CN106058167A - Porous silicon-based alloy composite - Google Patents
Porous silicon-based alloy composite Download PDFInfo
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- CN106058167A CN106058167A CN201610076649.0A CN201610076649A CN106058167A CN 106058167 A CN106058167 A CN 106058167A CN 201610076649 A CN201610076649 A CN 201610076649A CN 106058167 A CN106058167 A CN 106058167A
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Abstract
The invention discloses a porous silicon-based alloy composite. The porous silicon-based alloy composite comprises porous silicon-based alloy and a coating layer coating the surface of the porous silicon-based alloy, wherein the coating layer comprises a carbon coating and/or a polymer coating; the porous silicon-based alloy contains 50 to 95% of silicon by mass; the carbon coating accounts for 0.5 to 10% of the total mass of the porous silicon-based alloy composite; the polymer coating accounts for 0.5 to 50% of the total mass of the porous silicon-based alloy composite; and the polymer coating is a conductive polymer coating, a cross-linked polymer coating or a specific function group polymer coating, the conductive polymer coating accounts for 0.5 to 50% of the total mass of the porous silicon-based alloy composite, the cross-linked polymer coating accounts for 0.5 to 10% of the total mass of the porous silicon-based alloy composite, and the specific function group polymer coating accounts for 0.5 to 50% of the total mass of the porous silicon-based alloy composite. The porous silicon-based alloy composite is low in cost, has good electrochemical performance and can effectively improve energy density of a battery.
Description
Technical field
The present invention relates to a kind of negative electrode active material, especially relate to a kind of porous silicon-base alloy composite materials.
Background technology
In recent years, the fast development in the fields such as portable type electronic product, electric automobile, energy-accumulating power station, right
Energy storage technology is had higher requirement.Lithium ion battery becomes this due to its high energy density
The primary selection in a little fields, but still the market requirement to energy density can not be met.
At present, the main graphite cathode of negative pole of lithium ion battery, its specific capacity is 372mAh/g, seriously limits
Make the further lifting of lithium ion energy density.Silicon is subject to because having the highest theoretical lithium storage content extensively
General concern, becomes the first-selected negative pole of lithium ion battery of future generation.But elemental silicon exists during storage lithium
Huge volumetric expansion (300%), causes silicon grain that efflorescence occurs because of stress, loses with conductive agent
Make electrical contact with, and the SEI film on silicium cathode surface constantly decomposes and formed, thus cause the circulation of silicium cathode
Poor-performing, it is difficult to meet business application.
For this problem, current each scientific research institutions and company all use certain methods to improve silicium cathode
Cyclical stability, mainly has nanorize and forms the methods such as composite with other materials.Wherein porous silicon
Material receives publicity because it has the cycle performance of improvement.The preparation of porous silica material at present mainly has
Chemical reduction method, electrochemical reduction method.But, in said method, due to chemical reduction method system
There is the uncontrollable factor of product in Bei, it is possible to generate the risk of silicide, reduce stock utilization；
It is relatively low that electrochemical electrolysis method is then faced with utilization rate, reacts uneven situation.Said method all exists
The problems such as preparation condition harshness, high cost, the product obtained is difficult to meet commercial applications.
Summary of the invention
The present invention is the problem being difficult to meet commercial applications in order to solve the silicium cathode material product of prior art,
Provide a kind of low cost, there is good electrical chemical property, it is possible to the energy density of effective raising battery is many
Hole silicon-base alloy composite.
To achieve these goals, the present invention is by the following technical solutions:
A kind of porous silicon-base alloy composite materials of the present invention, described porous silicon-base alloy composite materials includes porous
Silicon-base alloy and be coated on the clad of porous silicon-base alloy surface, described clad include carbon coating layer and/or
Polymer covering layer, the weight/mass percentage composition of described porous silicon-base Silicon In Alloys is 50～95%, and described carbon is coated with
The quality of layer accounts for the 0.5～10% of porous silicon-base alloy composite materials gross mass, and described polymer covering layer is conduction
Polymer covering layer, cross linked polymer clad or particular functional group's polymer covering layer, wherein conducting polymer
Clad accounts for the 0.5～50% of porous silicon-base alloy composite materials gross mass, and cross linked polymer clad accounts for porous silicon
The 0.5～10% of base alloy composite materials gross mass, it is multiple that particular functional group's polymer covering layer accounts for porous silicon-base alloy
The 0.5～50% of condensation material gross mass.This loose structure characteristic utilizing porous silicon composite material, for activated silica
Change in volume during storage lithium provides headspace, improves its structural stability, thus it is steady to improve its electrochemistry
Qualitative；Clad structure provides stable electrolyte interface for activated silica, improves the ionic conductivity of silicon materials,
And improve the surface SEI membrane structure of silicon materials；The clad structure of certain content is conducive to safeguarding porous material
Structural stability, clad content is too low, is unfavorable for that uniform fold is on silicon materials surface, it is impossible to improve silicon materials
Electron conduction, and its mechanical stability is poor, is unfavorable for keeping its structural stability under stress；Bag
Coating too high levels, it is inconspicuous that electron conduction improves increase, the most also can reduce the capacity of material, bears silicon
The capacity of pole has a certain impact, and therefore in the present invention, the mass content of clad controls 0.5～50%；Porous
In silicon-base alloy, the weight/mass percentage composition of silicon is 50～95%, and the silicon crossing low content can cause utilization rate of raw materials relatively
Low, the capacity affecting porous silicon composite material plays.By the cladding of clad, the volumetric expansion of silicon can be limited
System, at material internal, decreases the stress in terms of pole piece vertical and horizontal, thus avoid in traditional electrode because
Stress and occur in that crackle, thus improve the cyclical stability of silicon electrode.The porous silicon-base alloy of the present invention is multiple
Condensation material has good electrical chemical property, it is possible to the effective energy density improving battery.
As preferably, described porous silicon-base alloy composite materials prepares by the following method:
(1) silicon-base alloy powder is placed in the first hydrofluoric acid solution, under stirring, adds silver nitrate molten
Liquid, filters after reaction, adds in the second hydrofluoric acid solution after filtrate being dried, and adds under stirring
Hydrogen peroxide solution, filtering drying after reaction, obtain porous silicon-base alloy powder.Fluohydric acid. and the work of silver nitrate solution
With being to become nano-Ag particles to form blindage at material surface electroless deposition, Fluohydric acid. and hydrogen peroxide solution can be right simultaneously
Material carries out corroding thus forms porous silicon-base alloy powder.
(2) after the porous silicon-base alloy powder in step (1) being mixed homogeneously with organic carbon source, at indifferent gas
Carrying out high-temperature calcination in body atmosphere, obtaining Surface coating after cooling has the porous silicon-base alloy powder of carbon coating layer, i.e.
For porous silicon-base alloy composite materials；Or the porous silicon-base alloy powder in step (1) is added containing conduction
Being polymerized in the solution of polymer, filter post-drying, obtaining Surface coating has the porous of conducting polymer clad
Silicon-base alloy powder, is porous silicon-base alloy composite materials；Or by the porous silicon-base alloy in step (1)
Adding in cross linked polymer, be polymerized after mix homogeneously at a temperature of 150～350 DEG C, obtaining Surface coating has friendship
The porous silicon-base alloy powder of linked polymer clad, is porous silicon-base alloy composite materials；Or by step (1)
In porous silicon-base alloy add containing particular functional group's polymer solution in, filter after stirring, be dried,
Surface coating has the porous silicon-base alloy powder of particular functional group's polymer covering layer, is porous silicon-base alloy multiple
Condensation material；Or Surface coating has the porous silicon-base alloy powder addition of carbon coating layer contain the molten of conducting polymer
Liquid is polymerized, filters post-drying, obtain porous silicon-base alloy composite；Or Surface coating is had carbon bag
The porous silicon-base alloy powder of coating adds in cross linked polymer, carries out high temperature polymerization, the most much after mix homogeneously
Hole silicon-base alloy composite；Or Surface coating has the porous silicon-base alloy powder of carbon coating layer add containing spy
Determine in the solution of functional polymer, filter after stirring, be dried, obtain porous silicon-base alloy composite.Many
Hole silicon-base alloy powder does not limits with the hybrid mode of organic carbon source, selects the most mixed according to the character of organic carbon source
Conjunction mode, such as include ball milling, soak, stir, solid phase or the mixing of liquid phase routine such as autoclave
Mode；Solution containing conducting polymer can be aqueous solution, it is also possible to for organic solvent solution, according to conduction
The character of polymer selects.
As preferably, in step (1), the particle diameter of described silicon-base alloy powder is 0.1～15 μm.The present invention
The particle diameter of middle silicon-base alloy powder selects the most crucial, and the alloy of lower particle diameter is difficult to be formed porous material, and more
The silicon alloy of high particle diameter is not suitable for as lithium ion battery negative material.
As preferably, described silicon-base alloy powder is Antaciron, silico-aluminum, Si-Ba alloy or silicomangan
Powder.Use process level alloy, there is the advantage of cheap/wide material sources.
As preferably, in step (1), the mass ratio of silicon-base alloy powder and the first hydrofluoric acid solution is 1:
4～15, the mass ratio of silver nitrate solution and the first hydrofluoric acid solution is 1:4～100, filtrate and the second hydrogen fluorine
The mass ratio of acid solution is 1:4～10, and the mass ratio of hydrogen peroxide and the second hydrofluoric acid solution is 1:4～50, the
The concentration of one hydrofluoric acid solution and the second hydrofluoric acid solution is 5mol/L, and silver nitrate solution concentration is
0.001～0.1mol/L, hydrogen peroxide concentration is 0.1～1mol/L.The solution exceeding this concentration range can affect nanometer
The deposition effect of silver, thus affect the preparation of porous material.
As preferably, in step (2), described organic carbon source is sucrose, glucose, Colophonium, polyacrylonitrile
Or polyvinyl alcohol.
As preferably, in step (2), high-temperature calcination temperature is 500～900 DEG C.Formed less than this temperature
Carbon conductive is poor, is unfavorable for improving the chemical property of silicium cathode；When being pyrolyzed higher than this temperature, to porous silicon
The structure of base alloy powder can have a negative impact.
As preferably, in step (2), described conducting polymer be polypyrrole, polythiophene, poly-di-thiophene,
Poly-(3,4-Ethylenedioxy Thiophene)-poly-(styrene sulfonic acid) or poly-to benzene；Described cross linked polymer is poly-third
Alkene nitrile；Described particular functional group's polymer is polyacrylic acid, polyvinyl alcohol, Polyethylene Glycol or polyimides.
Therefore, there is advantages that and provide a kind of porous silicon-base alloy composite materials, pass through
Silicon-base alloy powder is carried out porous and Surface coating to effectively improve the structural stability of silicon materials, improve
Its chemical property, the porous silicon-base alloy composite materials of the present invention is with low cost, structural stability and circulation
Good stability, has good electrical chemical property, it is possible to the effective energy density improving battery, can meet business
Application.
Detailed description of the invention
Below by detailed description of the invention, the present invention will be further described.
Embodiment 1
(1) be 0.1 μm by particle diameter, the weight/mass percentage composition of silicon be 50% Antaciron powder be placed in concentration
For 5mol/L, quality is in the first hydrofluoric acid solution of 4 times of Antaciron powder, adds under stirring
Concentration is 0.001mol/L, and quality is the silver nitrate solution of the first hydrofluoric acid solution 1/100, filters after reaction,
Adding concentration after filtrate being dried is 5mol/L, and quality is in the second hydrofluoric acid solution of filtrate 4 times,
Adding concentration under stirring is 0.1mol/L, and quality is the hydrogen peroxide solution of the second hydrofluoric acid solution 1/100,
Filtering drying after reaction, obtains porous silicon-base alloy powder；
(2) according to the quality of carbon coating layer account for porous silicon-base alloy composite materials gross mass 10% proportioning claim
After amount porous silicon-base alloy powder and sucrose, porous silicon-base alloy powder is mixed homogeneously with sucrose, at indifferent gas
Body atmosphere, carries out high-temperature calcination at 800 DEG C, obtaining Surface coating after cooling has the porous silicon-base alloy of carbon coating layer
Powder, is porous silicon-base alloy composite materials.
Embodiment 2
(1) be 15 μm by particle diameter, the weight/mass percentage composition of silicon be 95% Antaciron powder be placed in concentration
For 5mol/L, quality is in the first hydrofluoric acid solution of 15 times of Antaciron powder, adds under stirring
Concentration is 0.1mol/L, and quality is the silver nitrate solution of the first hydrofluoric acid solution 1/4, filters after reaction, incited somebody to action
It is 5mol/L that screening adds concentration after drying, and quality is in the second hydrofluoric acid solution of filtrate 10 times,
Adding concentration under stirring is 1mol/L, and quality is the hydrogen peroxide solution of the second hydrofluoric acid solution 1/50, instead
Should filtering drying afterwards, obtain porous silicon-base alloy powder；
(2) account for according to conducting polymer clad porous silicon-base alloy composite materials gross mass 0.5% proportioning
Weigh porous silicon-base alloy composite materials and poly-di-thiophene, under the conditions of atmosphere of inert gases and holding ice-water bath
Porous silicon-base alloy composite materials is added in chloroformic solution, stirs 0.5h after adding poly-di-thiophene, in four batches
Add catalyst anhydrous ferric chloride powder, filter after stirring reaction, pickling, obtain porous silicon-base alloy composite.
Embodiment 3
(1) be 1 μm by particle diameter, the weight/mass percentage composition of silicon be 65% Antaciron powder be placed in concentration
For 5mol/L, quality is in the first hydrofluoric acid solution of 8 times of Antaciron powder, adds under stirring
Concentration is 0.05mol/L, and quality is the silver nitrate solution of the first hydrofluoric acid solution 1/5, filters after reaction, will
It is 5mol/L that filtrate adds concentration after drying, and quality is in the second hydrofluoric acid solution of filtrate 5 times,
Adding concentration under stirring is 0.5mol/L, and quality is the hydrogen peroxide solution of the second hydrofluoric acid solution 1/60,
Filtering drying after reaction, obtains porous silicon-base alloy powder；
(2) the 20% of porous silicon-base alloy composite materials gross mass is accounted for according to particular functional group's polymer covering layer
Proportioning weigh porous silicon-base alloy composite materials and polyacrylic acid solution, porous silicon-base alloy composite materials is added
Entering in polyacrylic acid solution, after stirring 1h, Rotary Evaporators is dried, and obtains porous silicon-base alloy composite materials.
Porous silicon-base alloy composite materials the various embodiments described above obtained makes model as negative electrode active material
Being the button half-cell of 2025, the nano silicon material using particle diameter as 100nm makes type as negative electrode active material
Number be 2025 button half-cell as a comparison case, carry out reversible specific capacity and cycle performance head week charge and discharge respectively
Electrical efficiency is tested, and the result obtained is as follows:
From the above results, compared with nano-silicon, porous silicon composite material prepared by the present invention has excellence
Cycle performance, shows good chemical property, can be effectively improved the energy of lithium ion secondary lithium ion battery
Metric density, can be applicable to electric automobile, hybrid vehicle, mobile electronic device and other electronic products.
Embodiment described above is the one preferably scheme of the present invention, and the present invention not makees any form
On restriction, on the premise of without departing from the technical scheme described in claim, also have other variant and change
Type.
Claims (8)
1. a porous silicon-base alloy composite materials, it is characterised in that described porous silicon-base alloy composite materials includes
Porous silicon-base alloy and be coated on the clad of porous silicon-base alloy surface, described clad include carbon coating layer and
/ or polymer covering layer, the weight/mass percentage composition of described porous silicon-base Silicon In Alloys is 50～95%, described carbon bag
The quality of coating accounts for the 0.5～10% of porous silicon-base alloy composite materials gross mass, and described polymer covering layer is for leading
Electric polymer clad, cross linked polymer clad or particular functional group's polymer covering layer, wherein conducting polymer
Thing clad accounts for the 0.5～50% of porous silicon-base alloy composite materials gross mass, and cross linked polymer clad accounts for porous
The 0.5～10% of silicon-base alloy composite gross mass, particular functional group's polymer covering layer accounts for porous silicon-base alloy
The 0.5～50% of composite gross mass.
A kind of porous silicon-base alloy composite materials the most according to claim 1, it is characterised in that described porous
Silicon-base alloy composite prepares by the following method:
(1) silicon-base alloy powder is placed in the first hydrofluoric acid solution, under stirring, adds silver nitrate solution,
Filter after reaction, add in the second hydrofluoric acid solution after filtrate is dried, under stirring, add dioxygen
Aqueous solution, filtering drying after reaction, obtain porous silicon-base alloy powder；
(2) after the porous silicon-base alloy powder in step (1) being mixed homogeneously with organic carbon source, at noble gas atmosphere
Carrying out high-temperature calcination in enclosing, obtaining Surface coating after cooling has the porous silicon-base alloy powder of carbon coating layer, is many
Hole silicon-base alloy composite；
Or will the solution containing conducting polymer of the porous silicon-base alloy powder addition in step (1) be polymerized,
Filtering post-drying, obtaining Surface coating has the porous silicon-base alloy powder of conducting polymer clad, is porous silicon
Base alloy composite materials；
Or the porous silicon-base alloy in step (1) is added in cross linked polymer, it is carried out at after mix homogeneously
It is polymerized at a temperature of 150～350 DEG C, obtains the porous silicon-base alloyed powder of the crosslinking polymer covering layer of Surface coating
End, is porous silicon-base alloy composite materials；
Or the porous silicon-base alloy in step (1) is added in the solution containing particular functional group's polymer, after stirring
Filtering, be dried, obtaining Surface coating has the porous silicon-base alloy powder of particular functional group's polymer covering layer, is
Porous silicon-base alloy composite materials；
Or Surface coating has the porous silicon-base alloy powder of carbon coating layer add in the solution containing conducting polymer
Row polymerization, filters post-drying, obtains porous silicon-base alloy composite；
Or Surface coating has the porous silicon-base alloy powder of carbon coating layer add in cross linked polymer, mix homogeneously is laggard
Row high temperature polymerization, obtains porous silicon-base alloy composite；
Or Surface coating has the porous silicon-base alloy powder addition of carbon coating layer contain the molten of particular functional group's polymer
In liquid, filter after stirring, be dried, obtain porous silicon-base alloy composite.
A kind of porous silicon-base alloy composite materials the most according to claim 2, it is characterised in that step (1)
In, the particle diameter of described silicon-base alloy powder is 0.1～15 μm.
4. according to a kind of porous silicon-base alloy composite materials described in Claims 2 or 3, it is characterised in that described
Silicon-base alloy powder is Antaciron, silico-aluminum, Si-Ba alloy or silicomangan powder.
A kind of porous silicon-base alloy composite materials the most according to claim 2, it is characterised in that step (1)
In, the mass ratio of silicon-base alloy powder and the first hydrofluoric acid solution is 1:4～15, silver nitrate solution and the first hydrogen
The mass ratio of fluorspar acid solution is 1:4～100, and filtrate is 1:4～10 with the mass ratio of the second hydrofluoric acid solution,
The mass ratio of hydrogen peroxide and the second hydrofluoric acid solution is 1:4～50, and the first hydrofluoric acid solution and the second Fluohydric acid. are molten
The concentration of liquid is 5mol/L, and silver nitrate solution concentration is 0.001～0.1mol/L, and hydrogen peroxide concentration is
0.1～1mol/L.
A kind of porous silicon-base alloy composite materials the most according to claim 2, it is characterised in that step (2)
In, described organic carbon source is sucrose, glucose, Colophonium, polyacrylonitrile or polyvinyl alcohol.
A kind of porous silicon-base alloy composite materials the most according to claim 2, it is characterised in that step (2)
In, high-temperature calcination temperature is 500～900 DEG C.
A kind of porous silicon-base alloy composite materials the most according to claim 2, it is characterised in that step (2)
In, described conducting polymer is polypyrrole, polythiophene, poly-di-thiophene, poly-(3,4-Ethylenedioxy Thiophene)
-poly-(styrene sulfonic acid) or poly-to benzene；Described cross linked polymer is polyacrylonitrile；Described particular functional is reunited
Compound is polyacrylic acid, polyvinyl alcohol, Polyethylene Glycol or polyimides.
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Cited By (14)
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| CN106571457A (en) * | 2016-11-11 | 2017-04-19 | 深圳市鑫永丰科技有限公司 | Silicon-based negative electrode material and preparation method thereof |
| CN106935834A (en) * | 2017-04-21 | 2017-07-07 | 山东大学 | A kind of porous silicon negative material of compound carbon coating and preparation method thereof |
| CN108110240A (en) * | 2017-12-15 | 2018-06-01 | 山东大学 | A kind of nano-structure porous silicon base complex electrode material and preparation method thereof |
| CN108172781A (en) * | 2017-12-11 | 2018-06-15 | 浙江大学 | A kind of Si-C composite material of Argent grain doping and its preparation method and application |
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| CN111146410B (en) * | 2018-11-05 | 2021-03-02 | 宁德时代新能源科技股份有限公司 | Negative electrode active material and battery |
| CN111211316A (en) * | 2020-03-05 | 2020-05-29 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of conductive polymer polyaniline-coated porous silicon-based negative electrode material, product and application thereof |
| CN111384386A (en) * | 2020-03-25 | 2020-07-07 | 长沙矿冶研究院有限责任公司 | Negative electrode active material and preparation method thereof |
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