CN105826527B - A kind of porous silicon-carbon composite and its preparation method and application - Google Patents
A kind of porous silicon-carbon composite and its preparation method and application Download PDFInfo
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- CN105826527B CN105826527B CN201610164963.4A CN201610164963A CN105826527B CN 105826527 B CN105826527 B CN 105826527B CN 201610164963 A CN201610164963 A CN 201610164963A CN 105826527 B CN105826527 B CN 105826527B
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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
- H01—ELECTRIC ELEMENTS
- 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
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- 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 kind of preparation method of porous Si-C composite material, specially：Silication magnesium dust is placed in CO2It under/Ar mixed atmospheres, is heat-treated at 700~900 DEG C, then the porous silicon carbon/carbon-copper composite material is obtained through pickling and post processing；The CO2In/Ar mixed atmospheres, CO2Volume fraction be 10~90%.The present invention's is simple for process, is easy to repeat, it can be achieved that large-scale industrial production.The porous Si-C composite material being prepared is applied to as negative material in lithium ion battery, will significantly improve the cyclical stability of lithium ion battery.
Description
Technical field
The invention belongs to the preparation fields of composite material, and in particular to a kind of porous silicon-carbon composite and its preparation side
Method and application.
Background technology
Lithium ion battery is a kind of widely used rechargeable battery of modern society.Due to lithium in each metal have it is extremely low
Proportion, and have most negative electrode potential, so, when lithium is as battery material, will have high-energy density and high charge voltage
Etc. significant advantages.But when lithium as cell negative electrode material in use, its will to generate dendrite during lithium is precipitated inclined
Analysis, forms dendritic Li dendrite, and this Li dendrite, which is gradually grown up, will puncture through diaphragm, connects positive and negative anodes so that battery short circuit, hair
It is raw dangerous.So it is lithium metal that the lithium cell cathode material of nowadays industrialization, which is not, but a kind of stratified material, lithium ion can
It with continuous embedded and abjection between them, realizes and is charged and discharged, therefore, lithium battery full name is lithium ion battery or shakes
Chair form battery.
Up to now, the lithium ion battery negative material that can realize commercial application is mainly the carbon using graphite as representative
Material.Graphite is a kind of stratified material, has good electric conductivity, can be very good embedded lithium ion and volume hardly occurs
Change, so, graphite is in charge and discharge cycles with excellent stability.But graphite can accommodate lithium between layers
The space of ion is limited, consequently only that the highest theoretical specific capacity of 372mAh/g, this causes the carbon material that graphite is representative
It is increasingly difficult to meet the needs of modern society's particularly electronic product and electric vehicle industry are to height ratio capacity battery.
Silicon, is a kind of semi-conducting material of indirect forbidden band, it can form a plurality of types of alloys with lithium, as lithium from
In use, it has highest theoretical specific capacity (4200mAh/g) and relatively low electrode potential, this causes sub- cell negative electrode material
Silicon becomes the hot-candidate material of height ratio capacity and high charge voltage lithium cell negative pole.But silicon in lithium ion insertion and was deviate from
To up to 300% volume expansion and contraction occur for Cheng Zhong, and under continuous this violent volume change, silicon will gradually be broken
It splits and even crushes, completely disengaged until with electrode, lose electrical activity.In addition, the electric conductivity of silicon and bad, transmission charge
It is inefficient, this electrical transfer efficiency that will reduce entire battery.
In order to solve the problems, such as silicon as lithium ion battery negative material these, researchers both domestic and external propose many
Scheme.Wherein, the compound mode of silico-carbo receives most concerns, this is because：First, the electric conductivity of carbon is very good, silicon and
After carbon is compound, the electric conductivity of this system will be greatly improved.Then, the mechanical ductility of carbon is fine, can effectively alleviate silicon
Volume expansion, improve the cyclical stability of system.
(Shilong Jin, Hao Jiang, Yanjie Hu, the Jianhua Shen, 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 aeroge) is devised to answer
Condensation material is as carrier, the scheme being then supported on the silicon particle of nanometer among the network of aeroge.In this case, it is three-dimensional
Carbon material network will keep excellent electrical contact with silicon particle so that the electric conductivity of this system is significantly improved.In addition,
It still keeps being in electrical contact with three-dimensional carbon material network after silicon particle expansion, maintains the activity of silicon.But graphene and carbon
Nanotube and silicon nanoparticle are all expensive and be difficult to volume production, and therefore, the design of this material is difficult to industrialization.
Qinbai Yun etc. (Qinbai Yun, Xianying Qin, Wei Lv, Yan-Bing He, Baohua 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.) electrode that a kind of structure is similar to cement is devised, i.e., slurry coating is first made in graphene, silicon nanoparticle, PAN and existed
On collector, then PAN is cracked into carbon by high temperature, and obtained negative pole structure is：Nano silicon particles are dispersed in graphene and cracking
Among the three-dimensional network that carbon is formed so that the electric conductivity of system improves, and the volume expansion of silicon is also effectively alleviated.But with
Similar the problem of scheme above, graphene and silicon nanoparticle are expensive, it is difficult to volume production, therefore, this material system
Just it is difficult to realize industrialization.
(Wan-Jing Yu, Chang Liu, Peng-Xiang Hou, the Lili Zhang, Xu-Yi such as Wan-Jing Yu
Shan,Feng Li and Hui-Ming Cheng.Lithiation of Silicon Nanoparticles Confined
In Carbon Nanotubes.ACS NANO 2015,5063-5071.) it is deposited inside carbon nanotube by the method for CVD
Silicon particle so that silicon can be limited in inside carbon pipe, in this way, carbon nanotube can also expand therewith during silicon particle volume expansion, but
It is unlikely to rupture, can effectively alleviates the Volumetric expansion of silicon, thus with higher cyclical stability.But CVD is done
It is very high to equipment requirement that method deposits silicon particle in carbon nanotubes, it is difficult to which volume production, cost are high, it is difficult to go on industrialization it
Road.
Invention content
It is simple for process the present invention provides a kind of preparation method of porous silicon-carbon composite, be easy to repeat, it can be achieved that
Large-scale industrial production.Porous silicon-the carbon composite being prepared is applied to as negative material in lithium ion battery,
The cyclical stability of lithium ion battery will be significantly improved.
A kind of method for preparing porous silicon-carbon composite, specifically includes following steps：
Silication magnesium dust is placed in CO2Under/Ar mixed atmospheres, be heat-treated at 700~900 DEG C, then through pickling and
Post processing obtains the porous silicon-carbon/carbon-copper composite material；
The CO2In/Ar mixed atmospheres, CO2Volume fraction be 10~90%.
In the present invention, using magnesium silicide be raw material, CO2/ Ar gaseous mixtures are reaction gas, have successfully synthesized porous silico-carbo
Composite material.Magnesium silicide, which is utilized, in the invention is heated and is decomposed into silicon and magnesium and magnesium can restore carbon in carbon dioxide
Chemical principle when the porous silico-carbo that pickling thereafter obtains is as ion cathode material lithium, has very high specific capacity and excellent
Different cyclical stability.This method very simple, operating process is easy, and the instrument and equipment used is common to be easy to get, the raw material of use
It is finished industrial product, large-scale industrial production easy to implement.
In the present invention, a kind of very simple technique is utilized and has obtained porous silicon, porous silicon is born as lithium ion battery
During the material of pole, surface area is big, and active area is big, and the transmission range of lithium ion and electronics is short, and efficiency for charge-discharge will carry significantly
It is high.Moreover, porous structure effectively provides the space that silicon inwardly expands, it is violent in embedding lithium that this can alleviate silicon well
Outside Volumetric expansion realizes high cyclical stability and safety.The present invention, will while porous silicon is prepared
Carbon and porous silicon success are compound, obtain the composite material of porous silico-carbo.In this composite material, carbon is covered in the surface of silicon, and one
Aspect greatly improves the electric conductivity of system, on the other hand effectively alleviates the outside volume expansion of silicon.
Preferably, the CO2In/Ar mixed atmospheres, CO2Volume fraction be 20~80%.Further preferably, CO2
Volume fraction be 40~60%.It is found through experiment that at this point, carbon content highest in product.This may be because of CO2It is a kind of oxygen
The weaker gas of the property changed, the redox reaction with magnesium is often in dense CO2Even pure CO2It could occur under atmosphere.But
It is, since the C of reaction generation also has reproducibility, although its reproducibility is strong there is no magnesium metal, it is also possible that with dense
CO2Reaction so that the content of carbon is reduced in product.When carbon content is higher in product, carbon volume in deintercalate lithium ions to silicon
The cushioning effect of variation is more apparent, also stronger to the raising of whole system electric conductivity, therefore, is used as negative electrode of lithium ion battery
During materials'use, cycle performance is also just more stablized.
Preferably, the heat treatment time is 10~20h.
Preferably, the pickling uses the hydrochloric acid of a concentration of 0.5~5mol/L, processing time is 2~10h.
Preferably, the post processing includes washing, product centrifugation and vacuum drying.
The invention also discloses porous silicon-carbon composite according to above-mentioned method preparation and its in lithium ion battery
In application.Through experiment it is found that being used to assemble lithium ion using porous silicon-carbon composite prepared by the present invention as negative material
Battery can significantly improve the cyclical stability of lithium ion battery.
Compared with prior art, the present invention has technique effect beneficial below：
1) it in the preparation field of lithium cell cathode material, is put forward for the first time and prepares silico-carbo using carbon dioxide as carbon source
Composite material.In comparison, the carbon industrially coated often uses the organic matters such as pitch high anneal crack under an inert atmosphere
Solution obtains, in these carbon source cracking process, will a large amount of poisonous and hazardous gas of release, and carbon dioxide as carbon source not only
Abundance, it is cheap, without any environmental pollution, and a large amount of gas-carbon dioxide for causing greenhouse effects are consumed, be
A kind of environmentally friendly carbon source.
2) while porous silicon is prepared, the reaction of magnesium and carbon dioxide is cleverly utilized, thus by the technique of packet carbon
Step is merged into the preparation process of porous silicon, and porous silicon-carbon composite is prepared in one-step method.Packet carbon of the prior art
Technique needs the first organic matter carbon source ball milling mixing with liquid phase or solid phase, then dries, then carry out high-temperature heat treatment, not only technique
Complexity, and since the organic matter of liquid phase or solid phase is often uneven with the contact of silicon so that the carbon wrapped also is difficult to uniformly, very
Situations about not coated to many places of appearance.In contrast, using carbon dioxide as a kind of gaseous carbon source, you can with abundant
It is contacted with silicon, the carbon of generation can also more uniformly be coated on the surface of silicon, form one layer more uniformly, 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 is simple for process, is easy to repeat, and raw material sources enrich, is cheap, it can be achieved that large-scale industrialization is given birth to
Production.
Description of the drawings
Fig. 1 is the test result of porous silicon-carbon composite prepared by embodiment 1；Fig. 1 a and Fig. 1 b are its scanning electron microscope
Photo (SEM), Fig. 1 c are its transmission electron microscope photo (TEM), and Fig. 1 d are its x-ray probe power spectrum (EDS).
Fig. 2 be respectively by the lithium that negative material assembles of porous silicon-carbon composite prepared by embodiment 1 and comparative example from
The recycle ratio capacity curve of sub- battery and the comparison diagram of coulombic efficiency.Wherein, it is solid be the present embodiment product data point, it is empty
Gains in depth of comprehension are the data point of 1 product of comparative example.
Fig. 3 be respectively by the lithium that negative material assembles of porous silicon-carbon composite prepared by embodiment 3 and comparative example from
The recycle ratio capacity curve of sub- battery and the comparison diagram of coulombic efficiency.Wherein, it is solid be the present embodiment product data point, it is empty
Gains in depth of comprehension are the data point of 1 product of comparative example.
Fig. 4 be respectively by the lithium that negative material assembles of porous silicon-carbon composite prepared by embodiment 5 and comparative example from
The recycle ratio capacity curve of sub- battery and the comparison diagram of coulombic efficiency.Wherein, it is solid be the present embodiment product data point, it is empty
Gains in depth of comprehension are the data point of 1 product of comparative example.
Specific embodiment
Below by specific embodiment, the invention will be further described, but protection scope of the present invention be not limited to it is following
Embodiment.
Embodiment 1
1) magnesium silicide is heat-treated 20h at 700 DEG C, heat treatment process passes to excessive CO2Volume fraction is 80% CO2/
Ar gaseous mixtures are as reaction gas.
2) step 1) products therefrom is handled into 10h in certain density hydrochloric acid solution, wherein concentration of hydrochloric acid rubs for 0.5
You/liter, it reuses deionized water after acid processing and cleans 5 times, be then centrifuged for, be finally dried in vacuo.
The results are shown in Figure 1 for the relevant characterization of porous silicon-carbon composite that the present embodiment is prepared.As seen from the figure,
The present embodiment product is the porous structure with a large amount of equally distributed nanoscale hole holes, and the mass fraction of carbon is about 40%,
And the surface of silicon is evenly coated in the form of indefinite form carbon film, form the silico-carbo composite material with nucleocapsid structure.
Porous silicon-carbon composite that the present embodiment is prepared is made button cell and is tested for the property, obtains it
Circulation volume curve and the coulombic efficiency for often taking turns cycle.
Cycle specific capacity and coulombic efficiency are compared with porous silicon-carbon composite prepared by comparative example, as a result such as
Shown in Fig. 2.As seen from the figure, the porous silico-carbo capacity that after 50 cycles prepared by this technique is far above contrast material, cyclical stability
More excellent, the superiority of performance is clearly.
Embodiment 2
Preparation process is identical with embodiment 1, differs only in CO2In/Ar gaseous mixtures, CO2Volume fraction is 60%.
The pattern of porous silicon-carbon composite being prepared is similar to Example 1, but the mass fraction of carbon is about 45%.
Embodiment 3
1) magnesium silicide is heat-treated 15h at 800 DEG C, heat treatment process passes to excessive CO2Volume fraction is 50% CO2/
Ar gaseous mixtures are as reaction gas.
2) step 1) products therefrom is handled into 5h in certain density hydrochloric acid solution, wherein concentration of hydrochloric acid for 2.0 moles/
It rises, reusing deionized water after acid processing cleans 7 times, is then centrifuged for, is finally dried in vacuo.
The pattern of porous silicon-carbon composite that the present embodiment is prepared is similar to Example 1, but the quality of carbon
Score is about 46%.
Porous silicon-carbon composite that the present embodiment is prepared is made button cell and is tested for the property, is just recycled
Specific capacity and coulombic efficiency are compared with porous silicon-carbon composite prepared by comparative example, as shown in Figure 3.As seen from the figure, 50
For the porous silico-carbo capacity that after a cycle prepared by this technique far above contrast material, cyclical stability is more excellent, performance it is excellent
More property is clearly.
Embodiment 4
Preparation process is identical with embodiment 1, differs only in CO2In/Ar gaseous mixtures, CO2Volume fraction is 40%.
The pattern of porous silicon-carbon composite being prepared is similar to Example 1, but the mass fraction of carbon is about 46%.
Embodiment 5
1) magnesium silicide is heat-treated 10h at 900 DEG C, heat treatment process passes to excessive CO2Volume fraction is 20% CO2/
Ar gaseous mixtures are as reaction gas.
2) step 1) products therefrom is handled into 2h in certain density hydrochloric acid solution, wherein concentration of hydrochloric acid for 5 moles/
It rises, reusing deionized water after acid processing cleans 8 times, is then centrifuged for, is finally dried in vacuo.The correlation of obtained porous silicon
Test result is as shown in Figure 1.
The pattern of porous silicon-carbon composite that the present embodiment is prepared is similar to Example 1, but the mass fraction of carbon
About 41%.
Porous silicon-carbon composite that the present embodiment is prepared is made button cell and is tested for the property, is just recycled
Specific capacity and coulombic efficiency are compared with porous silicon-carbon composite prepared by comparative example, as shown in Figure 4.As seen from the figure, 50
For the porous silico-carbo capacity that after a cycle prepared by this technique far above contrast material, cyclical stability is more excellent, performance it is excellent
More property is clearly.
Comparative example
Using the preparation method in the patent document of Publication No. CN103779544A, specially：
First, by mass ratio 1：2 magnesium silicide and polyvinyl alcohol ball milling mixing.Then, first 350 DEG C of heat treatment 5h, then 700
DEG C heat treatment 15h, gaseous mixture of the heat-treating atmosphere for argon gas and air, argon gas volume fraction is 90%.Finally, heat treatment is produced
Object handles 5h, then centrifuge in the mixed acid solution of hydrochloric acid and hydrofluoric acid, and it is carbon source (herein for polyethylene that drying, which is obtained using organic matter,
Alcohol) porous silicon-carbon particle.
Claims (8)
- A kind of 1. method for preparing porous silicon-carbon composite, which is characterized in that step is as follows：Silication magnesium dust is placed in CO2It under/Ar mixed atmospheres, is heat-treated at 700~900 DEG C, then through pickling and post processing Obtain the porous silicon-carbon composite；The CO2In/Ar mixed atmospheres, CO2Volume fraction be 10~90%.
- 2. the method according to claim 1 for preparing porous silicon-carbon composite, which is characterized in that the CO2/ Ar is mixed It closes in atmosphere, CO2Volume fraction be 20~80%.
- 3. the method according to claim 1 for preparing porous silicon-carbon composite, which is characterized in that the CO2/ Ar is mixed It closes in atmosphere, CO2Volume fraction be 40~60%.
- 4. the method according to claim 1 for preparing porous silicon-carbon composite, which is characterized in that the heat treatment Time is 10~20h.
- 5. the method according to claim 1 for preparing porous silicon-carbon composite, which is characterized in that the pickling is adopted With the hydrochloric acid of a concentration of 0.5~5mol/L, processing time is 2~10h.
- 6. the method according to claim 1 for preparing porous silicon-carbon composite, which is characterized in that the post processing Including washing, product centrifugation and vacuum drying.
- 7. a kind of porous silicon-carbon composite prepared according to any method of claim 1~6.
- 8. a kind of application of porous silicon-carbon composite according to claim 7 in lithium ion battery.
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| CN107215874B (en) * | 2017-05-09 | 2020-03-10 | 武汉科技大学 | Preparation method of ant nest-shaped porous silicon for lithium ion battery |
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| 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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| CN110589831B (en) * | 2019-08-26 | 2021-10-15 | 浙江工业大学 | Method for preparing silicon/silicon carbide material at low temperature |
| CN110655056B (en) * | 2019-10-10 | 2021-06-29 | 许昌学院 | Preparation method of porous nano silicon-carbon composite material |
| CN111211306A (en) * | 2020-01-14 | 2020-05-29 | 山东大学 | MXene @ carbon @ porous silicon material and preparation method and application thereof |
| CN111477849B (en) * | 2020-04-14 | 2021-08-17 | 厦门理工学院 | Preparation method of porous Si/SiC/C material and negative electrode material |
| CN113725409A (en) * | 2021-07-29 | 2021-11-30 | 合肥国轩高科动力能源有限公司 | Silicon-based negative electrode material and preparation method thereof |
| CN114229854A (en) * | 2021-12-17 | 2022-03-25 | 新疆晶硕新材料有限公司 | Preparation method of silicon-oxygen-carbon composite material, negative plate and battery |
| CN114477184B (en) * | 2022-01-12 | 2023-05-26 | 浙江工业大学 | Preparation method of silicon carbide powder |
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