CN103035888A - Preparation method of silicon and graphene composite material - Google Patents
Preparation method of silicon and graphene composite material Download PDFInfo
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- CN103035888A CN103035888A CN2011103019519A CN201110301951A CN103035888A CN 103035888 A CN103035888 A CN 103035888A CN 2011103019519 A CN2011103019519 A CN 2011103019519A CN 201110301951 A CN201110301951 A CN 201110301951A CN 103035888 A CN103035888 A CN 103035888A
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Abstract
The invention relates to a preparation method of a silicon and graphene composite material. The silicon and graphene composite material is prepared by placing graphite oxide solids in a silicon-containing gas atmosphere for reduction reaction. The preparation process is relatively simple. Since impurities produced during reaction are gas substances and can be directly discharged, complex drying and purifying steps are not needed and the product can be directly obtained, the preparation efficiency is higher, the purity of the prepared composite material is high and the performance is guaranteed.
Description
[technical field]
The present invention relates to lithium ion battery, hybrid super capacitor field, relate in particular to the preparation method of a kind of silicon, graphene composite material.
[background technology]
The lithium ion battery of traditional commodities adopts lithium graphite system mostly, although the chemical property of this class system is excellent, but because itself storage lithium ability is lower, be 372mAh/g such as the theoretical lithium storage content of graphite, so novel transition metal oxide/graphite system attracts widespread attention.
In the intercalation materials of li ions at present, pure silicon is because having the highest theoretical lithium storage content (4200mAh/g), relatively low embedding lithium current potential, charge and discharge process is difficult for reuniting, have higher physical stability and chemical stability than other metal_based materials, become the study hotspot in lithium ion battery negative material field.But silica-base material because the effect of stress that bulk effect produces causes avalanche and the material efflorescence of silicon lattice structure easily, causes active material to break away from the electrode material system and loses activity in degree of depth removal lithium embedded process, therefore has very poor cyclical stability.Compound to mainly improved one's methods metals such as adopting Ni, Fe and Cu and silicon of silica-base material, formation is take silicon as the activated centre, activity take inert metal as dispersible carrier/inertia compound system when improving the electric conductivity of material, has improved the cycle performance of material.But this material forms the metallic silicon phase of inertia easily, and the molal weight of these metals itself is larger, belongs to non-intercalation materials of li ions, has therefore weakened to a certain extent the specific capacity of silica-base material; Metal itself has electron conduction in addition, does not possess ionic conductivity, so that electrolyte is difficult to immersion, thereby loses activity.Another method is exactly the method that material with carbon element coats, and is lower than the molal weight of metal, and electrolyte is easy to immerse, and effect will be got well than metal relatively, and material property has certain improvement, but relatively poor.
Graphene has good conductivity, the space distributes and higher mechanical performance, utilizes grapheme material to substitute traditional material with carbon element, and silicon, the graphene combination electrode material for preparing of being combined with silicon has good electrochemical stability.Traditional silicon, graphene combination electrode material mostly adopt wet method preparation, and the product that obtains need to carry out strict purification removal of impurities, and process is loaded down with trivial details, and efficient is low, and product usually is mixed with impurity, affect the performance of electrode material.
[summary of the invention]
Based on this, be necessary to provide a kind of process relative simple, can directly obtain the silicon of product, the preparation method of graphene composite material.
The preparation method of a kind of silicon, graphene composite material comprises the steps:
Provide or prepare graphite oxide;
Described graphite oxide is placed siliceous reducibility gas atmosphere, slowly be heated to 200～1200 ℃ with 10～100 ℃/minute and carry out reduction reaction, obtain described silicon, graphene composite material after the cooling, wherein, silicon accounts for 1～50% of described composite material weight.
Preferably, described preparation graphite oxide comprises the steps: graphite raw material, potassium peroxydisulfate and phosphorus pentoxide are added in 80 ℃ the concentrated sulfuric acid, stirs, and cooling is more than 6 hours, suction filtration, and washing is to neutral, and drying obtains biased sample; Described biased sample is added in 0 ℃ the concentrated sulfuric acid, add potassium permanganate, the temperature of system remains on below 20 ℃ again, then keeps after 2 hours in 35 ℃ oil bath, slowly add deionized water, after 15 minutes, add again the deionized water that contains hydrogen peroxide, until the color of the solution becomes glassy yellow, suction filtration while hot, be that 10% hydrochloric acid washs with concentration again, suction filtration, 60 ℃ of vacuumizes namely obtain graphite oxide.Further preferred, above-mentioned graphite raw material is purity more than or equal to 99.5% natural flake graphite.
Preferably, described siliceous reducibility gas is the mixture of gaseous silicon compound and reducibility gas, and perhaps described siliceous reducibility gas is to have the one-component of gaseous silicon compound of reproducibility or the mixture of many components.
Preferably, described gaseous silicon compound is gaseous silane, gaseous state halosilanes, gaseous state alkyl silane or gaseous state alkoxy silane.
Preferably, described halosilanes is SiF
4, SiCl
4Or SiHCl
3
Preferably, described alkyl silane is Si (CH
3)
4Or Si (CH
2CH
3)
4
Preferably, described alkoxy silane is tetramethoxy-silicane, a methoxytrimethylsilane, tetraethoxysilane.
Preferably, described reducibility gas is hydrogen.
Obtain silicon, graphene composite material by oxidation graphite solid being placed siliceous atmosphere carry out reduction reaction in this preparation process, preparation process is relatively simple, because the impurity that produces in the course of reaction is gaseous matter, can directly discharge, need not complicated dry purification step, can directly obtain product, thereby preparation efficiency is higher, the composite material purity that makes is high, and performance is guaranteed.
[description of drawings]
Fig. 1 is the silicon that makes of embodiment 1, the SEM photo of graphene composite material;
Fig. 2 is the XRD figure of the silicon that makes of embodiment 1, graphene composite material.
[embodiment]
Below main in conjunction with the drawings and the specific embodiments the preparation method of silicon, graphene composite material is described in further detail.
Present embodiment provides the preparation method of a kind of silicon, graphene composite material, and this composite material is the particle that comprises nanometer or the micron level of silicon and Graphene.Wherein, the mass fraction of silicon is 1～50% in the composite material.Graphene is layer structure, and the silicon particle is dispersed among the lamellar structure of Graphene, and silicon particle and Graphene can reach other mixing of molecular level, and good consistency and uniformity are arranged; Adsorb silicon grain on large stretch of graphene film, can offer silicon particle ionic conductivity, can significantly improve the electronic conductivity of silicon particle simultaneously.
The silicon of present embodiment, the preparation method of graphene composite material, preparation technology's flow process is as follows:
Reduction → silicon, graphene composite material in the reducibility gas atmosphere of graphite → graphite oxide → siliceous
Specifically comprise the steps:
Step S1: preparation graphite oxide.
Preferably, can adopt the preparation of following method, comprise the steps: graphite raw material, potassium peroxydisulfate and phosphorus pentoxide are added in 80 ℃ the concentrated sulfuric acid, stir, cooling is more than 6 hours, suction filtration, and washing is to neutral, and drying obtains biased sample; Again biased sample is added in 0 ℃ the concentrated sulfuric acid, add potassium permanganate, the temperature of system remains on below 20 ℃ again, then keeps after 2 hours in 35 ℃ oil bath, slowly add deionized water, after 15 minutes, add again the deionized water that contains hydrogen peroxide, until the color of the solution becomes glassy yellow, suction filtration while hot, be that 10% hydrochloric acid washs with concentration again, suction filtration, 60 ℃ of vacuumizes namely obtain graphite oxide.
Wherein, graphite raw material is preferably purity more than or equal to 99.5% natural flake graphite.
Step S2: the graphite oxide that makes among the step S1 is placed siliceous reducibility gas atmosphere, slowly be heated to 200～1200 ℃ with 10～100 ℃/minute and carry out reduction reaction, obtaining silicon, graphene composite material after the cooling under the reproducibility atmosphere again, wherein, the mass fraction of silicon is controlled between 1～50% in the composite material.
Siliceous reducibility gas is as the silicon source, and graphite oxide redox reaction occurs in siliceous reducibility gas atmosphere generates Graphene and elementary silicon, and Graphene forms layer structure, and elementary silicon is dispersed in the layer structure of Graphene.
Wherein, siliceous reducibility gas can be the mixture of gaseous silicon compound and reducibility gas, if self has reproducibility gaseous silicon compound, then siliceous reducibility gas can also be selected one-component or the multi-component mixture of the gaseous silicon compound with reproducibility.Gaseous silicon compound can be gaseous silane (SiH
4), gaseous state halosilanes, gaseous state alkyl silane or gaseous state alkoxy silane etc.Silane itself has stronger reproducibility, and when using silane as the silicon source, under heating condition, it can be directly and graphite oxide generation redox reaction generation Graphene and elementary silicon.Halosilanes can replace or polysubstituted silane for fluorine, chlorine, bromine, iodine etc. are single, such as silicon tetrafluoride (SiF
4), silicon tetrachloride (SiCl
4), tetrabromo silane (SiBr
4), a chlorine silicofluoroform (SiClF
3), trichlorosilane (SiHCl
3) etc., preferably prepare the relatively low silicon tetrafluoride of easy cost, silicon tetrachloride or trichlorosilane.Alkyl silane can be C
1～C
4The alkyl list replace or polysubstituted silane, such as tetramethylsilane (Si (CH
3)
4) or tetraethyl silane (Si (CH
2CH
3)
4) etc.Alkoxy silane can be C
1～C
4The alkoxyl list replaces or polysubstituted silane, such as tetramethoxy-silicane, a methoxytrimethylsilane, tetraethoxysilane etc.The hydrogen that reducibility gas is preferably commonly used.
Obtain silicon, graphene composite material by oxidation graphite solid being placed siliceous atmosphere carry out reduction reaction in the preparation process of above-mentioned silicon, graphene composite material, preparation process is relatively simple, because the impurity that produces in the course of reaction is gaseous matter, can directly discharge, need not complicated dry purification step, thereby preparation efficiency is higher, and the composite material purity that makes is high, and performance is guaranteed.Nano-micrometre grade silicon can be good at being dispersed between the lamella of Graphene in the composite material that obtains; Because the Graphene of sheet has larger specific area, so composite material has good porosity, good ionic conduction characteristic is arranged, and can be widely used as lithium ion battery, the negative material of ultracapacitor is made the field.
It below is the specific embodiment part
Wherein, gaseous silicon compound select be simple and easy to silane, silicon tetrachloride, silicon tetrafluoride, trichlorosilane, tetramethylsilane, tetramethoxy-silicane etc., in other embodiments, can also be one or more the combination in the siliceous reducibility gas of above-mentioned introduction.Reducibility gas is selected and is easy to get and free of contamination H
2, in other embodiments, can also select the gases such as CO.
Embodiment 1
Preparation technology's flow process is as follows:
Reduction → silicon, graphene composite material in the reducibility gas atmosphere of graphite raw material → graphite oxide → siliceous
(1) graphite raw material: 50 order purity are 99.5% natural flake graphite.
(2) graphite oxide: 20g graphite raw material, 10g potassium peroxydisulfate and 10g phosphorus pentoxide added in 80 ℃ the concentrated sulfuric acid, stir, cooling is more than 6 hours, suction filtration, and washing is to neutral, and drying gets biased sample;
Dried biased sample is added in 0 ℃, the concentrated sulfuric acid of 230mL, adds 60g potassium permanganate again, the temperature of system remains on below 20 ℃, then keeps slowly adding the 920mL deionized water after 2 hours in 35 ℃ oil bath;
After 15 minutes, in system, add the 2.8L deionized water again, until the mixture color becomes glassy yellow, suction filtration while hot, be that 10% hydrochloric acid washs with 5L concentration again, suction filtration namely obtained graphite oxide in 48 hours 60 ℃ of vacuumizes, wherein, containing 50mL concentration in the above-mentioned 2.8L deionized water is 30% hydrogen peroxide.
(3) reduce in the siliceous reducibility gas atmosphere: the graphite oxide powder that step (2) is made is put into and is connected with SiH
4Be warming up to 200 ℃ of reactions 10 hours with the slow speed of 10 ℃/min in the tube furnace of gas; Again with reacted powder at H
2Atmosphere under cool to room temperature with the furnace, obtain silicon, graphene composite material, wherein, the mass fraction of silicon is 1%, its SEM photo as shown in Figure 1, its XRD photo is as shown in Figure 2, wherein, be the characteristic peak of silicon at 28.4 ° and 47.6 ° as can be seen from Figure 2,26 ° and 42.8 ° is the Graphene characteristic peak, shows that the material that obtains is silicon and graphene composite material.
The mass fraction of silicon adopts the calcination method in the composite material, and calcination is 3 hours in 500 ℃ Muffle furnace, and quality is no longer reduced, Graphene is converted into gas fully, remaining is silica solid, and remaining solid is weighed, and calculates the mass fraction of silicon according to formula:
The mass fraction of silicon=(quality of remaining solid * 28/60) * 100%/initial mass
Embodiment 2
The preparation of graphite oxide is with embodiment 1.
The graphite oxide powder that makes put into be connected with SiH
4With H
2In the tube furnace of mist with the slow speed of 100 ℃/min be warming up to 400 ℃ the reaction 1 hour, again with reacted powder at H
2Atmosphere cool to room temperature with the furnace, obtain silicon, graphene composite material, wherein, the mass fraction of silicon is 20%.
Embodiment 3
The preparation of graphite oxide is with embodiment 1.
The graphite oxide powder that makes put into be connected with SiF
4With H
2The tube furnace of mist in be warming up to 400 ℃ of reactions 10 hours with the slow speed of 20 ℃/min, again with reacted powder at H
2Atmosphere cool to room temperature with the furnace, obtain silicon, graphene composite material, wherein, the mass fraction of silicon is 27.8%.
Embodiment 4
The preparation of graphite oxide is with embodiment 1.
The graphite oxide powder that makes put into be connected with SiHCl
3With H
2The tube furnace of mist in be warming up to 800 ℃ of reactions 8 hours with the slow speed of 50 ℃/min, again with reacted powder at H
2Atmosphere cool to room temperature with the furnace, obtain silicon, graphene composite material, wherein, the mass fraction of silicon is 42.5%.
Embodiment 5
The preparation of graphite oxide is with embodiment 1.
The graphite oxide powder that makes put into the tube furnace that is connected with tetramethylsilane and is warming up to 400 ℃ of reactions 10 hours with the slow speed of 40 ℃/min, again with reacted powder at H
2Atmosphere cool to room temperature with the furnace, obtain silicon, graphene composite material, wherein, the mass fraction of silicon is 28.5%.
Embodiment 6
The preparation of graphite oxide is with embodiment 1.
The graphite oxide powder that makes put into the tube furnace that is connected with tetramethoxy-silicane and is warming up to 500 ℃ of reactions 10 hours with the slow speed of 40 ℃/min, again with reacted powder at H
2Atmosphere cool to room temperature with the furnace, obtain silicon, graphene composite material, wherein, the mass fraction of silicon is 30.7%.
Embodiment 7
The preparation of graphite oxide is with embodiment 1.
The graphite oxide powder that makes put into be connected with SiCl
4With H
2The tube furnace of mist in be warming up to 1200 ℃ of reactions 5 hours with the slow speed of 100 ℃/min, again with reacted powder at H
2Atmosphere cool to room temperature with the furnace, obtain silicon, graphene composite material, wherein, the mass fraction of silicon is 50%.
The sample powder that the various embodiments described above are made depresses to disk at the pressure of 10MPa, uses the two electrical measurement four point probe tester testing conductivities of D41-11D/ZM type under the room temperature.When measuring current is shown as the probe coefficient, press electricalresistivityρ's button, then screen shows that directly the electricalresistivityρ is worth, and directly calculates conductivity according to γ=l/ ρ.The conductivity of measuring silicon that each embodiment obtains, graphene composite material by four probe method is as shown in table 1 below, can find out that from table 1 numerical value the silicon, graphene composite material of various embodiments of the present invention are with respect to the conductivity (6.7 * 10 of silicon
-2S/m) improve a lot.
Table 1
Can find out that from table 1 numerical value the silicon, graphene composite material of various embodiments of the present invention are with respect to the conductivity (6.7 * 10 of silicon
-2S/m) improve a lot.
The above embodiment has only expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to claim of the present invention.Should be pointed out that for the person of ordinary skill of the art without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection range of patent of the present invention should be as the criterion with claims.
Claims (9)
1. the preparation method of a silicon, graphene composite material is characterized in that, comprises the steps:
Provide or prepare graphite oxide;
Described graphite oxide is placed the atmosphere of siliceous reducibility gas, slowly be heated to 200～1200 ℃ with 10～100 ℃/minute and carry out reduction reaction, obtain described silicon, graphene composite material after the cooling, wherein, silicon accounts for 1～50% of described silicon, graphene composite material weight.
2. the preparation method of silicon as claimed in claim 1, graphene composite material, it is characterized in that, described preparation graphite oxide comprises the steps: graphite raw material, potassium peroxydisulfate and phosphorus pentoxide are added in 80 ℃ the concentrated sulfuric acid, stir, cooling is more than 6 hours, and suction filtration washs to neutral, drying obtains biased sample;
Described biased sample is added in 0 ℃ the concentrated sulfuric acid, add potassium permanganate, the temperature of system remains on below 20 ℃ again, then keeps after 2 hours in 35 ℃ oil bath, slowly add deionized water, after 15 minutes, add again the deionized water that contains hydrogen peroxide, until the color of the solution becomes glassy yellow, suction filtration while hot, be that 10% hydrochloric acid washs with concentration again, suction filtration, 60 ℃ of vacuumizes namely obtain graphite oxide.
3. the preparation method of silicon as claimed in claim 2, graphene composite material is characterized in that, described graphite raw material is purity more than or equal to 99.5% natural flake graphite.
4. the preparation method of silicon as claimed in claim 1, graphene composite material, it is characterized in that, described siliceous reducibility gas is the mixture of gaseous silicon compound and reducibility gas, and perhaps described siliceous reducibility gas is to have the one-component of gaseous silicon compound of reproducibility or the mixture of many components.
5. the preparation method of silicon as claimed in claim 4, graphene composite material is characterized in that, described gaseous silicon compound is gaseous silane, gaseous state halosilanes, gaseous state alkyl silane or gaseous state alkoxy silane.
6. the preparation method of silicon as claimed in claim 5, graphene composite material is characterized in that, described gaseous state halosilanes is SiF
4, SiCl
4Or SiHCl
3
7. the preparation method of silicon as claimed in claim 5, graphene composite material is characterized in that, described gaseous state alkyl silane is Si (CH
3)
4Or Si (CH
2CH
3)
4
8. the preparation method of silicon as claimed in claim 5, graphene composite material is characterized in that, described gaseous state alkoxy silane is tetramethoxy-silicane, a methoxytrimethylsilane, tetraethoxysilane.
9. such as the preparation method of claim 4 or 5 described silicon, graphene composite material, it is characterized in that described reducibility gas is hydrogen.
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Cited By (5)
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| CN103715405A (en) * | 2013-12-25 | 2014-04-09 | 深圳市贝特瑞纳米科技有限公司 | Silicon-graphene lithium-ion composite electrode material and preparation method thereof |
| CN105016330A (en) * | 2015-07-08 | 2015-11-04 | 常州市诚天电子有限公司 | Graphene preparation method |
| CN105355892A (en) * | 2015-12-15 | 2016-02-24 | 中南大学 | Preparation method of lithium ion battery cathode |
| CN106058207A (en) * | 2016-08-02 | 2016-10-26 | 中国科学技术大学 | Silicon-carbon composite material, preparation method thereof and negative pole for lithium-ion battery |
| CN111392719A (en) * | 2020-03-12 | 2020-07-10 | 兰州大学 | Silicon-doped graphene, preparation method thereof and silicon-doped graphene-based chemical resistance type nitrogen oxide room temperature sensor |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103715405A (en) * | 2013-12-25 | 2014-04-09 | 深圳市贝特瑞纳米科技有限公司 | Silicon-graphene lithium-ion composite electrode material and preparation method thereof |
| CN103715405B (en) * | 2013-12-25 | 2017-02-01 | 深圳市贝特瑞新能源材料股份有限公司 | Silicon-graphene lithium-ion composite electrode material and preparation method thereof |
| CN105016330A (en) * | 2015-07-08 | 2015-11-04 | 常州市诚天电子有限公司 | Graphene preparation method |
| CN105016330B (en) * | 2015-07-08 | 2017-12-22 | 常州市诚天电子有限公司 | A kind of preparation method of graphene |
| CN105355892A (en) * | 2015-12-15 | 2016-02-24 | 中南大学 | Preparation method of lithium ion battery cathode |
| CN106058207A (en) * | 2016-08-02 | 2016-10-26 | 中国科学技术大学 | Silicon-carbon composite material, preparation method thereof and negative pole for lithium-ion battery |
| CN111392719A (en) * | 2020-03-12 | 2020-07-10 | 兰州大学 | Silicon-doped graphene, preparation method thereof and silicon-doped graphene-based chemical resistance type nitrogen oxide room temperature sensor |
| CN111392719B (en) * | 2020-03-12 | 2021-02-09 | 兰州大学 | Silicon-doped graphene, preparation method thereof and silicon-doped graphene-based chemical resistance type nitrogen oxide room temperature sensor |
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