CN109904429A - A kind of preparation method of Si-C composite material - Google Patents
A kind of preparation method of Si-C composite material Download PDFInfo
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Abstract
The present invention relates to field of lithium more particularly to a kind of preparation methods of Si-C composite material.The preparation method includes: that organosilicon 1) is dissolved in petroleum ether, is formulated as oily solution；2) polyethylene glycol/polycaprolactone/polyethyleneglycol triblock copolymer is added into oily solution, pre- liquid is obtained after being stirred to react；3) oil-soluble phenolic resin is added into pre- liquid, obtains mixed liquor, mixed liquor and water are mixed according to a certain percentage, stirring to its formation turbid；4) turbid is spun on substrate surface, progress predrying, which is placed in protective atmosphere, calcines to get the Si-C composite material of powdery is arrived.Raw material sources of the present invention are extensive, low in cost；Preparation method is succinctly efficient, more environmentally protective without plating and heavy metal or noble metal catalyst；Obtained Si-C composite material carbon shell structure is complete and uniform, integrally has good chemical property, cycle performance and mechanical property；The stability of silicon is high, and antibody product swelliong power is strong.
Description
Technical field
The present invention relates to field of lithium more particularly to a kind of preparation methods of Si-C composite material.
Background technique
As the rapid growth and economic sustainable development, energy-output ratio of world population are continuously increased.Devoting Major Efforts To Developing and
Carry out the certainty that new energy is sustainable development.Lithium ion battery has that specific energy is big, operating voltage is high, memory-less effect and right
Advantages of environment protection is not only widely used in the compact electric apparatus such as mobile phone, camera, notebook, but also electronic
Application in the Large Electrics equipment such as vehicle, satellite, fighter plane is also by favor.The promotion and application range of performance of lithium ion battery
The decline for widening the raising and cost that depend greatly on negative electrode material performance.Currently, commercialized lithium-ion electric
Pond negative electrode material is usually carbon-based material, such as graphite, carbonaceous mesophase spherules, their specific capacity is lower, and structure is inadequate
Stablize, is unable to undergo high current charge-discharge.So while lithium ion battery at this stage has substantially met portable small device
It needs, but large-sized power lithium ion battery material therefor needed for electric vehicle still needs to our improvement and research and development.
In non-carbon electrode, silicon has high theoretical specific capacitance, lower storage lithium response voltage platform, and silicon is one
Material kind cheap and easy to get, is distributed extremely wide in nature, and the content in the earth's crust is only second to oxygen, therefore silicon-based anode material
Material is the novel high-energy material of a kind of great development prospect.However, the electronic conductivity and ionic conductivity of silicon are low, lead to it
The dynamic performance of electrochemical reaction is poor；The cyclical stability of common pure silicon is poor, and phase transformation of silicon during lithiumation
A series of problems, such as larger stress can be generated with volume expansion, cause lead rupture dusting, resistance increase and cycle performance rapid drawdown
Generation.
To solve problems, silicon powder and carbon source material are mainly subjected to ball for the research of silicon based anode material at present
It is pyrolyzed after mill mixing, to prepare Si-C composite material, it is whole to increase the stability of silicon, negative electrode material by way of carbon packet silicon
Electronic conductivity and ionic conductivity, and the Study of Volume Expansion in battery charge and discharge process can be alleviated, improve silicon substrate
The cycle performance of material.
In the preparation process of existing Si-C composite material, usually there is following two method: first is that making using metallic silver
Three-dimensional porous silicon materials are made for the method for catalyst inducement chemical attack, are then mixed with carbon source by the method for ball milling
It closes, carbon-coated silicon carbon material is obtained after sintering；Second is that be sintered under the conditions of argon gas using silicon monoxide, using itself
Disproportionated reaction generates silicon and silica, then prepares porous silicon by the method for etching, finally by obtained mixture and
Carbon source is roasted by certain mass than after mixing.Such method has that catalyst is at high cost, cost of material is high, operating method
Step is many and diverse to be difficult to control, stability difference and unobvious etc. a series of defect of performance improvement effect in preparation process.For
Problems are solved, those skilled in the art are small effective.
As Patent Office of the People's Republic of China's silicon-carbon cathode material preparation method and porous silicon carbosphere disclosed on September 28th, 2018 is negative
The application for a patent for invention of pole material, application publication number CN108598430A, preparation method include: grinding silicon powder slurry, are obtained
Silicon powder slurry after to mill.Graphitization processing is carried out to micropowder, obtains graphitized carbon micro mist.Silicon powder slurry after Ball-stirring mill is stirring
Continue cladding carbon source to be added, and be ultrasonically treated, and same to graphitized carbon micro mist is added after mill in silicon powder slurry during mixing
When stir, be then spray-dried, obtain silicon-carbon microballoon.Carbonization treatment is carried out to silicon-carbon microballoon, obtains silicon carbide carbon microballoon.
Processing is performed etching to silicon carbide carbon microballoon, drying then is washed to silicon carbide carbon microballoon, obtains porous silicon carbosphere cathode material
Material.
The for another example preparation method of Patent Office of the People's Republic of China's silicon-carbon cathode material disclosed on December 22nd, 2017, silicon-carbon cathode material
The application for a patent for invention of material and lithium ion battery, application publication number CN107507972A, preparation method includes the following steps:
Using silicon alloy powder as raw material, obtained porous after removing remaining metal in silicon alloy powder in addition to silicon through pickling processes
Silicon；Porous silicon is put into carbon precursor, carbon coating processing is carried out, forms the Si-C composite material for having carbon coating layer；By silicon
Carbon composite carries out carbonization treatment, obtains silicon-carbon cathode material.
But the being evenly coated property of Si-C composite material obtained by both the above technical solution, outer layer carbon shell is poor, i.e.,
Appearance carbon shell uneven distribution, performance of the network-like Porous Silicon structures of interior three-dimensional in anti-volume expansion is general, and is occurring
The problems such as impaired silicon structure, dusting still easily occur after volume expansion.
Summary of the invention
It is lower to solve high existing Si-C composite material one side preparation cost, complex process and yield, on the other hand
The problem of phenomena such as silicon materials are easy to cause to be damaged due to phase transformation and volume expansion, dusting occurs, the present invention provides a kind of silicon
The preparation method of carbon composite.It first has to realize the purpose that low cost prepares carbon packet silicon structure form Si-C composite material,
And further ensure that prepared Si-C composite material has very excellent chemical property on this basis, and ensure to prepare
The environmental protection of process and efficiently.
To achieve the above object, the present invention uses following technical scheme.
A kind of preparation method of Si-C composite material, the preparation method include following preparation step:
1) organosilicon is dissolved in petroleum ether, is formulated as oily solution；
2) polyethylene glycol/polycaprolactone/polyethyleneglycol triblock copolymer is added into oily solution, is obtained after being stirred to react pre-
Liquid；
3) oil-soluble phenolic resin is added into pre- liquid, obtains mixed liquor, mixed liquor and water are mixed according to a certain percentage, stir
Turbid is formed to it；
4) turbid is spun on substrate surface, progress predrying, which is placed in protective atmosphere, calcines to get multiple to the silicon-carbon of powdery
Condensation material.
In the technical solution of the present invention, first using organosilicon as silicon source, the oiliness that is configured after organosilicon is dissolved
Solution is stirred to react after adding polyethylene glycol/polycaprolactone/polyethyleneglycol triblock copolymer (abbreviation triblock copolymer),
Oil-soluble phenolic resin is added, connection can occur with the polycaprolactone part of triblock copolymer, produce for oil-soluble phenolic resin
Raw assembling effect, obtains mixed liquor, mixed liquor can generate complete carbon packet silicon precursor after adding water.Should during, first by
It is a kind of amphiphilic triblock copolymer in triblock copolymer used in the present invention, polyethylene glycol end is hydrophilic, gathers oneself
Lactone end oleophylic, and water and petroleum ether are immiscible, therefore form emulsion after adding water, triblock copolymer is moved in emulsion
The interface of water droplet and petroleum ether, polycaprolactone is in petroleum ether, polyethylene glycol end is inserted into water droplet, and further organosilicon connects
Touching water hydrolyzes, and hydrolysate is coated by triblock copolymer, so formed a kind of oil-soluble phenolic resin be in outermost end,
The special construction that triblock copolymer is in middle layer, organosilicon hydrolyzation product is core assembles particle, in subsequent spin coating, predrying
After calcining, oil-soluble phenolic resin and triblock copolymer, as silicon source, form carbon as carbon source, organosilicon hydrolyzation product
Packet silicon structure spherical particles, i.e. Si-C composite material.In the Si-C composite material, carbon thickness of the shell is uniform, and due to itself three
Block copolymer forms the structure of spiral lamellar after assembling, is formed by carbon shell and maintains microstructure to a certain extent,
Specific surface area is larger, mechanical property is outstanding；And internal silicon is amorphous silicon, and organosilicon hydrolyzation product is by carbon source packet
Cover, carry out being formed by silicon carbide particles after further calcining can be more tiny, thus also have great specific surface area and electrification
Learn activity.Whole Si-C composite material has very excellent chemical property, and internal silicon is not susceptible to volume expansion, i.e.,
Just the high integrity for being also able to maintain whole Si-C composite material is expanded.Outer layer carbon shell has good electronic conductivity
And ionic conductivity, the stability of silicon is high, and the cycle performance of whole Si-C composite material is very excellent.
Preferably, the step 1) organosilicon is ethyl orthosilicate.
When organosilicon is ethyl orthosilicate, the polyethylene glycol end of triblock copolymer can react with ethyl orthosilicate,
It is connected to the silicon in ethyl orthosilicate on the polyethylene glycol of triblock copolymer.When therefore selecting ethyl orthosilicate as silicon source,
Subsequent reactions and product structure equally change.It is formed by triblock copolymer in assembling particle and is connected with the poly- of silicon source
Ethylene glycol end insertion water droplet, polycaprolactone are in oil liquid, and oil-soluble phenolic resin be in outermost end and with polycaprolactone portion
Split-phase connects.In the subsequent final product Si-C composite material being prepared, silicon is no longer amorphous silicon, but with long chain
Based on polyethylene glycol, it is grown in inside carbon shell and forms silicon nanorod array and/or silicon nanowires, compared to amorphous silicon,
With bigger specific surface area and antibody product expansion character, and carbon shell inner space is bigger, utilization rate is higher therefore obtained
Si-C composite material overall performance is further optimized.
Preferably, organic silicon concentration is 0.1~1.2mol/L in the step 1) oily solution.
Organosilicon is as silicon source, and silicone content is too low in the too low then obtained Si-C composite material of concentration, and performance is poor, concentration
It is excessively high, it will lead to organosilicon and largely hydrolyzed in water droplet, assemble grain structure and be destroyed, cannot achieve preparation.In the concentration model
In enclosing, it can be ensured that smoothly prepare the Si-C composite material with superperformance.
Preferably, the step 2) polyethylene glycol/polycaprolactone/polyethyleneglycol triblock copolymer is molten with every liter of oiliness
The ratio addition of 5~60mmol is added in liquid.
What triblock copolymer mainly play a part of is similar " rope ", itself is separately connected oil-soluble phenolic resin
It is directly reacted with organosilicon hydrolyzation product or one end as silicon source, is inserted into water droplet with ethyl orthosilicate, form carbon packet silicon structure,
On the other hand itself is similarly used as carbon source during subsequent calcination, and can make to be formed by carbon shell have it is high uniform
Property, and spiral multi-layer sheet structure when its self assembly is kept to a certain extent.Therefore for its dosage without excessive, dosage is excessive not only
It will cause the wasting of resources, can also make silicon ingredient in preparation-obtained Si-C composite material uneven, part Si-C composite material
Middle silicon content is higher, another part silicon content is lower；And its dosage it is too small when, then will lead to its organosilicon hydrolyzation product or positive silicon
Acetoacetic ester can not form impurity by complete capture/connection, in obtained product, reduce efficiency of pcr product.
Preferably, the concentration of step 3) the mixed liquor oil-soluble phenolic resin is 0.3~1.5mol/L.
For oil-soluble phenolic resin as carbon source, it is too low to play concentration, and it is excessively thin to will lead to carbon shell, reduces Si-C composite material
Antibody accumulates expansion character, and the excessive generation wasting of resources of dosage, is also easy to cause not the chemical property of Si-C composite material
Benefit influences.
Preferably, step 3) mixed liquor and water are mixed according to the ratio of volume ratio 100:2~5.
Add dilutional hyponatremia that can then generate apparent layering, product can not be made, excessively few efficiency of pcr product that then will lead to is low, at this
In proportional region, it can be ensured that the yield of product is higher.
Preferably, the step 4) substrate is glass substrate.
Glass substrate is with good stability, will not react, and high temperature resistance is preferable, later separation product side
Just.
Preferably, the step 4) pre-drying process is controlled at 60~80 DEG C, when predrying a length of 0.5~2h.
Petroleum ether can be recycled in pre-drying process, realize the recycling to petroleum ether.
Preferably, in the step 4) calcination process calcination temperature be 550~580 DEG C, heating rate be 1~2 DEG C/
Min, calcination time are 3~6h.
It restores silicon and carbon in silicon source and carbon source in calcination process and forms the Si-C composite material of well-formed.Calcining
Temperature is excessively high, and to will lead to product microstructure impaired, too low, and it is poor to will lead to reduction effect, calcines effect within this temperature range
Most preferably.
The beneficial effects of the present invention are:
1) raw material sources are extensive, low in cost；
2) preparation method is succinctly efficient, more environmentally protective without plating and heavy metal or noble metal catalyst；
3) the Si-C composite material carbon shell structure obtained by is complete and uniform, integrally has good chemical property, cyclicity
Energy and mechanical property；
4) stability of silicon is high, and antibody product swelliong power is strong.
Detailed description of the invention
Fig. 1 is the preparation process schematic diagram of the unformed Si-C composite material of the present invention；
Fig. 2 is the preparation process schematic diagram of nano-array Si-C composite material.
Specific embodiment
Further clear detailed description explanation is made to the present invention below in conjunction with specific embodiment and Figure of description.This
Field those of ordinary skill will realize the present invention based on these explanations.In addition, being related in following the description
The embodiment of the present invention be generally only an of the invention branch embodiment, instead of all the embodiments.Therefore, it is based on this hair
Embodiment in bright, those of ordinary skill in the art's every other reality obtained without making creative work
Example is applied, should fall within the scope of the present invention.
Unless otherwise specified, the raw materials used present invention is substances obtained by commercially available or those skilled in the art；Such as nothing
Specified otherwise, method therefor of the present invention are the methods known to those skilled in the art.
Examples 1 to 5
A kind of preparation method of Si-C composite material, the preparation method include following preparation step:
1) 1,1,3,3- tetramethyl disiloxane is dissolved in petroleum ether, is formulated as oily solution；
2) polyethylene glycol/polycaprolactone/polyethyleneglycol triblock copolymer is added into oily solution, is obtained after being stirred to react pre-
Liquid；
3) oil-soluble phenolic resin (selecting 2402 phenolic resin) is added into pre- liquid, obtains mixed liquor, mixed liquor and water is pressed
It is mixed according to certain proportion, stirring to its formation turbid；
4) turbid is spun on glass baseplate surface, progress predrying to film forming, which is placed in nitrogen atmosphere, calcines to get powder is arrived
The Si-C composite material of shape.
Wherein, the specific preparation parameter of Examples 1 to 5 is as shown in following table table 1.
The specific preparation parameter of 1 Examples 1 to 5 of table
Wherein, Examples 1 to 5 prepares the process of Si-C composite material as shown in Figure 1, Si-C composite material obtained by it
The structure of amorphous silicon is coated for spherical carbon shell, the Si-C composite material of the structure not only has excellent chemical property, also
It can be avoided the generation for the problems such as volume expansion generated in charge and discharge process due to silicon materials causes negative electrode material dusting.
Embodiment 6~10
The preparation method and preparation parameter of embodiment 6~10 are successively corresponding with Examples 1 to 5, and unique distinctive points are reality
It applies 1,1,3,3- tetramethyl disiloxane used in step 1) in example 1~5 and replaces with ethyl orthosilicate.
Embodiment 6~10 prepares the process of Si-C composite material as shown in Fig. 2, the Si-C composite material obtained by it is ball
Shape carbon shell coat nanometer silicon array structure, the structure compared to Si-C composite material obtained by Examples 1 to 5 structure,
Further optimized on chemical property, is showed in terms of cycle performance more excellent.
Detection:
Performance detection is carried out to Examples 1 to 10.Partial detection is as shown in following table table 2.The testing result data are
20 valid data average values.Detection mainly divides following two parts: one, physical property detects: according to national standard GB/T 24533-
Method carries out grain to Si-C composite material obtained by Examples 1 to 10 in 2009 " silicon/carbon/graphite in lithium ion batteries class negative electrode materials "
The detection of degree, specific surface area, compacted density etc.；Two, silicon-carbon obtained by Examples 1 to 10 is answered in conventional sectional method
Condensation material prepares negative electrode tab, and is assembled into button cell and is detected (0.01~2V of charge-discharge magnification 0.5C/ voltage range).Its
Specific assembling process is by LA132 binder, SP conductive agent, distilled water and Si-C composite material with mass ratio 1:3:200:96's
Ratio mixing, using LiPF6(1mol/L)/EC-EMC-DMC (1:1:1) electrolyte, lithium metal to electrode and polyethylene film,
It is assembled in glove box.
2 testing result of table
From upper table table 2 it will be evident that Si-C composite material obtained by the present invention has splendid physical property and electricity
Chemical property, compared to conventional silicium cathode material, cycle performance has huge promotion, substantially can after 100 circulations
The capacity for keeping 96% or more capacity, and having part that can even keep 97%.Also, it is remained under cryogenic
It is enough to keep preferably chemical property.Compared to conventional silicon-carbon cathode material on the market, properties have very aobvious
The promotion effect of work.
Claims (9)
1. a kind of preparation method of Si-C composite material, which is characterized in that the preparation method includes following preparation step:
1) organosilicon is dissolved in petroleum ether, is formulated as oily solution；
2) polyethylene glycol/polycaprolactone/polyethyleneglycol triblock copolymer is added into oily solution, is obtained after being stirred to react pre-
Liquid；
3) oil-soluble phenolic resin is added into pre- liquid, obtains mixed liquor, mixed liquor and water are mixed according to a certain percentage, stir
Turbid is formed to it；
4) turbid is spun on substrate surface, progress predrying, which is placed in protective atmosphere, calcines to get multiple to the silicon-carbon of powdery
Condensation material.
2. a kind of preparation method of Si-C composite material according to claim 1, which is characterized in that step 1) is described organic
Silicon is ethyl orthosilicate.
3. a kind of preparation method of Si-C composite material according to claim 1 or 2, which is characterized in that step 1) is described
Organic silicon concentration is 0.1~1.2mol/L in oily solution.
4. a kind of preparation method of Si-C composite material according to claim 1, which is characterized in that step 2) the poly- second
The ratio addition of 5~60mmol is added with every liter of oily solution for glycol/polycaprolactone/polyethyleneglycol triblock copolymer.
5. a kind of preparation method of Si-C composite material according to claim 1, which is characterized in that the step 3) mixing
The concentration of liquid oil-soluble phenolic resin is 0.3~1.5mol/L.
6. a kind of preparation method of Si-C composite material according to claim 1 or 5, which is characterized in that step 3) mixing
Liquid and water are mixed according to the ratio of volume ratio 100:2~5.
7. a kind of preparation method of Si-C composite material according to claim 1, which is characterized in that the step 4) substrate
For glass substrate.
8. a kind of preparation method of Si-C composite material according to claim 1, which is characterized in that the step 4) predry
Dry process control temp is 60~80 DEG C, when predrying a length of 0.5~2h.
9. a kind of preparation method of Si-C composite material according to claim 1, which is characterized in that the step 4) calcining
Calcination temperature is 550~580 DEG C in the process, and heating rate is 1~2 DEG C/min, and calcination time is 3~6h.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110364707A (en) * | 2019-06-28 | 2019-10-22 | 徐州硕祥信息科技有限公司 | A kind of preparation method of lithium cell cathode material |
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| CN102123967A (en) * | 2008-08-13 | 2011-07-13 | 康宁股份有限公司 | Synthesis of ordered mesoporous carbon-silicon nanocomposites |
| CN107204445A (en) * | 2017-05-26 | 2017-09-26 | 郑州中科新兴产业技术研究院 | A kind of lithium ion battery three-dimensional porous silicon-carbon cathode material and preparation method thereof |
| CN109346696A (en) * | 2018-10-11 | 2019-02-15 | 桑德集团有限公司 | Silicon-carbon cathode material and preparation method thereof |
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2019
- 2019-03-06 CN CN201910167988.3A patent/CN109904429B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102123967A (en) * | 2008-08-13 | 2011-07-13 | 康宁股份有限公司 | Synthesis of ordered mesoporous carbon-silicon nanocomposites |
| CN107204445A (en) * | 2017-05-26 | 2017-09-26 | 郑州中科新兴产业技术研究院 | A kind of lithium ion battery three-dimensional porous silicon-carbon cathode material and preparation method thereof |
| CN109346696A (en) * | 2018-10-11 | 2019-02-15 | 桑德集团有限公司 | Silicon-carbon cathode material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110364707A (en) * | 2019-06-28 | 2019-10-22 | 徐州硕祥信息科技有限公司 | A kind of preparation method of lithium cell cathode material |
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