) * | 2012-11-21 | 2013-03-20 | 蚌埠鑫源石英材料有限公司 | Preparation method of hollow silicon dioxide spherical powdery material |
| CN105070890A (en) * | 2015-07-20 | 2015-11-18 | 北京化工大学 | Titanium oxide-coated porous hollow silicon ball composite electrode material and preparation method therefor |
-
2016
- 2016-03-07 CN CN201510953072.2A patent/CN105529451A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102208634A (en) * | 2011-05-06 | 2011-10-05 | 北京科技大学 | Porous silicon/carbon composite material and preparation method thereof |
| CN102976341A (en) * | 2012-11-21 | 2013-03-20 | 蚌埠鑫源石英材料有限公司 | Preparation method of hollow silicon dioxide spherical powdery material |
| CN105070890A (en) * | 2015-07-20 | 2015-11-18 | 北京化工大学 | Titanium oxide-coated porous hollow silicon ball composite electrode material and preparation method therefor |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106684364A (en) * | 2017-01-26 | 2017-05-17 | 南京大学 | Nano porous material and preparation method thereof |
| CN106684364B (en) * | 2017-01-26 | 2020-04-24 | 南京大学 | Nano porous material and preparation method thereof |
| US11069885B2 (en) | 2017-09-13 | 2021-07-20 | Unifrax I Llc | Silicon-based anode material for lithium ion battery |
| US11652201B2 (en) | 2017-09-13 | 2023-05-16 | Unifrax I Llc | Silicon-based anode material for lithium ion battery |
| CN114074942A (en) * | 2021-11-17 | 2022-02-22 | 青岛科技大学 | Method for preparing simple substance silicon by using joule heat |
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Application publication date: 20160427 |