CN106099113A - A kind of nucleocapsid structure Si-C composite material and preparation method thereof - Google Patents
A kind of nucleocapsid structure Si-C composite material and preparation method thereof Download PDFInfo
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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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
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Abstract
The invention discloses a kind of nucleocapsid structure Si-C composite material and preparation method thereof, this composite has nucleocapsid structure；Described nucleocapsid structure includes the shell being made up of carbon-coating and the kernel being made up of porous nano silicon；Between described shell and kernel, there is void layer；Its preparation method is for carry out magnesiothermic reduction reaction by silica dioxide granule by magnesium powder, after reduzate carries out in-stiu coating by organic polymer carbon source, carbonization, carbonizing production uses Fluohydric acid. corrosion, obtain Si-C composite material, this Si-C composite material good stability, and silicon volumetric expansion can be buffered well, improve material conductivity, thus ensure the cyclical stability of electrode；Si-C composite material preparation process is simple, and raw material sources are extensive, is suitable for industrialized production.
Description
Technical field
The present invention relates to the preparation method of a kind of lithium ion battery negative material, particularly relate to one and there is nucleocapsid structure
Si-C composite material and preparation method thereof, belong to technical field of lithium ion.
Background technology
Since entering 21 century, along with development and the scientific and technological progress of society, electronic product, electric automobile and energy storage electricity
Station has increasing need for high-energy-density and long-life lithium ion battery.But, current business-like lithium ion battery is extensively adopted
Be graphite negative electrodes material, its theoretical capacity relatively low (372mAh/g), be difficult to meet demand.Silicon has as negative material
There is high theoretical specific capacity (4200mAh/g), receive the extensive concern of research worker.Owing to silicon is in charge and discharge process,
The deintercalation of lithium ion can cause the change in volume that it is huge, produces broken, the efflorescence of granule so that silicon active substance is from collector
On come off, ultimately result in electrode interior structural damage, and then have influence on the chemical property of battery.Found by research, subtract
The size of little silicon materials can alleviate its change in volume in charge and discharge process effectively to nanoscale, and carbon cladding also may be used simultaneously
Material conductivity and the effect of suppression volumetric expansion is improved to play.The excellent properties that Si-C composite material is had makes it be expected to
Substituting graphite negative electrodes material, extensive, the constitutionally stable nano-silicone wire/carbon composite material material of preparing of low cost is to realize it
The basis of commercial applications.
Wang etc. use resorcinol-formaldehyde to be carbon source, add nano silicon material and obtain silicon-carbon aeroge, obtain after sintering
Carbon cladding silica-base material [G.X.Wang, et al.Electrochemistry Communications, 2004,6 (7):
689-692], but the carbon-coating being coated with easily is destroyed after iterative cycles, it is difficult to meet the demand of reality application.Patent
CN102623680A discloses the preparation method of a kind of silicon-carbon composite cathode material with three-dimensional preformed hole structure, this method
By removing the silicon dioxide of silicon particle surface cladding in carbon base body, thus obtain three-dimensional reserved between silicon particle and carbon base body
Expansion space, although this method effectively improves the charge-discharge performance of material, however it is necessary that and first generate silicon dioxide
Removing silicon dioxide again, step complexity is unfavorable for large-scale production, and does not solve problem prepared by nano-silicon low cost.Patent
CN 104979539A utilizes zinc oxide to do template, deposits layer of silicon dioxide and carbon-coating respectively, after magnesiothermic reduction in template
Obtaining the silicon-carbon nanometer rod composite material of hollow structure, this method equally obtains preferable chemical property, but mould
The preparation of plate and etching add preparation cost, the CVD complex process used by carbon cladding, are unfavorable for large-scale production.
Utilize silicon dioxide and magnesium powder generation reduction reaction to prepare nano-silicon and there is the advantage that method is simple, with low cost,
It it is considered as one of method being suitable for large-scale application at present.But during preparing Si-C composite material, due to magnesium heat
Reduction is exothermic reaction, and the heat accumulation of local can cause the generation of side reaction in system to generate carborundum impurity phase.Carborundum
There is no the reactivity with lithium, not only result in the decline of material specific capacity, also affect lithium ion in electrode material
Interface is transmitted.This specific capacity being substantially reduced prepared material and high rate performance.How magnesiothermic reduction is utilized to prepare structure steady
The commercial application promoting silicon-carbon cathode material is had great importance by fixed Si-C composite material.
Summary of the invention
The deficiency existed for existing lithium ion battery silicon-carbon composite, it is an object of the invention to be to provide one
There is the Si-C composite material of special nucleus shell structure, this Si-C composite material good stability, and discharge and recharge can be buffered well
Silicon volumetric expansion in journey, improves material conductivity, thus ensures the cyclical stability of electrode.
Another object of the present invention is to be to provide a kind of simple, low cost, described silicon-carbon of preparing without side reaction to answer
The method of condensation material, the method can be with large-scale production.
In order to realize above-mentioned technical purpose, the invention provides a kind of nucleocapsid structure Si-C composite material, this silicon-carbon is combined
Material has nucleocapsid structure；In described nucleocapsid structure includes the shell being made up of carbon-coating and is made up of porous nano silicon
Core；Between described shell and kernel, there is void layer.
The Si-C composite material of the offer of the present invention has special nucleocapsid structure, and its core is porous nano silicon, and shell is carbon
, particularly between kernel and shell, there is void layer in layer.Carbon-coating not only can improve the electric conductivity of material, and can prevent silicon core from breaking
Granular fall, it is ensured that the stability of material structure, and void layer is that in battery charge and discharge process, the volumetric expansion of silicon provides slow
Rush space, effectively prevent composite from rupturing pulverizing in charge and discharge process due to change in volume, thus ensure following of electrode
Ring is stable.
Preferably scheme, the size of described kernel is 10nm～10 μm.
Preferably scheme, the thickness of described shell is 1～200nm.
Present invention also offers the preparation method of described nucleocapsid structure Si-C composite material, the method includes following step
Rapid:
1) silica dioxide granule carries out magnesiothermic reduction reaction by magnesium powder, obtains Si@SiO2Intermediate；
2) described Si@SiO2After intermediate carries out in-stiu coating by organic polymer carbon source, carbonization, obtain C@Si@SiO2
Intermediate；
3) described C@Si@SiO2Intermediate uses Fluohydric acid. corrosion, to obtain final product.
In technical scheme, by magnesium reduction process, make silica sections be reduced generation silicon, mainly obtain
Silicon coated silica intermediate Si@SiO2；Use in-stiu coating method again, at Si@SiO2Carbon-coating clad, then profit are prepared in surface
Remove the nano-silicon of silicon dioxide and partial reduction generation with Fluohydric acid. selectivity after, obtain carbon-coating coated Si composite C@
Si.The removing of silicon dioxide and part silicon is not only for leave corresponding spatial volume between carbon-coating with silicon core, and generates
Porous nano silicon kernel, by controlling the size of void layer, it is ensured that silicon grain free wxpansion in carbon-coating and overall knot
Structure is not destroyed.
Preferably scheme, 1) in, after silica dioxide granule is mixed homogeneously with magnesium powder, it is placed in the airtight of full protective atmosphere
In environment, it is warming up to 600～800 DEG C with the heating rate of 1～20 DEG C/min, carries out reduction reaction 1～12h, obtain Si@SiO2
Intermediate.Preferably the condition of magnesiothermic reduction, can control magnesiothermic reduction degree well, thus realize porous nano silicon structure
Control.The process of magnesiothermic reduction also not only there occurs 2Mg+SiO2The reaction of → Si+2MgO, also there occurs 2Mg+Si → Mg2Si and
Mg2Si+SiO2The a series of reaction such as → 2Si+2MgO, the most not only the surface of silicon dioxide there occurs that reduction generates silicon, its
Inside also has small part reducing silica and generates silicon, so defining porous nano in follow-up Fluohydric acid. corrosion process
Silicon kernel；The silicon grain that silica surface reduction simultaneously obtains is the most tiny, and activity is big, it is easy to corroded at hydroflouric acid
Journey reacts with Fluohydric acid., between charcoal shell and porous nano silicon kernel, forms void layer.
More preferably scheme, silicon dioxide is 1:0.4～1:1 with the mass ratio of magnesium powder.
More preferably scheme, silica dioxide granule particle diameter is 10nm～10 μm.
Preferably scheme, 2) in, described Si@SiO2Intermediate and organic polymer carbon source are dissolved in solvent, after mix homogeneously,
Stirring is evaporated, and gained solid mixture is polished, is placed under protective atmosphere, heats up with the heating rate of 1～20 DEG C/min
To 600～1200 DEG C, carry out carbonization 1～12h, obtain C@Si@SiO2Intermediate.Preferably in-stiu coating and carbonization condition, can be
Si@SiO2Intermediate surface prepares uniform carbon-coating.
Preferably scheme, organic polymer carbon source and Si@SiO2The mass ratio of intermediate is 100:1～1:100.
Preferably scheme, organic polymer carbon source is polyvinyl alcohol, polypropylene, Colophonium, phenolic resin, epoxy resin, Portugal
At least one in grape sugar, sugarcane sugar and starch.Preferably organic polymer carbon source is water-soluble high-molecular material, or is readily soluble
In the macromolecular material of organic solvent, these organic polymer carbon sources are prone to by solvent medium Si@SiO2Intermediate is carried out
In-stiu coating.
Preferably scheme, 3) in, described C@Si@SiO2The hydrogen fluorine that intermediate uses mass percent concentration to be 1～40%
Acid carries out impregnation process 0.01～6h.
More preferably scheme, protective atmosphere is at least one in nitrogen, argon and hydrogen.
The preparation method of the nucleocapsid structure Si-C composite material of the present invention, comprises the following steps:
The first step: silica dioxide granule (particle diameter is 10nm～10 μm) is mixed all according to quality 1:0.4～1:1 with magnesium powder
After even, it be placed in the closed environment of full protective atmosphere, be warming up to 600～800 DEG C with the heating rate of 1～20 DEG C/min
Reaction 1～12h；After reaction terminates, taking out product, described product joins the hydrochloric acid and/or sulphuric acid that concentration is 0.5～4mol/L
Solution washs 1～24h, after filtering drying, obtains intermediate product Si@SiO2；
Second step: by organic polymer carbon source and Si@SiO2During 100:1～1:100 is dissolved in solvent in mass ratio, mixing is all
After even, solution is stirred under the conditions of 60～120 DEG C and is evaporated, gained mixture grind after under protective atmosphere, with 1～20 DEG C/
The heating rate of min is warming up to 600～1200 DEG C of reactions 1～12h, and reaction obtains the C@Si@SiO of carbon cladding after terminating2；
3rd step: by C@Si@SiO2It is dissolved in immersion treatment 0.01～6h in the hydrofluoric acid solution that concentration is 1～40wt%,
Remove residue SiO2And after a small amount of silicon, filtration washing obtains the end product C@Si with nucleocapsid structure.
Compared with prior art, technical scheme has the advantage that
1) Si-C composite material that technical scheme obtains has special nucleocapsid structure, including porous nano silicon
, particularly between kernel and shell, there is void layer in kernel and carbon-coating shell.Carbon-coating not only can improve the electric conductivity of material, and
Can prevent from silicon core from crushing to be scattered, it is ensured that the stability of material structure, and void layer is the volume of silicon in battery charge and discharge process
Expansion provides cushion space, effectively prevents composite from rupturing pulverizing in charge and discharge process due to change in volume, thus
Ensure the stable circulation of electrode.
2) technical scheme, during preparing Si-C composite material, first passes through magnesiothermic reduction silicon dioxide, then wraps
Cover carbon, efficiently avoid the generation of the side reaction things such as carborundum.
3) technical scheme is by realizing Si-C composite material hollow by controlling magnesium thermit degree
The regulation and control of the size of gap layer and the regulation and control of porous nano silicon structure.
4) technical scheme, being not required to use nano-silicon is raw material, and raw material sources are wide, low cost, and flow process is simple, can
Control, it is not necessary to expensive manufacture equipment, is suitable for large-scale production, and practical application foreground is good.
Accompanying drawing explanation
[Fig. 1] is the X-ray diffractogram of the product of comparative example 1 preparation: as can be seen from the figure first carbon coated magnesium again
Material prepared by thermal reduction has an obvious miscellaneous peak at about 36 °, shows that reaction generates carborundum impurity.
[Fig. 2] is the transmission electron microscope picture of the product of comparative example 2 preparation: as can be seen from the figure divide after magnesiothermic reduction
The product not utilizing hydrochloric acid and hydrofluoric acid treatment to obtain has obvious loose structure.
[Fig. 3] is the X-ray diffractogram of the product of embodiment 1 preparation: as can be seen from the figure by the technology of the present invention
Si-C composite material prepared by scheme does not has carborundum impurity component.
[Fig. 4] is the transmission electron microscope picture of the silica precursor that embodiment 1 uses: as can be seen from the figure before reduction
Silicon dioxide is smooth medicine ball.
[Fig. 5] is the Si@SiO of embodiment 1 preparation2The transmission electron microscope picture of intermediate product: as can be seen from the figure magnesium heat is also
The intermediate product that after former, HCl treatment obtains has maintained overall pattern, and does not have obvious loose structure.
[Fig. 6] is the transmission electron microscope picture of the C@Si product of embodiment 1 preparation: as can be seen from the figure silicon core is fixed by one layer of nothing
Type carbon is wrapped up, carbon shell and the silicon obvious void layer of internuclear existence.
[Fig. 7] is 50 discharge and recharges when lithium ion battery negative material of the Si-C composite material of embodiment 1 preparation
Capacity Plan: as can be seen from the figure the reversible specific capacity first of this battery is 1791mAh/g, after circulation 50 circle, reversible specific capacity is
1690mAh/g。
Detailed description of the invention
The concrete steps of the present invention are described by the following examples, but the scope of the claims in the present invention protection is not implemented
Example limits.
The term used in the present invention, except as otherwise noted, typically has those of ordinary skill in the art and generally manages
The implication solved.
Below in conjunction with specific embodiment and with reference to data, the present invention is described in further detail.Should be understood that these embodiments are only
It is in order to demonstrate the invention, rather than limits the scope of the present invention by any way.
In the examples below, the various processes not described in detail and method are conventional methods as known in the art.
Below in conjunction with specific embodiment, the present invention is further described.
Comparative example 1
Take 1g diameter and be about the silica spheres of 250nm as raw material, be dissolved in ethanol with phenolic resin according to mass ratio 1:1
In solvent, stir at 80 DEG C to ethanol volatilization completely, be mixed thing grind careful after under an argon atmosphere, with 5 DEG C/min's
Heating rate is warming up to 800 DEG C of reaction 2h.Reaction terminates rear products therefrom C@SiO2After mixing homogeneously with 0.8g metal magnesium powder, put
Put in the closed environment of full argon, be warming up to 700 DEG C of reaction 6h with the heating rate of 5 DEG C/min.After reaction terminates, take out
Product is dissolved in the hydrochloric acid of 1mol/L reaction 6h.It is re-dissolved in after filtering drying in the Fluohydric acid. of mass fraction 5% reacting 0.5h, mistake
Filter obtains product after drying.The X-ray diffractogram of product is as it is shown in figure 1, contain substantial amounts of carbonization sila in product
Matter composition.
The material prepared and conductive black and sodium alginate 8:1:1 in mass ratio are modulated into slurry, are coated in copper
On paper tinsel, after 60 DEG C of dry 12h, make anode plate for lithium ionic cell.With button lithium battery CR2025 as simulated battery, lithium metal
Sheet is as to electrode, and electrolyte consists of 1MLiPF6(ethylene carbonate: diethyl carbonate=1:1, v/v), barrier film is
Celgard2400, is completed in the glove box of full argon.Preparation-obtained battery is in the electric current density of 100mA/g
Under, discharge and recharge interval is that 0.01-1.5V completes charge-discharge test.The reversible specific capacity first of this battery is 546mAh/g, circulation
After 50 circles, reversible specific capacity is 308mAh/g.
Comparative example 2
Take 1g diameter and be about the silica spheres of 250nm as raw material, after mixing homogeneously with 0.8g metal magnesium powder, be placed on
It is full of in the closed environment of argon, is warming up to 700 DEG C of reaction 6h with the heating rate of 5 DEG C/min.After reaction terminates, take out product
It is dissolved in the hydrochloric acid of 1mol/L reaction 6h.It is re-dissolved in after filtering drying in the Fluohydric acid. of mass fraction 5% reacting 0.5h, crosses diafiltration
Product is obtained after washing drying.As in figure 2 it is shown, there is substantial amounts of hole in product in the transmission electron microscope picture of product.
The material prepared is made anode plate for lithium ionic cell, and assembling test battery according to the method for comparative example 1.
Test result shows, the reversible specific capacity first of this battery is 2375mAh/g, and after circulation 50 circle, reversible specific capacity is 551mAh/
g。
Embodiment 1
Take 1g diameter and be about the silica spheres of 250nm as raw material, after mixing homogeneously with 0.8g metal magnesium powder, be placed on
It is full of in the closed environment of argon, is warming up to 700 DEG C of reaction 6h with the heating rate of 5 DEG C/min.After reaction terminates, take out product
It is dissolved in the hydrochloric acid of 1mol/L reaction 6h.By intermediate product Si@SiO obtained above after filtering drying2With phenolic resin according to
Mass ratio 1:1 is dissolved in alcohol solvent, stirs to ethanol volatilization completely at 80 DEG C, be mixed thing grind careful after at argon gas
Under atmosphere, it is warming up to 800 DEG C of reaction 2h with the heating rate of 5 DEG C/min.Reaction terminates rear products therefrom C@Si@SiO2It is dissolved in quality
Reacting 0.5h in the Fluohydric acid. of mark 5%, filtration washing obtains product C@Si after drying.The X-ray of its product C@Si is spread out
Penetrate figure as it is shown on figure 3, the transmission electron microscope picture of the silica precursor used as shown in Figure 4, its gained intermediate product Si@
SiO2Transmission electron microscope picture as it is shown in figure 5, the transmission electron microscope picture of its product C@Si as shown in Figure 6.The porous nano of products therefrom
Silicon nuclear diameter is about 250nm, and carbon layers having thicknesses is about 10nm.
The material prepared is made anode plate for lithium ionic cell, and assembling test battery according to the method for comparative example 1.
Being the charge/discharge capacity figure of this battery charging and discharging 50 times as shown in Figure 7, the reversible specific capacity first of this battery is 1791mAh/g,
After circulation 50 circle, reversible specific capacity is 1690mAh/g.
Embodiment 2
Take 1g diameter and be about the silica spheres of 100nm as raw material, after mixing homogeneously with 0.5g metal magnesium powder, be placed on
It is full of in the closed environment of argon and hydrogen, is warming up to 650 DEG C of reaction 2h with the heating rate of 2 DEG C/min.After reaction terminates, take
Go out product and be dissolved in the sulphuric acid of 0.5mol/L reaction 4h.By intermediate product Si@SiO obtained above after filtering drying2With sucrose
Be dissolved in aqueous solution solvent according to mass ratio 1:10, stir to moisture evaporation complete at 100 DEG C, be mixed thing grind careful after
In a nitrogen atmosphere, it is warming up to 700 DEG C of reaction 4h with the heating rate of 10 DEG C/min.Reaction terminates rear products therefrom C@Si@
SiO2Being dissolved in the Fluohydric acid. of mass fraction 2% reaction 2h, filtration washing obtains product C@Si after drying.Products therefrom
Porous nano silicon nuclear diameter is about 100nm, and carbon layers having thicknesses is about 50nm.
The material prepared is made anode plate for lithium ionic cell, and assembling test battery according to the method for comparative example 1.
The reversible specific capacity first of this battery is 982mAh/g, and after circulation 50 circle, reversible specific capacity is 924mAh/g.
Embodiment 3
Take 1g diameter and be about the silica dioxide granule of 500nm as raw material, after mixing homogeneously with 0.7g metal magnesium powder, place
In the closed environment of full argon, it is warming up to 700 DEG C of reaction 4h with the heating rate of 10 DEG C/min.After reaction terminates, take out
Product is dissolved in the hydrochloric acid of 2mol/L reaction 8h.By intermediate product Si@SiO obtained above after filtering drying2With polyvinyl alcohol
Be dissolved in n-butanol solvent according to mass ratio 1:15, stir at 90 DEG C to ethanol volatilization completely, be mixed thing grind careful after
Under argon and nitrogen mixture atmosphere, it is warming up to 900 DEG C of reaction 6h with the heating rate of 20 DEG C/min.Reaction terminates rear gained and produces
Thing C@Si@SiO2Being dissolved in the Fluohydric acid. of mass fraction 10% reaction 0.5h, filtration washing obtains product C@Si after drying.
The porous nano silicon nuclear diameter of products therefrom is about 500nm, and carbon layers having thicknesses is about 20nm.
The material prepared is made anode plate for lithium ionic cell, and assembling test battery according to the method for comparative example 1.
The reversible specific capacity first of this battery is 853mAh/g, and after circulation 50 circle, reversible specific capacity is 798mAh/g.
Embodiment 4
Take 1g diameter and be about the silica spheres of 1 μm as raw material, after mixing homogeneously with 0.8g metal magnesium powder, be placed on and fill
In the closed environment of full argon, it is warming up to 750 DEG C of reaction 6h with the heating rate of 4 DEG C/min.After reaction terminates, take out product molten
4h is reacted in the hydrochloric acid of 3mol/L.By intermediate product Si@SiO obtained above after filtering drying2With epoxy resin according to matter
Amount is dissolved in acetone solvent than 2:1, stirs to acetone volatilization completely at 80 DEG C, be mixed thing grind careful after at argon and hydrogen
Under gas atmosphere, it is warming up to 1000 DEG C of reaction 5h with the heating rate of 10 DEG C/min.Reaction terminates rear products therefrom C@Si@SiO2Molten
Reacting 1h in the Fluohydric acid. of mass fraction 10%, filtration washing obtains product C@Si after drying.The porous of products therefrom
Nano-silicon nuclear diameter is about 1 μm, and carbon layers having thicknesses is about 10nm.
The material prepared is made anode plate for lithium ionic cell, and assembling test battery according to the method for comparative example 1.
The reversible specific capacity first of this battery is 1956mAh/g, and after circulation 50 circle, reversible specific capacity is 1802mAh/g.
Embodiment 5
Take 1g diameter and be about the silica dioxide granule of 2 μm as raw material, after mixing homogeneously with 0.9g metal magnesium powder, be placed on
It is full of in the closed environment of hydrogen, is warming up to 700 DEG C of reaction 8h with the heating rate of 5 DEG C/min.After reaction terminates, take out product
It is dissolved in the sulphuric acid of 1mol/L reaction 10h.By intermediate product Si@SiO obtained above after filtering drying2With polypropylene according to matter
Amount is dissolved in methanol solvate than 1:2, stirs to methanol volatilization completely at 60 DEG C, be mixed thing grind careful after in argon gas atmosphere
Under, it is warming up to 600 DEG C of reaction 8h with the heating rate of 20 DEG C/min.Reaction terminates rear products therefrom C@Si@SiO2It is dissolved in quality
Reacting 2h in the Fluohydric acid. of mark 5%, filtration washing obtains product C@Si after drying.The porous nano silicon core of products therefrom
Diameter is about 2 μm, and carbon layers having thicknesses is about 20nm.
The material prepared is made anode plate for lithium ionic cell, and assembling test battery according to the method for comparative example 1.
The reversible specific capacity first of this battery is 898mAh/g, and after circulation 50 circle, reversible specific capacity is 814mAh/g.
Embodiment 6
Take 1g diameter and be about the silica dioxide granule of 8 μm as raw material, after mixing homogeneously with 1g metal magnesium powder, be placed on and fill
In the closed environment of full argon, it is warming up to 650 DEG C of reaction 10h with the heating rate of 10 DEG C/min.After reaction terminates, take out product
It is dissolved in the hydrochloric acid of 2mol/L reaction 8h.By intermediate product Si@SiO obtained above after filtering drying2With glucose according to matter
Amount is dissolved in aqueous solvent than 1:1, stirs to moisture evaporation complete at 110 DEG C, be mixed thing grind careful after at nitrogen atmosphere
Under, it is warming up to 800 DEG C of reaction 6h with the heating rate of 15 DEG C/min.Reaction terminates rear products therefrom C@Si@SiO2It is dissolved in quality
Reacting 1h in the Fluohydric acid. of mark 20%, filtration washing obtains product C@Si after drying.The porous nano silicon of products therefrom
Nuclear diameter is about 8 μm, and carbon layers having thicknesses is about 5nm.
The material prepared is made anode plate for lithium ionic cell, and assembling test battery according to the method for comparative example 1.
The reversible specific capacity first of this battery is 1690mAh/g, and after circulation 50 circle, reversible specific capacity is 1548mAh/g.
Claims (10)
1. a nucleocapsid structure Si-C composite material, it is characterised in that: there is nucleocapsid structure；Described nucleocapsid structure includes by carbon
Shell that layer is constituted and the kernel that is made up of porous nano silicon；Between described shell and kernel, there is void layer.
Nucleocapsid structure Si-C composite material the most according to claim 1, it is characterised in that: the size of described kernel is 10nm
～10 μm, the thickness of described shell is 1～200nm.
3. the preparation method of the nucleocapsid structure Si-C composite material described in claim 1 or 2, it is characterised in that: include following step
Rapid:
1) silica dioxide granule carries out magnesiothermic reduction reaction by magnesium powder, obtains Si@SiO2Intermediate；
2) described Si@SiO2After intermediate carries out in-stiu coating by organic polymer carbon source, carbonization, obtain C@Si@SiO2Middle
Body；
3) described C@Si@SiO2Intermediate uses Fluohydric acid. corrosion, to obtain final product.
The preparation method of nucleocapsid structure Si-C composite material the most according to claim 3, it is characterised in that: 1) in, dioxy
After silicon carbide particle is mixed homogeneously with magnesium powder, it is placed in the closed environment of full protective atmosphere, with the intensification speed of 1～20 DEG C/min
Rate is warming up to 600～800 DEG C, carries out reduction reaction 1～12h, obtains Si@SiO2Intermediate.
The preparation method of nucleocapsid structure Si-C composite material the most according to claim 4, it is characterised in that: described dioxy
Silicon carbide particle is 1:0.4～1:1 with the mass ratio of magnesium powder.
6. according to the preparation method of the nucleocapsid structure Si-C composite material described in claim 4 or 5, it is characterised in that: described
Silica dioxide granule particle diameter is 10nm～10 μm.
The preparation method of nucleocapsid structure Si-C composite material the most according to claim 3, it is characterised in that: 2) in, described
Si@SiO2Intermediate and organic polymer carbon source are dissolved in solvent, and after mix homogeneously, stirring is evaporated, and gained solid mixture is through grinding
After mill, be placed under protective atmosphere, be warming up to 600～1200 DEG C with the heating rate of 1～20 DEG C/min, carry out carbonization 1～
12h, obtains C@Si@SiO2Intermediate.
The preparation method of nucleocapsid structure Si-C composite material the most according to claim 7, it is characterised in that: described is organic
Macromolecule carbon source and Si SiO2The mass ratio of intermediate is 100:1～1:100.
9. according to the preparation method of the nucleocapsid structure Si-C composite material described in claim 7 or 8, it is characterised in that: described
Organic polymer carbon source is in polyvinyl alcohol, polypropylene, Colophonium, phenolic resin, epoxy resin, glucose, sugarcane sugar and starch
At least one.
The preparation method of nucleocapsid structure Si-C composite material the most according to claim 3, it is characterised in that: 3) in, described
C@Si@SiO2Intermediate use mass percent concentration be 1～40% Fluohydric acid. carry out impregnation process 0.01～6h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201610503372.5A CN106099113B (en) | 2016-06-30 | 2016-06-30 | A kind of core-shell structure Si-C composite material and preparation method thereof |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106848273A (en) * | 2017-01-19 | 2017-06-13 | 深圳市沃特玛电池有限公司 | A kind of preparation method of Si-C composite material |
| CN107317012A (en) * | 2017-06-28 | 2017-11-03 | 山东大学深圳研究院 | A kind of high performance lithium ion secondary battery negative material Si/C composites and preparation method thereof |
| CN108394899A (en) * | 2018-03-29 | 2018-08-14 | 深圳市贝特瑞新能源材料股份有限公司 | A kind of absorbent charcoal material and preparation method thereof |
| CN109761239A (en) * | 2019-01-18 | 2019-05-17 | 齐鲁工业大学 | It is a kind of sensing, photoelectricity or lithium ion battery composite material and preparation method |
| WO2019104460A1 (en) * | 2017-11-28 | 2019-06-06 | 桑胜伟 | Method for preparing composite conductive paste |
| CN110085852A (en) * | 2019-05-28 | 2019-08-02 | 中国科学院重庆绿色智能技术研究院 | Conductive structure and electrode |
| CN110323418A (en) * | 2018-03-30 | 2019-10-11 | 中国石油化工股份有限公司 | Si-C composite material and its preparation method and application |
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| CN111816862A (en) * | 2020-07-31 | 2020-10-23 | 广东凯金新能源科技股份有限公司 | High-stability silicon-carbon negative electrode material and preparation method thereof |
| CN112242504A (en) * | 2019-07-18 | 2021-01-19 | 北京清创硅谷科技有限公司 | Silicon carbide coated hollow silicon material, preparation method thereof, and electrode and electrochemical device using same |
| US11069885B2 (en) | 2017-09-13 | 2021-07-20 | Unifrax I Llc | Silicon-based anode material for lithium ion battery |
| CN113363433A (en) * | 2021-05-10 | 2021-09-07 | 万向一二三股份公司 | Preparation method of silicon-based composite lithium battery negative electrode material |
| WO2021258232A1 (en) * | 2020-06-22 | 2021-12-30 | 苏州楚捷新材料科技有限公司 | Preparation method for si/c negative electrode material having elastic shell layer-coated structure for lithium ion battery |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102157731A (en) * | 2011-03-18 | 2011-08-17 | 上海交通大学 | Silicon and carbon compound anode material of lithium ion battery and preparation method of silicon and carbon compound anode material |
| CN102623680A (en) * | 2012-04-05 | 2012-08-01 | 中南大学 | Silicon-carbon composite cathode material with three-dimensional preformed hole structure and preparation method thereof |
| CN103531760A (en) * | 2013-10-28 | 2014-01-22 | 北京化工大学 | Porous silicon carbon composite microsphere with yolk-eggshell structure and preparation method therefor |
| CN104332621A (en) * | 2014-09-27 | 2015-02-04 | 奇瑞汽车股份有限公司 | Method for preparing hollow nano silicon microsphere through metal thermal reduction and lithium ion battery |
| KR20160037334A (en) * | 2014-09-26 | 2016-04-06 | (주)에스제이신소재 | The porous silicon based negative active material for a secondary battery and manufacturing method, and rechargeable lithium ion battery including the same |
-
2016
- 2016-06-30 CN CN201610503372.5A patent/CN106099113B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102157731A (en) * | 2011-03-18 | 2011-08-17 | 上海交通大学 | Silicon and carbon compound anode material of lithium ion battery and preparation method of silicon and carbon compound anode material |
| CN102623680A (en) * | 2012-04-05 | 2012-08-01 | 中南大学 | Silicon-carbon composite cathode material with three-dimensional preformed hole structure and preparation method thereof |
| CN103531760A (en) * | 2013-10-28 | 2014-01-22 | 北京化工大学 | Porous silicon carbon composite microsphere with yolk-eggshell structure and preparation method therefor |
| KR20160037334A (en) * | 2014-09-26 | 2016-04-06 | (주)에스제이신소재 | The porous silicon based negative active material for a secondary battery and manufacturing method, and rechargeable lithium ion battery including the same |
| CN104332621A (en) * | 2014-09-27 | 2015-02-04 | 奇瑞汽车股份有限公司 | Method for preparing hollow nano silicon microsphere through metal thermal reduction and lithium ion battery |
Non-Patent Citations (2)
| Title |
|---|
| XIAOLIN LI，ET AL.: "Hollow core–shell structured porous Si–C nanocomposites for Li-ion battery anodes", 《JOURNAL OF MATERIALS CHEMISTRY》 * |
| YU ZHOU，ET AL.: "Scalable synthesis of Si/SiO2@C composite from micro-silica particles for high performance lithium battery anodes", 《POWDER TECHNOLOGY》 * |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106848273A (en) * | 2017-01-19 | 2017-06-13 | 深圳市沃特玛电池有限公司 | A kind of preparation method of Si-C composite material |
| CN107317012A (en) * | 2017-06-28 | 2017-11-03 | 山东大学深圳研究院 | A kind of high performance lithium ion secondary battery negative material Si/C composites and preparation method thereof |
| US11652201B2 (en) | 2017-09-13 | 2023-05-16 | Unifrax I Llc | Silicon-based anode material for lithium ion battery |
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| WO2019104460A1 (en) * | 2017-11-28 | 2019-06-06 | 桑胜伟 | Method for preparing composite conductive paste |
| CN108394899A (en) * | 2018-03-29 | 2018-08-14 | 深圳市贝特瑞新能源材料股份有限公司 | A kind of absorbent charcoal material and preparation method thereof |
| CN110323418A (en) * | 2018-03-30 | 2019-10-11 | 中国石油化工股份有限公司 | Si-C composite material and its preparation method and application |
| CN109761239A (en) * | 2019-01-18 | 2019-05-17 | 齐鲁工业大学 | It is a kind of sensing, photoelectricity or lithium ion battery composite material and preparation method |
| CN110085852A (en) * | 2019-05-28 | 2019-08-02 | 中国科学院重庆绿色智能技术研究院 | Conductive structure and electrode |
| CN112242504A (en) * | 2019-07-18 | 2021-01-19 | 北京清创硅谷科技有限公司 | Silicon carbide coated hollow silicon material, preparation method thereof, and electrode and electrochemical device using same |
| CN110556528A (en) * | 2019-10-15 | 2019-12-10 | 浙江锂宸新材料科技有限公司 | Porous silicon/carbon shell composite material and preparation method and application thereof |
| WO2021258232A1 (en) * | 2020-06-22 | 2021-12-30 | 苏州楚捷新材料科技有限公司 | Preparation method for si/c negative electrode material having elastic shell layer-coated structure for lithium ion battery |
| CN111816862A (en) * | 2020-07-31 | 2020-10-23 | 广东凯金新能源科技股份有限公司 | High-stability silicon-carbon negative electrode material and preparation method thereof |
| CN113363433A (en) * | 2021-05-10 | 2021-09-07 | 万向一二三股份公司 | Preparation method of silicon-based composite lithium battery negative electrode material |
| CN113856707A (en) * | 2021-09-18 | 2021-12-31 | 深圳市东有新材料科技有限公司 | Hollow nano aluminum fluoride ball with high catalytic efficiency and preparation method thereof |
| CN117727916A (en) * | 2024-02-07 | 2024-03-19 | 长沙矿冶研究院有限责任公司 | Silicon-oxygen-carbon composite material containing silicon carbide coating and preparation method and application thereof |
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