CN105489867A - Porous carbon and silicon material and preparation method thereof - Google Patents
Porous carbon and silicon material and preparation method thereof Download PDFInfo
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- 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
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- 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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- 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
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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Abstract
The invention discloses a porous carbon and silicon material and a preparation method thereof. The preparation method comprises the following steps: an organic polymeric monomer, a cross-linked monomer, a surfactant, a pore forming agent and nano-silicon powder are added proportionally to a reactor to serve as a continuous phase and stirred at the room temperature; an aqueous solution containing an initiator is added dropwise slowly to the continuous phase, the mixture is stirred for 5-10 min, a stable emulsion is formed, and the volume fraction of a disperse phase is 60%-90% of the total volume fraction of the emulsion; the emulsion is transferred into a mold for polymerization; a sample is extracted and dried, and a precursor of the porous carbon and silicon composite material is prepared; the precursor of the porous carbon and silicon composite material is subjected to heat treatment in nitrogen atmosphere; the material is carbonized, and the porous carbon and silicon composite material is obtained. When the material prepared with the method is used as a negative electrode material of a lithium battery, the volume expansion of the lithium battery in charge-discharge processes is relieved effectively, and the cycle stability of the lithium battery is enhanced; the defects of low specific surface area, irregular and difficult-to-control pore structure and poor pore communication of the conventional porous carbon and silicon material are overcome.
Description
Technical field
The invention belongs to technical field of lithium ion, particularly relate to a kind of porous carbon silicon materials and preparation method thereof.
Background technology
In recent years, the fast development of China's electronic information and ev industry, greatly facilitates the research and apply of high performance lithium ion battery.Compared with traditional battery, lithium ion battery has the advantages such as energy density is high, power output is large, self discharge is little, cycle performance is superior, charge/discharge rates is fast, environmental pollution is little, long service life, is high performance chemical electric power source the most promising at present.Electrode material is the principal element affecting performance of lithium ion battery.The negative material mainly graphite-like material with carbon element of conventional lithium ion battery, but this kind of negative material also exists theoretical capacity lower (only having 372mAh/g), the shortcomings such as, high rate during charging-discharging more responsive to electrolyte is poor, these shortcomings strongly limit the further raising of performance of lithium ion battery.Therefore, for improving the performance of lithium ion battery, the non-carbon lithium ion battery negative material of research and development high power capacity seems particularly urgent.Compared with conventional graphite negative material, silicon has the theoretical specific capacity (4200mAh/g) of superelevation and lower de-lithium current potential (<0.5V), and the voltage platform of silicon is higher than graphite, when charging, lithium is analysed on the more difficult surface that causes, and security performance is better.So silicon materials have become one of selection of lithium ion battery negative material upgrading.But in charge and discharge process, easily there is volume Swelling and contraction, cause structure collapses, finally cause cycle performance of battery greatly to reduce and aggravate the decay of battery capacity in silicon as lithium ion battery negative material.For solving this difficult problem, silicon and material with carbon element can be prepared into the composite porous change suppressing volume in its charge and discharge process, thus improve its cycle performance.Patent CN102208634A discloses a kind of porous silicon carbon composite and preparation method thereof, with tetraethoxysilane, silicon tetrachloride, methyl-silicone oil, silication sodium for raw material, prepare porous silica, then porous silica is reduced to porous silicon, then adopt organic carbon source polarity coated, heat-treat under an inert atmosphere subsequently, prepare porous silicon carbon composite.Patent CN104009210A discloses a kind of preparation method of porous carbon silicon composite, take rice husk as raw material, adopts the method for metallothermic reduction and purifying to obtain the Si-C composite material with loose structure.
But porous silicon carbon composite prepared by said method also exists that pore-size distribution is wide, pore structure is irregular and the shortcoming the such as connectivity in easy-regulating, hole is not poor, specific area is low, these shortcomings seriously limit its application in electrochemical field.
Summary of the invention
The object of the present invention is to provide a kind of porous carbon silicon materials and preparation method thereof, be intended to solve existing porous silicon carbon composite method of preparing and also exist that pore-size distribution is wide, pore structure is irregular and the problem that connectivity in easy-regulating, hole is not poor, specific area is low.
The present invention is achieved in that a kind of preparation method of porous carbon silicon materials, and the preparation method of described porous carbon silicon materials comprises:
Polymerizable organic monomer, cross-linking monomer, surfactant, pore-foaming agent and nano silica fume are joined as continuous phase in reactor by proper proportion, and stirs at 25 ~ 40 DEG C, stir speed (S.S.) 400 ~ 600 revs/min; The mass content of each component in continuous phase is respectively above: 20 ~ 60%, 10 ~ 40%, 5 ~ 15%, 5 ~ 15%, 5 ~ 20%.
Slowly be added drop-wise in continuous phase as decentralized photo by the aqueous solution containing initator, within about 30 ~ 40 minutes, dropwise, then continue stirring 5 ~ 10 minutes, until the final emulsion forming stable and uniform, the volume fraction of decentralized photo accounts for 60 ~ 90% of total emulsion volume;
Emulsion is transferred in mould, be polymerized 12 ~ 24 hours at 45 ~ 65 DEG C of temperature;
By the presoma of Sample extraction, dry obtained porous carbon silicon composite;
Heat-treated in nitrogen atmosphere by the porous carbon silicon composite presoma obtained, heat treatment temperature is 200 ~ 350 DEG C, and the duration is 3 ~ 5 hours;
Material is carried out carbonization, and carburizing temperature is 700 ~ 900 DEG C, and the duration is 2 ~ 6 hours, finally obtains porous carbon silicon composite.
Further, described polymerizable organic monomer be in styrene, acrylonitrile, p-chloromethyl styrene, ethylhexyl acrylate in one or more.
Further, described cross-linking monomer is divinylbenzene.
Further, described surfactant is one or both the combination in Span80, polyglycerol polyricinoleate.
Further, described pore-foaming agent is the one in toluene, chlorobenzene, 1,2-dichloro-benzenes etc.
Further, described nano silica fume uses the coated process of front carbon.
Further, described initator is one or both in potassium peroxydisulfate, dibenzoyl peroxide, azodiisobutyronitrile.
Further, the preparation method of described porous carbon silicon materials comprises:
By styrene 5ml, divinylbenzene 5ml, Span803ml, toluene 3ml, nano silica fume 1 gram mixes composition continuous phase; At 25 DEG C, dropwise added in continuous phase by the aqueous solution 90ml being dissolved with 0.5g potassium peroxydisulfate, and constantly stir as decentralized photo, rotating speed is 400 revs/min; Within 30 minutes, dropwise;
After dropping terminates, continue stirring 10 minutes, form uniform and stable emulsion;
Emulsion is transferred in homemade mould, is placed in the water-bath of 65 DEG C and reacts 24 hours;
By obtained solid material in apparatus,Soxhlet's with absolute ethyl alcohol extracting 5 hours, in the vacuum drying oven of 80 DEG C dry 24 hours afterwards, obtain the presoma of porous carbon silicon composite;
350 DEG C of heat treatment 5 hours, 900 DEG C of carbonizations 4 hours, obtains porous carbon silicon composite in an inert atmosphere.
Another object of the present invention is to the porous carbon silicon composite providing a kind of preparation method of described porous carbon silicon materials to prepare, described porous carbon silicon composite carbon content accounts for 70 ~ 90%, silicone content accounts for 10 ~ 30%, has second hole structure, and the size in hole is between 2 ~ 50nm and 1 ~ 10 μm.
The present invention proposes a kind of take pickering emulsion as the method for Template preparation porous carbon silicon composite, effectively to alleviate the volumetric expansion problem in lithium ion battery charge and discharge process, strengthens cyclical stability.Instant invention overcomes that porous carbon silicon materials specific area was low, pore structure is irregular and the shortcomings such as the connectivity in difficult control, hole difference in the past, a kind of new porous carbon silicon materials and preparation method thereof are provided; The porous carbon silicon composite prepared has the pore structure of comparatively rule, and average pore size is about 5 ~ 25nm, and specific area reaches 600 ~ 900m
2/ g, the aperture of macropore is about 1 ~ 10 μm, about have between each macropore 20 diameters be 1 ~ 2 μm aperture be connected, connectivity is good.Therefore, the present invention's pickering emulsion makes template, the porous carbon silicon composite of preparation has second hole structure, and the macropore of mutual UNICOM is conducive to the infiltration of electrolyte solution, and nano level micropore is conducive to the contact area improving porous carbon silicon composite and electrolyte solution.Porous carbon silicon composite prepared by the present invention is when being used as the negative material of lithium ion battery, due to the loose structure that it is special, for the embedding of lithium ion in its charge and discharge process or the change in volume of deviating from and causing provide enough spaces, there is higher specific capacity and good cyclical stability, the porous carbon silicon composite wherein prepared is as electrode anode material initial charge capacity up to a 945.6mAh/g, and the capability retention after 40 times that charges is 87.5%.
Accompanying drawing explanation
Fig. 1 is preparation method's flow chart of the porous carbon silicon materials that the embodiment of the present invention provides.
Fig. 2 is the electron scanning micrograph of the porous carbon silicon materials sample that the embodiment of the present invention 1 provides.
Fig. 3 is nitrogen adsorption desorption curve and the pore size distribution curve figure of the porous carbon silicon materials that the embodiment of the present invention 1 provides.
Fig. 4 be the porous carbon silicon composite that obtains with the embodiment of the present invention 1 for negative material, under 100mA/g current density, volume change curve charts after 40 circulations of charging.
Fig. 5 is the electron scanning micrograph of the porous carbon silicon materials sample that the embodiment of the present invention 4 provides.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
Below in conjunction with accompanying drawing, application principle of the present invention is explained in detail.
As shown in Figure 1, the preparation method of the porous carbon silicon materials of the embodiment of the present invention comprises the following steps:
S101: polymerizable organic monomer, cross-linking monomer, surfactant, pore-foaming agent and nano silica fume are joined as continuous phase in reactor by proper proportion, and in stirred at ambient temperature;
S102: be slowly added drop-wise in continuous phase by the aqueous solution containing initator, dropwises, then continues stirring 5 ~ 10 minutes for about 40 minutes, until the final emulsion forming stable and uniform, the volume fraction of decentralized photo accounts for 60 ~ 90% of total emulsion volume;
S103: emulsion transferred in mould, is polymerized 12 ~ 24 hours at 45 ~ 65 DEG C of temperature;
S104: by the presoma of Sample extraction, dry obtained porous carbon silicon composite;
S105: heat-treated in nitrogen atmosphere by the porous carbon silicon composite presoma obtained, heat treatment temperature is 200 ~ 350 DEG C, and the duration is 3 ~ 5 hours;
S106: above-mentioned material is carried out carbonization, carburizing temperature is 700 ~ 900 DEG C, and the duration is 2 ~ 6 hours, finally obtains porous carbon silicon composite.
Described polymerizable organic monomer be in styrene, acrylonitrile, p-chloromethyl styrene, ethylhexyl acrylate in one or more.
Described cross-linking monomer is divinylbenzene.
Described surfactant is the combination of one or more in Span80, polyglycerol polyricinoleate.
Described pore-foaming agent is the one in toluene, chlorobenzene, 1,2-dichloro-benzenes etc.
Described nano silica fume uses the coated process of front carbon.
Described initator is one or both in potassium peroxydisulfate, dibenzoyl peroxide, azodiisobutyronitrile.
According to porous silicon carbon composite prepared by said method, carbon content accounts for 70 ~ 90%, and silicone content accounts for 10 ~ 30%, has second hole structure, and the size in hole is between 2 ~ 50nm and 1 ~ 10 μm.
Concrete steps of the present invention comprise:
Polymerizable organic monomer, cross-linking monomer, surfactant, pore-foaming agent and nano silica fume are joined as continuous phase in reactor by proper proportion, and stirs at 25 ~ 40 DEG C, stir speed (S.S.) 400 ~ 600 revs/min; The mass content of each component is respectively above: polymerizable organic monomer 20 ~ 60%, cross-linking monomer 10 ~ 40%, surfactant 5 ~ 15%, pore-foaming agent 5 ~ 15%, nano silica fume 5 ~ 20%.
Slowly be added drop-wise in continuous phase as decentralized photo by the aqueous solution containing initator, within 30 ~ 40 minutes, dropwise, then continue stirring 5 ~ 10 minutes, until the final emulsion forming stable and uniform, the volume fraction of decentralized photo accounts for 60 ~ 90% of total emulsion volume;
Emulsion is transferred in mould, be polymerized 12 ~ 24 hours at 45 ~ 65 DEG C of temperature;
By the presoma of Sample extraction, dry obtained porous carbon silicon composite;
Heat-treated in nitrogen atmosphere by the porous carbon silicon composite presoma obtained, heat treatment temperature is 200 ~ 350 DEG C, and the duration is 3 ~ 5 hours;
Material is carried out carbonization, and carburizing temperature is 700 ~ 900 DEG C, and the duration is 2 ~ 6 hours, finally obtains porous carbon silicon composite.
Below in conjunction with specific embodiment, application principle of the present invention is further described.
Embodiment 1
First by styrene 5ml, divinylbenzene 5ml, Span803ml, toluene 3ml, nano silica fume 1 gram mixes composition continuous phase; At 25 DEG C, the aqueous solution 90ml being dissolved with 0.5g potassium peroxydisulfate is dropwise added in continuous phase as decentralized photo, and constantly stirs, within 30 minutes, drip off.After dropping terminates, continue stirring 10 minutes, form uniform and stable emulsion.Then emulsion is transferred in homemade mould, be placed in the water-bath of 65 DEG C and react 24 hours.By obtained solid material in apparatus,Soxhlet's with absolute ethyl alcohol extracting 5 hours, in the vacuum drying oven of 80 DEG C dry 24 hours afterwards, obtain the presoma of porous carbon silicon composite.Last 350 DEG C of heat treatment in an inert atmosphere 5 hours, 900 DEG C of carbonizations 4 hours, obtains porous carbon silicon composite.Carbon content 90% in carbon-silicon composite material, silicone content 10%, porosity 90%.
Fig. 2 is the SEM figure of porous carbon silicon composite prepared by this example, as can be seen from the figure, the porous carbon silicon composite diameter macropores of preparation is about 2 ~ 8 μm, the less hole about having 10 ~ 20 diameters to be about 1 ~ 2 μm between each macropore is connected, the structure of macropore is very regular and pore-size distribution is more even, nano silicon particles is deposited on hole wall equably, and above design feature makes this porous carbon silicon materials have good connectedness.
Take nitrogen as adsorbed gas, at relative pressure (P/P
0) under the condition of 0.05-0.99,77K, the porous carbon silicon materials using nitrogen adsorption-desorption instrument obtained to this example are tested, and result as shown in Figure 3.As can be seen from Figure 3, the adsorption-desorption curve of this sample presents the characteristic feature of LangmuirIV type adsorption isotherm, and by multiple spot BET method calculating in the scope of relative pressure 0.05-0.3, the specific area of this sample is about 900m
2/ g, pore-size distribution is measured by BJH method, and the average pore size of this sample is about 5 ~ 25nm and pore-size distribution is narrower as can be seen from Figure 3.
By in example 1 preparation porous carbon silicon composite be active electrode material, Kynoar black with conductive acetylene is mixed into uniform slurry for 60:20:20 in mass ratio, and is coated on the negative pole as battery on Copper Foil; Be to electrode with lithium metal; to be dissolved in lithium hexafluoro phosphate that in ethylene carbonate and dimethyl carbonate solvent that volume ratio is 1:1, concentration is lmol/L as electrolyte; Cellgard2400 is barrier film; button cell is assembled under argon shield; carry out constant current charge-discharge performance test; charging/discharging voltage is 0.01 ~ 1.0V, the electrochemistry cyclic curve of current density to be 100mA/g, Fig. 4 the be composite electrode of above-mentioned preparation.As can be seen from Figure 4, initial charge capacity is 828.7mAh/g, and circulate after 40 times, electrode reversible capacity is 725.1mAh/g, and the capability retention after 40 times that charges is 87.5%.Above result shows, porous carbon silicon materials prepared by example 1 are a kind of excellent electrode materials, and this material not only has height ratio capacity, also maintains good cyclical stability simultaneously.
Embodiment 2
First by divinylbenzene 10ml, Span802ml, chlorobenzene 3ml, nano silica fume 2 grams mixes composition continuous phase; At 40 DEG C, the aqueous solution 90ml being dissolved with 0.5g potassium peroxydisulfate is dropwise added in continuous phase as decentralized photo, and constantly stirs, within 30 minutes, drip off.After dropping terminates, continue stirring 10 minutes, form uniform and stable emulsion.Then emulsion is transferred in homemade mould, be placed in the water-bath of 65 DEG C and react solidification 24 hours.By obtained solid material in apparatus,Soxhlet's with absolute ethyl alcohol extracting 5 hours, in the vacuum drying oven of 80 DEG C dry 24 hours afterwards, obtain the presoma of porous carbon silicon composite.Last 350 DEG C of heat treatment in an inert atmosphere 5 hours, 900 DEG C of carbonizations 2 hours, obtains porous carbon silicon composite.Carbon content 80% in carbon-silicon composite material, silicone content 20%, porosity 90%.
According to the method identical with embodiment 1, a kind of porous carbon silicon composite that this example is obtained is assembled into lithium ion battery and carries out electrochemical property test, this electrode initial charge capacity is 945.6mAh/g, circulate after 40 times, electrode reversible capacity is 645.8mAh/g, and the capability retention after 40 times that charges is 68.3%.
Embodiment 3
First by styrene 10ml, divinylbenzene 10ml, Span802ml, chlorobenzene 3ml, nano silica fume 2 grams mixes composition continuous phase; At room temperature, the aqueous solution 75ml being dissolved with 0.5g potassium peroxydisulfate is dropwise added in continuous phase as decentralized photo, and constantly stirs, within 30 minutes, drip off.After dropping terminates, continue stirring 10 minutes, form uniform and stable emulsion.Then emulsion is transferred in homemade mould, be placed in the water-bath of 65 DEG C and react 24 hours.By obtained solid material in apparatus,Soxhlet's with absolute ethyl alcohol extracting 5 hours, in the vacuum drying oven of 80 DEG C dry 24 hours afterwards, obtain the presoma of porous carbon silicon composite.Last 350 DEG C of heat treatment in an inert atmosphere 5 hours, 700 DEG C of carbonizations 2 hours, obtains porous carbon silicon composite.Carbon content 80% in carbon-silicon composite material, silicone content 20%, porosity 79%.
According to the method identical with embodiment 1, a kind of porous carbon silicon composite that this example is obtained is assembled into lithium ion battery and carries out electrochemical property test, this electrode initial charge capacity is 875.2mAh/g, circulate after 40 times, electrode reversible capacity is 616.1mAh/g, and the capability retention after 40 times that charges is 70.4%.
Embodiment 4
First by acrylonitrile 5ml, divinylbenzene 5ml, polyglycerol polyricinoleate 3ml, toluene 3ml, dibenzoyl peroxide 0.5g, nano silica fume 1 gram mixes composition continuous phase; Under 35 degrees Celsius, the aqueous solution 75ml being dissolved with 0.5g potassium peroxydisulfate is dropwise added in continuous phase as decentralized photo, and constantly stirs, within 40 minutes, drip off.After dropping terminates, continue stirring 10 minutes, form uniform and stable emulsion.Then emulsion is transferred in homemade mould, be placed in the water-bath of 65 DEG C and react 24 hours.By obtained solid material in apparatus,Soxhlet's with absolute ethyl alcohol extracting 5 hours, in the vacuum drying oven of 80 DEG C dry 24 hours afterwards, obtain the presoma of porous carbon silicon composite.Last 350 DEG C of heat treatment in an inert atmosphere 5 hours, 900 DEG C of carbonizations 3 hours, obtains porous carbon silicon composite.Carbon content 90% in carbon-silicon composite material, silicone content 10%, porosity 88%.
Fig. 5 is the SEM figure of porous carbon silicon composite prepared by this example, as can be seen from the figure, the porous carbon silicon composite diameter macropores of preparation is about 1 ~ 10 μm, the aperture about having 20 ~ 30 diameters to be about 1 ~ 3 μm between every two macropores is connected, compared with the material prepared with embodiment 1, the aperture of macropore becomes large, pore-size distribution broadens, but still maintain the typical porous character of this material, silicon nanoparticle is deposited on hole wall equably, and these design features make this material be provided with good connectedness.
According to the method identical with embodiment 1, a kind of porous carbon silicon composite that this example is obtained is assembled into lithium ion battery and carries out electrochemical property test, this electrode initial charge capacity is 674.6mAh/g, circulate after 40 times, electrode reversible capacity is 462.1mAh/g, and the capability retention after 40 times that charges is 68.5%.
Embodiment 5
First by acrylonitrile 5ml, divinylbenzene 5ml, polyglycerol polyricinoleate 2ml, 1,2-dichloro-benzenes 3ml, dibenzoyl peroxide 0.5g, nano silica fume 2 grams mixes composition continuous phase; At 35 DEG C, the aqueous solution 75ml being dissolved with 0.5g potassium peroxydisulfate is dropwise added in continuous phase as decentralized photo, and constantly stirs, within 40 minutes, drip off.After dropping terminates, continue stirring 10 minutes, form uniform and stable emulsion.Then emulsion is transferred in homemade mould, be placed in the water-bath of 65 DEG C and react 24 hours.By obtained solid material in apparatus,Soxhlet's with absolute ethyl alcohol extracting 5 hours, in the vacuum drying oven of 80 DEG C dry 24 hours afterwards, obtain the presoma of porous carbon silicon composite.Last 350 DEG C of heat treatment in an inert atmosphere 5 hours, 700 DEG C of carbonizations 3 hours, obtains porous carbon silicon composite.Carbon content 80% in carbon-silicon composite material, silicone content 20%, porosity 88%.
According to the method identical with embodiment 1, a kind of porous carbon silicon composite that this example is obtained is assembled into lithium ion battery and carries out electrochemical property test, this electrode initial charge capacity is 724.6mAh/g, circulate after 40 times, electrode reversible capacity is 414.4mAh/g, and the capability retention after 40 times that charges is 57.2%.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (9)
1. a preparation method for porous carbon silicon materials, is characterized in that, the preparation method of described porous carbon silicon materials comprises:
Polymerizable organic monomer, cross-linking monomer, surfactant, pore-foaming agent and nano silica fume are joined as continuous phase in reactor by proper proportion, and stirs at 25 ~ 40 DEG C, stir speed (S.S.) 400 ~ 600 revs/min; The mass content of each component is respectively above: polymerizable organic monomer 20 ~ 60%, cross-linking monomer 10 ~ 40%, surfactant 5 ~ 15%, pore-foaming agent 5 ~ 15%, nano silica fume 5 ~ 20%.
Slowly be added drop-wise in continuous phase as decentralized photo by the aqueous solution containing initator, within 30 ~ 40 minutes, dropwise, then continue stirring 5 ~ 10 minutes, until the final emulsion forming stable and uniform, the volume fraction of decentralized photo accounts for 60 ~ 90% of total emulsion volume;
Emulsion is transferred in mould, be polymerized 12 ~ 24 hours at 45 ~ 65 DEG C of temperature;
By the presoma of Sample extraction, dry obtained porous carbon silicon composite;
Heat-treated in nitrogen atmosphere by the porous carbon silicon composite presoma obtained, heat treatment temperature is 200 ~ 350 DEG C, and the duration is 3 ~ 5 hours;
Material is carried out carbonization, and carburizing temperature is 700 ~ 900 DEG C, and the duration is 2 ~ 6 hours, finally obtains porous carbon silicon composite.
2. the preparation method of porous carbon silicon materials as claimed in claim 1, it is characterized in that, described polymerizable organic monomer is one or more in styrene, acrylonitrile, p-chloromethyl styrene, ethylhexyl acrylate.
3. the preparation method of porous carbon silicon materials as claimed in claim 1, it is characterized in that, described cross-linking monomer is divinylbenzene.
4. the preparation method of porous carbon silicon materials as claimed in claim 1, it is characterized in that, described surfactant is one or both the combination in Span80, polyglycerol polyricinoleate.
5. the preparation method of porous carbon silicon materials as claimed in claim 1, it is characterized in that, described pore-foaming agent is the one in toluene, chlorobenzene, 1,2-dichloro-benzenes.
6. the preparation method of porous carbon silicon materials as claimed in claim 1, is characterized in that, described nano silica fume uses the coated process of front carbon.
7. the preparation method of porous carbon silicon materials as claimed in claim 1, is characterized in that, described initator is one or both in potassium peroxydisulfate, dibenzoyl peroxide, azodiisobutyronitrile.
8. the preparation method of porous carbon silicon materials as claimed in claim 1, it is characterized in that, the preparation method of described porous carbon silicon materials comprises:
By styrene 5ml, divinylbenzene 5ml, Span803ml, toluene 3ml, nano silica fume 1 gram mixes composition continuous phase; At 25 DEG C, dropwise added in continuous phase by the aqueous solution 90ml being dissolved with 0.5g potassium peroxydisulfate, and constantly stir as decentralized photo, rotating speed is 400 revs/min; Within 30 minutes, dropwise;
After dropping terminates, continue stirring 10 minutes, form uniform and stable emulsion;
Emulsion is transferred in homemade mould, is placed in the water-bath of 65 DEG C and reacts 24 hours;
By obtained solid material in apparatus,Soxhlet's with absolute ethyl alcohol extracting 5 hours, in the vacuum drying oven of 80 DEG C dry 24 hours afterwards, obtain the presoma of porous carbon silicon composite;
350 DEG C of heat treatment 5 hours, 900 DEG C of carbonizations 4 hours, obtains porous carbon silicon composite in an inert atmosphere.
9. the porous carbon silicon materials prepared of the preparation method of porous carbon silicon materials as described in claim 1-8 any one, it is characterized in that, comprise according to mass content: polymerizable organic monomer 20 ~ 60%, cross-linking monomer 10 ~ 40%, surfactant 5 ~ 15%, pore-foaming agent 5 ~ 15%, nano silica fume 5 ~ 20%; Described porous carbon silicon composite carbon content accounts for 70 ~ 90%, and silicone content accounts for 10 ~ 30%, has second hole structure, and the size in hole is between 2 ~ 50nm and 1 ~ 10 μm.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106450192A (en) * | 2016-10-14 | 2017-02-22 | 浙江天能能源科技股份有限公司 | Silicon/carbon composite material for lithium ion battery and preparation method and application thereof |
| CN107069010A (en) * | 2017-04-24 | 2017-08-18 | 广东烛光新能源科技有限公司 | A kind of silicon-carbon cathode material and preparation method thereof |
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| CN111384375A (en) * | 2018-12-29 | 2020-07-07 | 上海杉杉科技有限公司 | Silicon-carbon negative electrode material, preparation method and application thereof, and lithium ion battery prepared from silicon-carbon negative electrode material |
| CN109529770B (en) * | 2018-12-29 | 2021-09-14 | 中国科学院兰州化学物理研究所 | Method for preparing porous carbon adsorbent material by taking semicoke-stable Pickering emulsion as template |
| CN112614998A (en) * | 2020-12-16 | 2021-04-06 | 陈君飞 | N, S in-situ porous carbon doped lithium ion battery cathode material and preparation method thereof |
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