CN105826527A - Porous silicon-carbon composite material and preparation method and application thereof - Google Patents
Porous silicon-carbon composite material and preparation method and application thereof Download PDFInfo
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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
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- 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
Abstract
The invention discloses a preparation method of a porous silicon-carbon composite material.The preparation method specifically comprises the steps that magnesium silicide powder is placed in a CO2-Ar mixed atmosphere to be subjected to heat treatment at the temperature of 700 DEG C-900 DEG C and then subjected to acid pickling and aftertreatment to obtain the porous silicon-carbon composite material, wherein the volume fraction of CO2 in the CO2-Ar mixed atmosphere is 10%-90%.According to the preparation method, the technology is simple, repetition is easy to achieve, and large-scale industrialized production can be achieved.When the porous silicon-carbon composite material prepared through the method is applied to a lithium ion battery by serving as a negative electrode material, the circulating stability of the lithium ion battery can be significantly improved.
Description
Technical field
The invention belongs to the preparation field of composite, be specifically related to a kind of porous silicon-carbon composite
And its preparation method and application.
Background technology
Lithium ion battery is the widely used rechargeable battery of a kind of modern society.Owing to lithium is at each metal
In there is extremely low proportion, have again the most negative electrode potential, so, when lithium is as battery material, will
There is the significant advantage such as high-energy-density and high charge voltage.But, when lithium is as battery cathode
During materials'use, it will produce dendritic segregation during separating out lithium, form dendritic Li dendrite,
This Li dendrite is gradually grown up and be will puncture through barrier film, connects both positive and negative polarity so that battery short circuit, causes danger.
So, the lithium cell cathode material of nowadays industrialization is not lithium metal, but a kind of stratified material,
Lithium ion can the most constantly embed and deviate from, it is achieved charging and discharging, therefore, and lithium electricity
Pond full name is lithium ion battery or rocking chair type battery.
Up to now, it is possible to the lithium ion battery negative material realizing commercial application is mainly with graphite
For the material with carbon element represented.Graphite is a kind of stratified material, has good electric conductivity, can well
Embed lithium ion and the change of volume occurs hardly, so, graphite has excellent when charge and discharge cycles
Different stability.But, it is limited that graphite can accommodate the space of lithium ion between layers, because of
And the highest theoretical specific capacity of only 372mAh/g, this material with carbon element making graphite be representative is increasingly
It is difficult to meet modern society's particularly electronic product and the electric automobile industry need to height ratio capacity battery
Ask.
Silicon, is the semi-conducting material in a kind of indirect forbidden band, and it can form polytype alloy with lithium,
When using as lithium ion battery negative material, it has the highest theoretical specific capacity
(4200mAh/g) with relatively low electrode potential, this makes silicon become height ratio capacity and high charge voltage
The hot-candidate material of lithium cell negative pole.But, silicon, during Lithium-ion embeding and abjection, will occur
The volumetric expansion of up to 300% and contraction, under continuous this violent change in volume, silicon will be by
Gradually rupturing and even pulverize, until completely disengaging from electrode, losing electrical activity.Additionally, the conduction of silicon
Property and bad, its transmission electric charge inefficient, this will reduce whole battery electrical transfer efficiency.
In order to solve silicon these problems as lithium ion battery negative material, researchers both domestic and external
Propose many schemes.Wherein, the mode that silico-carbo is combined receives most concerns, this is because:
First, the electric conductivity of carbon is the best, after silicon and carbon are combined, will improve the conduction of this individual system greatly
Property.Then, the mechanical ductility of carbon is fine, can effectively alleviate the volumetric expansion of silicon, improves system
Cyclical stability.
(Shilong Jin, Hao Jiang, Yanjie Hu, Jianhua Shen, the and such as Shilong Jing
Chunzhong Li.Face-to-Face Contact and Open-Void Coinvolved SiC
Nanohybrids Lithium-Ion Battery Anodes with Extremely Long Cycle Life.
Adv.Funct.Mater.2015,25,5395-5401.) a kind of graphene/carbon nano-tube three-dimensional gas is devised
The silicon grain of nanometer, as carrier, is then supported in the middle of the network of aeroge by gel complex material
Scheme.Like this, three-dimensional material with carbon element network will keep excellent electrical contact with silicon grain so that
The electric conductivity of this individual system is significantly improved.Additionally, silicon grain expand after still with three-dimensional
Material with carbon element network keeps electrical contact, maintains the activity of silicon.But, Graphene and CNT and
Silicon nanoparticle is the most expensive and is difficult to volume production, and therefore, the design of this material is difficult to industrialization.
(Qinbai Yun, Xianying Qin, Wei Lv, Yan-Bing He, the Baohua such as Qinbai Yun
Li,Feiyu Kang,Quan-Hong Yang.‘Concrete’inspired construction of a
siliconcarbon hybrid electrode for high performance lithium ion battery.
CARBON 93 (2015) 59-67.) devise a kind of electrode being similar to that cement, Ji Jiangshi
Ink alkene, silicon nanoparticle, PAN first make slurry coating on a current collector, and then high temperature is by PAN
Being cracked into carbon, the negative pole structure obtained is: nano silicon particles is dispersed in Graphene and cracks what carbon was constituted
Among three-dimensional network so that the electric conductivity of system improves, and the volumetric expansion of silicon is the most effectively alleviated.
But, similar with the problem of scheme above, Graphene and silicon nanoparticle are expensive, it is difficult to amount
Producing, therefore, this material system is the most just difficult to industrialization.
Wan-Jing Yu etc. (Wan-Jing Yu, Chang Liu, Peng-Xiang Hou, Lili Zhang,
Xu-Yi Shan,Feng Li and Hui-Ming Cheng.Lithiation of Silicon Nanoparticles
Confined in Carbon Nanotubes.ACS NANO 2015,5063-5071.) by CVD's
Way is at CNT inside deposition silicon grain so that silicon can be limited in inside carbon pipe, so, and silicon
When particle volume expands, CNT also can expand therewith, but is unlikely to rupture, and can effectively alleviate silicon
Volumetric expansion, thus there is higher cyclical stability.But, the way of CVD is being received
In rice carbon pipe, deposition silicon grain is the highest to equipment requirements, it is difficult to volume production, cost is high, it is difficult to go on
Industrialization road.
Summary of the invention
The invention provides the preparation method of a kind of porous silicon-carbon composite, technique is simple, it is easy to
Repeat, large-scale industrial production can be realized.The porous silicon prepared-carbon composite conduct
Negative material is applied in lithium ion battery, will significantly improve the cyclical stability of lithium ion battery.
A kind of method preparing porous silicon-carbon composite, specifically includes following steps:
Magnesium silicide powder is placed in CO2Under/Ar mixed atmosphere, at 700～900 DEG C, carry out heat treatment,
Described porous silicon-carbon/carbon-copper composite material is obtained again through pickling and post processing；
Described CO2In/Ar mixed atmosphere, CO2Volume fraction be 10～90%.
In the present invention, use magnesium silicide is raw material, CO2/ Ar gaseous mixture is reaction gas, successfully synthesizes
Go out porous silicon-carbon composite.This invention make use of magnesium silicide decomposes to be silicon and magnesium, and
Magnesium can restore the chemical principle of the carbon in carbon dioxide, and the porous silicon that pickling thereafter obtains-
When carbon is as ion cathode material lithium, there is the highest specific capacity and excellent cyclical stability.The party
Method is very simple, and operating process is easy, and the instrument and equipment of use is common to be easy to get, and the raw material of employing is
Finished industrial product, easily realizes large-scale industrial production.
In the present invention, make use of the very simple technique of one to obtain porous silicon, porous silicon is as lithium
During ion battery cathode material, its surface area is big, and active area is big, the transmission of lithium ion and electronics away from
From short, efficiency for charge-discharge will be greatly improved.And, it is inside that the structure of porous effectively provides silicon
The space expanded, this can well alleviate the outside Volumetric expansion that silicon is violent when embedding lithium, real
Existing high cyclical stability and safety.The present invention is while preparing porous silicon, by carbon with many
Hole silicon is successfully combined, and obtains the composite of porous silico-carbo.In this composite, carbon covers
The surface of silicon, on the one hand greatly improves the electric conductivity of system, on the other hand effectively alleviates silicon
Outside volumetric expansion.
As preferably, described CO2In/Ar mixed atmosphere, CO2Volume fraction be 20～80%.
Further preferably, CO2Volume fraction be 40～60%.Finding through test, now, in product, carbon contains
Measure the highest.This is possibly due to CO2Being the more weak gas of a kind of oxidisability, its oxidation with magnesium is also
Former reaction is often at dense CO2The purest CO2Could occur under atmosphere.But, owing to reaction is raw
The C become also has reproducibility, although it is strong that its reproducibility does not has magnesium metal, but, it is also possible that
With dense CO2Reaction so that in product, the content of carbon reduces.When in product, carbon content is the highest, carbon pair
Silicon cushioning effect of change in volume when deintercalate lithium ions is the most obvious, puies forward whole system electric conductivity
Height is the strongest, and therefore, when it uses as lithium ion battery negative material, its cycle performance is the most more
Add stable.
As preferably, described heat treatment time is 10～20h.
As preferably, the hydrochloric acid that described pickling uses concentration to be 0.5～5mol/L, the process time is
2～10h.
As preferably, described post processing includes that washing, product are centrifugal and are vacuum dried.
The invention also discloses the porous silicon-carbon composite prepared according to above-mentioned method, and
Application in lithium ion battery.Understand through test, the porous silicon-carbon composite prepared with the present invention
It is used for assembling lithium ion battery as negative material, the stable circulation of lithium ion battery can be significantly improved
Property.
Compared with prior art, the present invention has a following useful technique effect:
1) in the preparation field of lithium cell cathode material, propose first to use carbon dioxide as carbon source
Prepare silico-carbo composite.Comparatively speaking, industrial be coated with carbon may often be such that use Colophonium
Obtain Deng Organic substance Pintsch process under an inert atmosphere, in these carbon source cracking process, by big for release
The poisonous and hazardous gas of amount, and carbon dioxide is as carbon source not only abundance, low price, nothing
Any environmental pollution, and consume the gas-carbon dioxide causing greenhouse effect in a large number, it is a kind of
Environmentally friendly carbon source.
2) while preparing porous silicon, make use of the reaction of magnesium and carbon dioxide cleverly, thus
By in the Process step combination of bag carbon to the preparation process of porous silicon, one-step method prepare porous silicon-
Carbon composite.Bag carbon technique of the prior art needs first and liquid phase or the Organic substance carbon source ball of solid phase
Mill mixing, is then dried, then carries out high-temperature heat treatment, not only complex process, and due to liquid phase or
The Organic substance of solid phase and the contact of silicon are the most uneven so that the carbon wrapped also is difficult to uniformly, even go out
Now a lot of local situations about not being coated with.In contrast, using carbon dioxide as the carbon source of a kind of gaseous state,
I.e. can fully contact with silicon, the carbon of generation can also more uniformly be coated on the surface of silicon, is formed
One layer more uniform, finer and close carbon film.It is applied in lithium ion battery as cathode material,
The cyclical stability of battery can be more excellent.
3) this technique is simple, it is easy to repeat, and abundant raw material source, cheap, can realize big
The industrialized production of scale.
Accompanying drawing explanation
Fig. 1 is the test result of the porous silicon-carbon composite of embodiment 1 preparation；Fig. 1 a and Fig. 1 b is it
Stereoscan photograph (SEM), Fig. 1 c be its transmission electron microscope photo (TEM), Fig. 1 d be that its x penetrates
Line probe power spectrum (EDS).
Fig. 2 is that the porous silicon-carbon composite prepared with embodiment 1 and comparative example respectively is for negative material group
The recycle ratio capacity curve of the lithium ion battery of dress and the comparison diagram of coulombic efficiency.Wherein, solid it is
The data point of the present embodiment product, hollow must be the data point of comparative example 1 product.
Fig. 3 is that the porous silicon-carbon composite prepared with embodiment 3 and comparative example respectively is for negative material group
The recycle ratio capacity curve of the lithium ion battery of dress and the comparison diagram of coulombic efficiency.Wherein, solid it is
The data point of the present embodiment product, hollow must be the data point of comparative example 1 product.
Fig. 4 is that the porous silicon-carbon composite prepared with embodiment 5 and comparative example respectively is for negative material group
The recycle ratio capacity curve of the lithium ion battery of dress and the comparison diagram of coulombic efficiency.Wherein, solid it is
The data point of the present embodiment product, hollow must be the data point of comparative example 1 product.
Detailed description of the invention
Below by specific embodiment, the invention will be further described, but protection scope of the present invention is not
It is confined to following example.
Embodiment 1
1) by magnesium silicide at 700 DEG C of heat treatment 20h, heat treatment process passes to the CO of excess2Volume integral
Number is the CO of 80%2/ Ar gaseous mixture is as reaction gas.
2) by step 1) products therefrom processes 10h, wherein hydrochloric acid in certain density hydrochloric acid solution
Concentration is 0.5 mol/L, re-uses deionized water and cleans 5 times, be then centrifuged for, finally after acid treatment
It is vacuum dried.
The relevant characterization result of porous silicon-carbon composite that the present embodiment prepares is as shown in Figure 1.
As seen from the figure, the present embodiment product is the loose structure with a large amount of equally distributed nanoscale hole,
The mass fraction of its carbon is about 40%, and is evenly coated at the surface of silicon with the form of indefinite form carbon film,
Form the silico-carbo composite with nucleocapsid structure feature.
Porous silicon-the carbon composite prepared by the present embodiment is made button cell and is carried out performance survey
Examination, obtains its circulation volume curve and often takes turns the coulombic efficiency of circulation.
It is right that the porous silicon-carbon composite prepared with regard to recycle ratio capacity and coulombic efficiency and comparative example is carried out
Ratio, result is as shown in Figure 2.As seen from the figure, the porous silico-carbo that after 50 circulations prepared by this technique holds
Amount is far above contrast material, and cyclical stability is more excellent, and the superiority of its performance is clearly.
Embodiment 2
Preparation process is identical with embodiment 1, differs only in CO2In/Ar gaseous mixture, CO2
Volume fraction is 60%.The pattern of the porous silicon-carbon composite prepared is similar to Example 1,
But the mass fraction of carbon is about 45%.
Embodiment 3
1) by magnesium silicide at 800 DEG C of heat treatment 15h, heat treatment process passes to the CO of excess2Volume integral
Number is the CO of 50%2/ Ar gaseous mixture is as reaction gas.
2) by step 1) products therefrom processes 5h, wherein hydrochloric acid in certain density hydrochloric acid solution
Concentration is 2.0 mol/L, re-uses deionized water and cleans 7 times, be then centrifuged for, finally after acid treatment
It is vacuum dried.
The pattern of porous silicon-carbon composite that the present embodiment prepares is similar to Example 1,
But the mass fraction of carbon is about 46%.
Porous silicon-the carbon composite prepared by the present embodiment is made button cell and is carried out performance survey
Examination, it is right that the porous silicon-carbon composite prepared with regard to recycle ratio capacity and coulombic efficiency and comparative example is carried out
Ratio, as shown in Figure 3.As seen from the figure, the porous silico-carbo capacity that after 50 circulations prepared by this technique is remote
Higher than contrast material, cyclical stability is more excellent, and the superiority of its performance is clearly.
Embodiment 4
Preparation process is identical with embodiment 1, differs only in CO2In/Ar gaseous mixture, CO2
Volume fraction is 40%.The pattern of the porous silicon-carbon composite prepared is similar to Example 1,
But the mass fraction of carbon is about 46%.
Embodiment 5
1) by magnesium silicide at 900 DEG C of heat treatment 10h, heat treatment process passes to the CO of excess2Volume integral
Number is the CO of 20%2/ Ar gaseous mixture is as reaction gas.
2) by step 1) products therefrom processes 2h, wherein hydrochloric acid in certain density hydrochloric acid solution
Concentration is 5 mol/L, re-uses deionized water and cleans 8 times, be then centrifuged for after acid treatment, the most laggard
Row vacuum drying.The dependence test result of the porous silicon obtained is as shown in Figure 1.
The pattern of porous silicon-carbon composite that the present embodiment prepares is similar to Example 1, but
The mass fraction of carbon is about 41%.
Porous silicon-the carbon composite prepared by the present embodiment is made button cell and is carried out performance survey
Examination, it is right that the porous silicon-carbon composite prepared with regard to recycle ratio capacity and coulombic efficiency and comparative example is carried out
Ratio, as shown in Figure 4.As seen from the figure, the porous silico-carbo capacity that after 50 circulations prepared by this technique is remote
Higher than contrast material, cyclical stability is more excellent, and the superiority of its performance is clearly.
Comparative example
Use the preparation method in the patent documentation of Publication No. CN103779544A, particularly as follows:
First, by magnesium silicide and the mixing of polyvinyl alcohol ball milling of mass ratio 1:2.Then, first 350 DEG C
Heat treatment 5h, then 700 DEG C of heat treatment 15h, heat-treating atmosphere is the gaseous mixture of argon and air, argon
Air volume mark is 90%.Finally, heat-treated products is located in the mixed acid solution of hydrochloric acid and Fluohydric acid.
Reason 5h, then is centrifuged, dry the porous silicon that obtains with Organic substance as carbon source (herein as polyvinyl alcohol)-
Carbon granule.
Claims (8)
1. the method preparing porous silicon-carbon composite, it is characterised in that step is as follows:
Magnesium silicide powder is placed in CO2Under/Ar mixed atmosphere, at 700～900 DEG C, carry out heat treatment,
Described porous silicon-carbon/carbon-copper composite material is obtained again through pickling and post processing；
Described CO2In/Ar mixed atmosphere, CO2Volume fraction be 10～90%.
The method preparing porous silicon-carbon composite the most according to claim 1, its feature exists
In, described CO2In/Ar mixed atmosphere, CO2Volume fraction be 20～80%.
The method preparing porous silicon-carbon composite the most according to claim 1, its feature exists
In, described CO2In/Ar mixed atmosphere, CO2Volume fraction be 40～60%.
The method preparing porous silicon-carbon composite the most according to claim 1, its feature exists
In, described heat treatment time is 10～20h.
The method preparing porous silicon-carbon composite the most according to claim 1, its feature exists
In, the hydrochloric acid that described pickling uses concentration to be 0.5～5mol/L, the process time is 2～10h.
The method preparing porous silicon-carbon composite the most according to claim 1, its feature exists
In, described post processing includes that washing, product are centrifugal and are vacuum dried.
7. porous silicon-carbon composite that prepared by a method according to claims 1 to 6.
8. porous silicon-carbon composite according to claim 7 is in lithium ion battery
Application.
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| CN107215874A (en) * | 2017-05-09 | 2017-09-29 | 武汉科技大学 | A kind of preparation method of ant nest shape porous silicon for lithium ion battery |
| CN107742715A (en) * | 2017-10-25 | 2018-02-27 | 山东大学 | A kind of preparation method of lithium cell cathode material nano-structure porous silicon |
| CN108023076A (en) * | 2017-11-30 | 2018-05-11 | 武汉科技大学 | A kind of cellular Si-C composite material, its preparation method and application |
| CN108269989A (en) * | 2018-02-09 | 2018-07-10 | 武汉科技大学 | A kind of carbon coating micron silicon, preparation method and application |
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| CN110679013A (en) * | 2017-09-07 | 2020-01-10 | 华盛顿州立大学 | Battery with carbon coated macroscopic pore silicon anode |
| US10797308B2 (en) * | 2017-09-07 | 2020-10-06 | Washington State University | Batteries with anodes of carbon-coated macro-porous silicon |
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