CN106532047A - Silylene/graphene composite material, and preparation method and applications thereof - Google Patents
Silylene/graphene composite material, and preparation method and applications thereof Download PDFInfo
- Publication number
- CN106532047A CN106532047A CN201610934738.4A CN201610934738A CN106532047A CN 106532047 A CN106532047 A CN 106532047A CN 201610934738 A CN201610934738 A CN 201610934738A CN 106532047 A CN106532047 A CN 106532047A
- Authority
- CN
- China
- Prior art keywords
- graphene
- silene
- graphite
- composite material
- engagement
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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 provides a silylene/graphene composite material, and a preparation method and applications thereof. According to the preparation method, a silicon material and a graphene material are mixed, and are processed with high shear stress generated at the interfaces between screw rod engaged screw elements in extruder screw rotating process; the silicon material is taken as a grinding medium of the graphene material; and at the same time, relatively strong Van der Waals bonds are formed between the silicon material and graphene sheets, and rearrangement of silicon atoms on the graphene sheets is realized because of the sheet characteristics of graphene so as to form the silylene/graphene composite material. Mechanical exfoliation and physical shearing are adopted, exfoliation of graphene sheets and growth of silylene are completed via one step operation at the same time, complex high vacuum silylene growth technology is avoided, application of gas materials which are capable of inducing heavy pollution is avoided, cost is reduced, industrial application value is extremely high, and the silylene/graphene composite material is suitable to be taken as a lithium battery anode material.
Description
Technical field
The present invention relates to field of nano material preparation, and in particular to a kind of silene/graphene composite material and its preparation side
Method and application.
Background technology
Graphene is a kind of single atomic thickness and has sp2The slab construction of the carbon atom of bond, in theory, with complete
U.S. hexagonal reticulated structure, is presented excellent electronic stability, thermal conductivity, optical property, mechanical property etc..2004, Britain was graceful thorough
Two scientists of this especially big are found that Graphene using the method that micromechanics is peeled off, and obtain Nobel's thing in 2010
Prize of science.After Graphene is found, due to its excellent performance and huge market application foreground caused physics and
The research boom in the fields such as material science.
Silicon belongs to the IV races element of the periodic table of elements with carbon, equally occupies extremely important in nature and materialogy
Status.2007, Verri et al. proposed that silicon can form the monoatomic layer structure of similar graphite and it is named as silene
（silicene）.Silene possesses the Dirac type electronic structure similar with Graphene, and equally there are six linear dispersions its Brillouin zone
Dirac cone.Thus, the novel quantum effect that great majority are found in Graphene, can find corresponding version in silene
This.And, silene system is also equipped with some advantages that Graphene system does not have, and for example, has higher spin(-)orbit in silene
Coupling, therefore bigger energy gap can be opened in its Dirac point, so as to realize observable quantum logic gates
（QSHE）.Silicon materials are easily obtained and prepare and compatible with existing silicon semiconductor industry, therefore silene has extremely wide in application
Wealthy prospect.By the Graphene and silicon materials compound composite more powerful by function is obtained.
Chinese invention patent application number 201210353611.5 discloses a kind of Two-dimensional silylene film and preparation method thereof.Should
Silicon atom group is released in Catalytic Layer from gaseous state silicon source by method using chemical vapor deposition or physical gas phase deposition technology
And form silylene film；The thickness of the Catalytic Layer is 25nm ~ 25mm, and catalyst layer temperature control is between 20 ~ 1600 DEG C.This
Inventive method is simple, be easily achieved.The silylene film for preparing is heavy for which by three, four, five or seven silicon atoms
Multiple unit the two-dimensional layer film being connected by covalent bond, comprising the number of plies of silene be 1 ~ 200 layer.But, this
The bright gaseous state silicon source corrosivity for using is strong, dangerous high, needs complicated gas raw material storage conveying equipment, and potential safety hazard is big,
Operating difficulties.
Chinese invention patent application number 201210470694.6 discloses a kind of preparation method of silylene material.The method is
Under vacuum conditions, by appropriate Semiconducting Silicon Materials hydatogenesis to transition metal substrate, the transition metal substrate is iridium
(111) face, then whole sample is made annealing treatment, the silicon that will be covered in substrate surface interacts, and forms hexagonal honeybee
The membranaceous structure of sequential 2 D of nest shape arrangement, so as to obtain silylene material.This new material is not being write letters similar to Graphene
Potentiality are had a wide range of applications in terms of breath electronics and device developmental research.But, the method uses rare (111) face monocrystalline
As substrate raw material, it is unfavorable for industrialization large-scale production, is unfavorable for reduces cost.
Chinese invention patent application number 201510344931.8 discloses a kind of spongy 3 SiC 2/graphite alkene and CNT is multiple
The preparation method of negative material is closed, the composite is made up of silica flour, Graphene and CNT, weight hundred wherein shared by silica flour
Divide than being 50%～90%, Graphene is 2%～35%, CNT is 1%～25%；The present invention adopts freeze-drying or super
Composite obtained in the method for critical drying, original skeleton structure of reservation are formed with CNT as skeletal support unit,
With Graphene as built pore structure face, the 3 D stereo conductive network composite construction of countless holes is supported jointly, and
Silica flour is adsorbed in its internal void.The conductivity of composite material is high, and structural elasticity is big, and adsorptivity is strong, effectively inhibits silicon
Volumetric expansion during impulse electricity, improves the cyclical stability of material.Present invention process is simple, environmental protection,
Suitable industrialized production.If however, the program is combined with Graphene using the more slim silene of thickness, will further improve
The conductive capability of composite, and retain the mechanical property of Graphene itself, it is more suitable for the cathode material of battery.
In sum, also no silene/graphene composite material in currently available technology, does not more have one kind prepare silicon
The methods and applications of alkene/graphene composite material.
The content of the invention
For main at present using physically or chemically vapor deposition growth silylene material, the silene after growth is acted on substrate
It is relatively strong, it is difficult transfer.There is no the successful extension on semiconductor and insulator to synthesize the experiment of silene, also do not obtain such as Graphene
The silene of substrate individualism is independent of like that.This method Preparation equipment has high demands, and threshold is high, is only applicable to laboratory and grinds
Study carefully, it is impossible to realize industrialized production.Mechanical stripping method preparation method is simple, and preparation process is environment friendly and pollution-free, and production cost is more
It is cheap, favor is enjoyed in Graphene industrial production.The present invention proposes a kind of silene/graphene composite material and preparation method thereof
And application, silicon materials are engaged between screwing element interface generation height by screw rod in screw rod rotary course with after graphite material mixing
Shear stress, using silicon materials as graphite material abrasive media, simultaneously because can be formed between silicon materials and graphite flake layer
Stronger Van der Waals key, resets on graphene layer by the lamella characteristic silicon atom of graphite, forms silene/Graphene composite wood
Material.Mode of the present invention using mechanical stripping, is acted on by physical shear, is completed while graphite flake layer is peeled off by single stepping
The growth of silene, it is to avoid the technique that complicated high vacuum grows silene, it is thus also avoided that high pollution gas raw material, reduces technique
Cost, with very high industrial application value.
On the one hand, the present invention provides a kind of preparation method of silene/graphene composite material, including：
（1）Cleaning nano silicon particles and graphite granule；
（2）One layer of catalyst layer is uniformly wrapped up on described nano silicon particles, compound nano silicon particles, described catalysis is obtained
The thickness of oxidant layer is 3 ~ 10nm；
（3）The compound nano silicon particles and graphite granule are mixed by stirring in high mixer, nano silicon particles are made as grinding
Grinding media is evenly distributed in graphite, obtains composite particles, then is extruded by extruder, and the setting temperature of extruder is 600 ~
950 DEG C, the graphite in composite particles peels off into Graphene under high shear, and the silicon grain in composite particles is in high temperature ring
Resolve into silicon atom to reset in graphenic surface diffusion under border, Strong shear power and catalyst action, obtain silene/Graphene and be combined
Material, arranges collection device in extruder discharging mouth and collects silene/graphene composite material, be cooled to room temperature.
Preferably, the particle diameter of the nano silicon particles be 5 ~ 20nm, the graphite granule be crystalline flake graphite, expanded graphite,
At least one in highly oriented graphite, thermal cracking graphite, graphite oxide, the average grain diameter of the graphite granule is less than 1 millimeter.
Preferably, the cleaning nano silicon particles are comprised the following steps：
Ultrasound 0.5 ~ 1 minute first in HF solution, removes the silica on nano silicon particles surface, last deionized water punching
Wash, remove HF Liquid Residues, nano silicon particles are dried under 80 ~ 90 DEG C of argon gas protection；
The HF solution concentrations are 3.5 ~ 5%；
It is 99.9% that the argon gas is purity, and the ambient pressure of argon gas is 100 ~ 1000Pa.
Preferably, film of the catalyst layer prepared by a kind of metal in metal Ag, Au, Mo, Cu and Ti.
Preferably, the metallic film is coated on the nano silicon particles specially adopt evaporation, sputtering method, chemistry
At least one method in reducing process obtains the default metal integument.
Preferably, the speed of the high mixer stirring rotation is 500-1000rpm, and the extruder is engagement screws in the same direction
Machine.
Preferably, described extruder is meshed double screw machine in the same direction, in the same direction three screw machines of engagement, in the same direction four screw rods of engagement
The engagement screws machine in the same direction of machine or more multiscrew；
Described engagement screws machine in the same direction is combined on mandrel by screwing element, by arranging different screwing elements,
Graphite is continuously orientated along vertical and horizontal direction when screw rod rotates, shear and peel off so as to the Graphene for obtaining；
Described dispersion orientation section conveys the engagement spiral shell that screwing element, two groups of teeth shape disk, four groups of oblique angles are 60 ° by two group 56/56
Texel part, four groups of reverse 56/56 conveying screwing element compositions；
It is first that the engagement screw thread that the engagement screwing element that Duan Yousi groups oblique angle is 30 °, four groups of oblique angles are 45 ° is peeled off in described shearing
Part, four groups reverse 45 ° of engagement screwing element group, four groups 90 ° of right angle engagement screwing element, four groups reverse 60 ° of engagement spiral shell
Texel part is constituted.
On the other hand a kind of silene/graphene composite material is provided, is prepared from by said method, with silicon atom in stone
The Rotating fields reset on black alkene layer, are a kind of silene Rotating fields compound with Graphene.
Further, a kind of silene/graphene composite material is applied to the negative material of lithium battery.
Silene/graphene composite material prepared by of the invention is born with carbon as performance of lithium ion battery prepared by negative material
Pole material lithium ion battery the performance test results contrast, as shown in table 1.
Table 1：
| Performance indications | Specific capacity | Cycle life | Internal resistance value | Self-discharge rate |
| The present invention | 900mAh/g | 1000 | 4mOhm | 20% |
| Carbon negative pole material lithium ion battery | 370mAh/g | 400 | 14mOhm | 30% |
Silene cost is very high to adopt physics and chemical vapour deposition technique to prepare at present, is not suitable for the skill of large-scale industrial production
Art problem, and use hypertoxic dusty gas or rare noble metal, it is also possible to need to post-process silylene film
To improve its stability, and then cause complex disposal process, the problems such as production cycle and cost increase.Mechanical stripping method preparation side
Method is simple, and preparation process is environment friendly and pollution-free, and production cost is more cheap, and favor is enjoyed in Graphene industrial production.The present invention
A kind of silene/graphene composite material and its preparation method and application is proposed, after silicon materials are mixed with graphite material, passes through spiral shell
During bar rotating Vortex, between screw rod engagement screwing element, interface produces shearing force, using silicon materials as graphite material
Abrasive media, simultaneously because stronger Van der Waals key between silicon materials and graphite flake layer, can be formed, by the lamella characteristic of graphite
Silicon atom is reset in graphite linings, forms silene/graphene composite material.Mode of the present invention using mechanical stripping, by thing
Reason shear action, completes the growth of silene while graphite flake layer is peeled off by single stepping, it is to avoid complicated high vacuum growth
The technique of silene, it is thus also avoided that high pollution gas raw material, reduces process costs, with very high industrial application value.
A kind of silene/graphene composite material of the present invention and preparation method thereof, compared with prior art, the characteristics of its protrusion
With excellent effect it is：
1st, complete the growth of silene while graphite flake layer is peeled off by single stepping of the present invention, it is to avoid complicated high vacuum life
The technique of long silene, it is thus also avoided that high pollution gas raw material, reduces process costs.
2nd, the present invention adopts simple mechanical stripping method, is easily prepared for silene composite, is suitable for industrializing big rule
Mould is produced.
3rd, conventional metallic catalyst raw material is present invention employs, it is with low cost.
4th, the present invention provides powerful shearing force using screw machine and peels off graphite and silicon, obtains silene/Graphene composite wood
Material, operation platform are low, are suitable for industrialization promotion.
Specific embodiment
Below by way of specific embodiment, the present invention is described in further detail, but this should not be interpreted as the present invention
Scope be only limitted to Examples below.In the case of without departing from said method thought of the present invention, according to ordinary skill
Various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
The present embodiment is comprised the following steps:
（1）Cleaning nano silicon particles and graphite granule.The particle diameter of selected nano silicon particles is 5nm, and graphite granule is graphite
The average grain diameter of grain is 0.9 millimeter of crystalline flake graphite.
Cleaning nano silicon particles are comprised the following steps：Ultrasound 0.5 minute first in the HF solution that solution concentration is 3.5%,
The silica on nano silicon particles surface is removed, last deionized water is rinsed, and is removed HF Liquid Residues, in 80 DEG C of purity is
99.9%, the ambient pressure of argon gas is drying nano silicon particles under the argon gas protection of 100Pa.
（2）Using evaporation, nano silicon particles are put in vacuum chamber, control background vacuum for 1.0 × 10-3Pa, adopts
Resistance wire evaporates, and monitors coating process using crystal oscillator instrument, and setting evaporation current is 100A, and coated film deposition speed is 0.04 nm/s,
On described nano silicon particles, uniform parcel layer of metal Ag obtains compound nano silicon particles, metal Ag as catalyst layer
Thickness be 3nm.
（3）The compound nano silicon particles are mixed by stirring in high mixer with graphite granule, makees nano silicon particles
It is evenly distributed in graphite for abrasive media, obtains composite particles, then extruded by meshed double screw machine in the same direction, described is in the same direction
Engagement screws machine is combined on mandrel by screwing element, by arranging different screwing elements, graphite is revolved in screw rod
Continuously it is orientated along vertical and horizontal direction when turning, shears and peel off so as to the Graphene for obtaining；
Described dispersion orientation section conveys the engagement spiral shell that screwing element, two groups of teeth shape disk, four groups of oblique angles are 60 ° by two group 56/56
Texel part, four groups of reverse 56/56 conveying screwing element compositions；
It is first that the engagement screw thread that the engagement screwing element that Duan Yousi groups oblique angle is 30 °, four groups of oblique angles are 45 ° is peeled off in described shearing
Part, four groups reverse 45 ° of engagement screwing element group, four groups 90 ° of right angle engagement screwing element, four groups reverse 60 ° of engagement spiral shell
Texel part is constituted.The setting temperature for arranging extruder is 600 DEG C, and the graphite in composite particles is peeled off under high shear
Graphene, the silicon grain in composite particles resolve into silicon atom in graphite under hot environment, Strong shear power and catalyst action
Alkene diffusion into the surface is reset, and obtains silene/graphene composite material, arranges collection device in extruder discharging mouth and collects silene/stone
Black alkene composite, is cooled to room temperature.
Using the silene/graphene composite material obtained in embodiment 1 as cell negative electrode material, anode LiMn2O4,
Electrolyte is that the performance of lithium ion battery for of the carbonate-based solvent preparation for being dissolved with lithium hexafluoro phosphate is as shown in table 2.
Embodiment 2
The present embodiment is comprised the following steps:
（1）Cleaning nano silicon particles and graphite granule.The particle diameter of selected nano silicon particles is 10nm, and graphite granule is graphite
The expanded graphite of 0.5 millimeter of the average grain diameter of grain.
Cleaning nano silicon particles are comprised the following steps：First in the HF solution that solution concentration is 4%, ultrasound 0.5 minute, goes
Except the silica on nano silicon particles surface, last deionized water are rinsed, HF Liquid Residues are removed, are 99.9% in 85 DEG C of purity,
Argon gas protection lower drying nano silicon particles of the ambient pressure of argon gas for 300Pa.
（2）Using evaporation, nano silicon particles are put in vacuum chamber, control background vacuum for 1.0 × 10-3Pa, adopts
Resistance wire evaporates, and monitors coating process using crystal oscillator instrument, and setting evaporation current is 120A, and coated film deposition speed is 0.08nm/s,
On described nano silicon particles, uniform parcel layer of metal Au obtains compound nano silicon particles, metal Au as catalyst layer
Thickness be 5nm.
（3）The compound nano silicon particles are mixed by stirring in high mixer with graphite granule, makees nano silicon particles
It is evenly distributed in graphite for abrasive media, obtains composite particles, then extruded by meshed double screw machine in the same direction, described is in the same direction
Engagement screws machine is combined on mandrel by screwing element, by arranging different screwing elements, graphite is revolved in screw rod
Continuously it is orientated along vertical and horizontal direction when turning, shears and peel off so as to the Graphene for obtaining；
Described dispersion orientation section conveys the engagement spiral shell that screwing element, two groups of teeth shape disk, four groups of oblique angles are 60 ° by two group 56/56
Texel part, four groups of reverse 56/56 conveying screwing element compositions；
It is first that the engagement screw thread that the engagement screwing element that Duan Yousi groups oblique angle is 30 °, four groups of oblique angles are 45 ° is peeled off in described shearing
Part, four groups reverse 45 ° of engagement screwing element group, four groups 90 ° of right angle engagement screwing element, four groups reverse 60 ° of engagement spiral shell
Texel part is constituted.The setting temperature for arranging extruder is 700 DEG C, and the graphite in composite particles is peeled off under high shear
Graphene, the silicon grain in composite particles resolve into silicon atom in graphite under hot environment, Strong shear power and catalyst action
Alkene diffusion into the surface is reset, and obtains silene/graphene composite material, arranges collection device in extruder discharging mouth and collects silene/stone
Black alkene composite, is cooled to room temperature.
Using the silene/graphene composite material obtained in embodiment 2 as cell negative electrode material, anode LiMn2O4,
Electrolyte is that the performance of lithium ion battery for of the carbonate-based solvent preparation for being dissolved with lithium hexafluoro phosphate is as shown in table 2.
Embodiment 3
The present embodiment is comprised the following steps:
（1）Cleaning nano silicon particles and graphite granule.The particle diameter of selected nano silicon particles is 10nm, and graphite granule is graphite
The average grain diameter of grain is 0.5 millimeter of highly oriented graphite.
Cleaning nano silicon particles are comprised the following steps：First in the HF solution that solution concentration is 3.5%, ultrasound 1 minute, goes
Except the silica on nano silicon particles surface, last deionized water are rinsed, HF Liquid Residues are removed, are 99.9% in 80 DEG C of purity,
Argon gas protection lower drying nano silicon particles of the ambient pressure of argon gas for 100 ~ 1000Pa.
（2）Using sputtering method, nano silicon particles are put in vacuum chamber, control background vacuum for 1.0 × 10-3Pa, adopts
Mo metal targets, monitor coating process using crystal oscillator instrument, and used as shielding power supply, control DC current density is dc source
15mA/cm2, from for 6mm, sputtering pressure is 0.1Pa to target-substrate distance, uniform parcel layer of metal Mo on described nano silicon particles
As catalyst layer, compound nano silicon particles are obtained, the thickness of metal Mo is 6nm.
（3）The compound nano silicon particles are mixed by stirring in high mixer with graphite granule, makees nano silicon particles
It is evenly distributed in graphite for abrasive media, obtains composite particles, then by three screw machines of engagement extrusion in the same direction, described is in the same direction
Engagement screws machine is combined on mandrel by screwing element, by arranging different screwing elements, graphite is revolved in screw rod
Continuously it is orientated along vertical and horizontal direction when turning, shears and peel off so as to the Graphene for obtaining；
Described dispersion orientation section conveys the engagement spiral shell that screwing element, two groups of teeth shape disk, four groups of oblique angles are 60 ° by two group 56/56
Texel part, four groups of reverse 56/56 conveying screwing element compositions；
It is first that the engagement screw thread that the engagement screwing element that Duan Yousi groups oblique angle is 30 °, four groups of oblique angles are 45 ° is peeled off in described shearing
Part, four groups reverse 45 ° of engagement screwing element group, four groups 90 ° of right angle engagement screwing element, four groups reverse 60 ° of engagement spiral shell
Texel part is constituted.The setting temperature for arranging extruder is 600 DEG C, and the graphite in composite particles is peeled off under high shear
Graphene, the silicon grain in composite particles resolve into silicon atom in graphite under hot environment, Strong shear power and catalyst action
Alkene diffusion into the surface is reset, and obtains silene/graphene composite material, arranges collection device in extruder discharging mouth and collects silene/stone
Black alkene composite, is cooled to room temperature.
Using the silene/graphene composite material obtained in embodiment 3 as cell negative electrode material, anode LiMn2O4,
Electrolyte is that the performance of lithium ion battery for of the carbonate-based solvent preparation for being dissolved with lithium hexafluoro phosphate is as shown in table 2.
Embodiment 4
The present embodiment is comprised the following steps:
（1）Cleaning nano silicon particles and graphite granule.The particle diameter of selected nano silicon particles is 15nm, and graphite granule is graphite
The average grain diameter of grain is 0.4 millimeter of graphite oxide.
Cleaning nano silicon particles are comprised the following steps：Ultrasound 1 minute first in the HF solution that solution concentration is 5%, removes
The silica on nano silicon particles surface, last deionized water are rinsed, and remove HF Liquid Residues, are 99.9% in 80 DEG C of purity, argon
Argon gas protection lower drying nano silicon particles of the ambient pressure of gas for 800Pa.
（2）Using sputtering method, nano silicon particles are put in vacuum chamber, control background vacuum for 1.0 × 10-3Pa, adopts
Ti metal targets, monitor coating process using crystal oscillator instrument, and used as shielding power supply, control DC current density is dc source
20mA/cm2, from for 10mm, sputtering pressure is 3.0Pa to target-substrate distance, the uniform parcel layer of metal on described nano silicon particles
Mo obtains compound nano silicon particles as catalyst layer, and the thickness of metal Ti is 6nm.
（3）The compound nano silicon particles are mixed by stirring in high mixer with graphite granule, makees nano silicon particles
It is evenly distributed in graphite for abrasive media, obtains composite particles, then by four screw machines of engagement extrusion in the same direction, described is in the same direction
Engagement screws machine is combined on mandrel by screwing element, by arranging different screwing elements, graphite is revolved in screw rod
Continuously it is orientated along vertical and horizontal direction when turning, shears and peel off so as to the Graphene for obtaining；
Described dispersion orientation section conveys the engagement spiral shell that screwing element, two groups of teeth shape disk, four groups of oblique angles are 60 ° by two group 56/56
Texel part, four groups of reverse 56/56 conveying screwing element compositions；
It is first that the engagement screw thread that the engagement screwing element that Duan Yousi groups oblique angle is 30 °, four groups of oblique angles are 45 ° is peeled off in described shearing
Part, four groups reverse 45 ° of engagement screwing element group, four groups 90 ° of right angle engagement screwing element, four groups reverse 60 ° of engagement spiral shell
Texel part is constituted.The setting temperature for arranging extruder is 800 DEG C, and the graphite in composite particles is peeled off under high shear
Graphene, the silicon grain in composite particles resolve into silicon atom in graphite under hot environment, Strong shear power and catalyst action
Alkene diffusion into the surface is reset, and obtains silene/graphene composite material, arranges collection device in extruder discharging mouth and collects silene/stone
Black alkene composite, is cooled to room temperature.
Using the silene/graphene composite material obtained in embodiment 4 as cell negative electrode material, anode LiMn2O4,
Electrolyte is that the performance of lithium ion battery for of the carbonate-based solvent preparation for being dissolved with lithium hexafluoro phosphate is as shown in table 2.
Embodiment 5
The present embodiment is comprised the following steps:
（1）Cleaning nano silicon particles and graphite granule.The particle diameter of selected nano silicon particles is 5nm, and graphite granule is graphite
The average grain diameter of grain is the crystalline flake graphite less than 1 millimeter.
Cleaning nano silicon particles are comprised the following steps：Ultrasound 0.5 minute first in the HF solution that solution concentration is 3.5%,
The silica on nano silicon particles surface is removed, last deionized water is rinsed, and is removed HF Liquid Residues, in 80 DEG C of purity is
99.9%, the ambient pressure of argon gas is drying nano silicon particles under the argon gas protection of 100 ~ 1000Pa.
（2）Nano silicon particles are put in chemical ware.Using chemical reduction method plated film, raw material is copper sulphate 5.0g/L,
37% formaldehyde 15mL/L, sodium potassium tartrate tetrahydrate 50g/L, sodium carbonate is 3g/L, and temperature is 25 DEG C of room temperature, first mixing copper sulphate solution, wine
Then stone acid potassium sodium solution, sodium carbonate liquor are added dropwise formalin, and whole process adopts air stirring, on nano silicon particles
Uniform parcel layer of metal Cu obtains compound nano silicon particles as catalyst layer, and the thickness of Ni metal is 10nm.
（3）The compound nano silicon particles are mixed by stirring in high mixer with graphite granule, makees nano silicon particles
It is evenly distributed in graphite for abrasive media, obtains composite particles, then by five screw machines of engagement extrusion in the same direction, described is in the same direction
Engagement screws machine is combined on mandrel by screwing element, by arranging different screwing elements, graphite is revolved in screw rod
Continuously it is orientated along vertical and horizontal direction when turning, shears and peel off so as to the Graphene for obtaining；
Described dispersion orientation section conveys the engagement spiral shell that screwing element, two groups of teeth shape disk, four groups of oblique angles are 60 ° by two group 56/56
Texel part, four groups of reverse 56/56 conveying screwing element compositions；
It is first that the engagement screw thread that the engagement screwing element that Duan Yousi groups oblique angle is 30 °, four groups of oblique angles are 45 ° is peeled off in described shearing
Part, four groups reverse 45 ° of engagement screwing element group, four groups 90 ° of right angle engagement screwing element, four groups reverse 60 ° of engagement spiral shell
Texel part is constituted.The setting temperature for arranging extruder is 950 DEG C, and the graphite in composite particles is peeled off under high shear
Graphene, the silicon grain in composite particles resolve into silicon atom in graphite under hot environment, Strong shear power and catalyst action
Alkene diffusion into the surface is reset, and obtains silene/graphene composite material, arranges collection device in extruder discharging mouth and collects silene/stone
Black alkene composite, is cooled to room temperature.
Using the silene/graphene composite material obtained in embodiment 1 as cell negative electrode material, anode LiMn2O4,
Electrolyte is that the performance of lithium ion battery for of the carbonate-based solvent preparation for being dissolved with lithium hexafluoro phosphate is as shown in table 2.
Table 2
| Performance indications | Specific capacity | Cycle life | Internal resistance value | Self-discharge rate |
| Embodiment one | 900mAh/g | 1000 | 4mOhm | 20% |
| Embodiment two | 920mAh/g | 950 | 5.1mOhm | 23% |
| Embodiment three | 930mAh/g | 1030 | 4.3mOhm | 27% |
| Example IV | 890mAh/g | 1050 | 5.7mOhm | 19% |
| Embodiment five | 910mAh/g | 900 | 4.5mOhm | 28% |
Claims (9)
1. a kind of preparation method of silene/graphene composite material, it is characterised in that methods described adopts nano silicon particles conduct
Silicon source, comprises the following steps：
（1）Cleaning nano silicon particles and graphite granule；
（2）One layer of catalyst layer is uniformly wrapped up on described nano silicon particles, compound nano silicon particles, described catalysis is obtained
The thickness of oxidant layer is 3 ~ 10nm；
（3）The compound nano silicon particles and graphite granule are mixed by stirring in high mixer, nano silicon particles are made as grinding
Grinding media is evenly distributed in graphite, obtains composite particles, then is extruded by extruder, and the setting temperature of extruder is 600 ~
950 DEG C, the graphite in composite particles peels off into Graphene under high shear, and the silicon grain in composite particles is in high temperature ring
Resolve into silicon atom to reset in graphenic surface diffusion under border, Strong shear power and catalyst action, obtain silene/Graphene and be combined
Material, arranges collection device in extruder discharging mouth and collects silene/graphene composite material, be cooled to room temperature.
2. a kind of preparation method of silene/graphene composite material according to claim 1, it is characterised in that the silicon
The particle diameter of nano particle be 5 ~ 20nm, the graphite granule be crystalline flake graphite, expanded graphite, highly oriented graphite, thermal cracking graphite,
At least one in graphite oxide, the average grain diameter of the graphite granule is less than 1 millimeter.
3. the preparation method of a kind of silene/graphene composite material according to claim 1, it is characterised in that described clear
Wash nano silicon particles to comprise the following steps：
Ultrasound 0.5 ~ 1 minute first in HF solution, removes the silica on nano silicon particles surface, last deionized water punching
Wash, remove HF Liquid Residues, nano silicon particles are dried under 80 ~ 90 DEG C of argon gas protection；
The HF solution concentrations are 3.5 ~ 5%；
It is 99.9% that the argon gas is purity, and the ambient pressure of argon gas is 100 ~ 1000Pa.
4. the preparation method of a kind of silene/graphene composite material according to claim 1, it is characterised in that described to urge
Film of the agent layer prepared by a kind of metal in metal Ag, Au, Mo, Cu and Ti.
5. a kind of preparation method of silene/graphene composite material according to claim 4, it is characterised in that the gold
Category film is specially and adopts evaporation, sputtering method, and at least one method in chemical reduction method obtains the default metal parcel
Layer.
6. a kind of preparation method of silene/graphene composite material according to claim 1, it is characterised in that the height
The speed of mixed machine stirring rotation is 500-1000rpm, and the extruder is engagement screws machine in the same direction.
7. the preparation method of a kind of silene/graphene composite material according to claim 6, it is characterised in that described
Extruder is meshed double screw machine in the same direction, three screw machines of engagement, in the same direction four screw machines of engagement or more multiscrew is in the same direction in the same direction
Engagement screws machine；
Described engagement screws machine in the same direction is combined on mandrel by screwing element, by arranging different screwing elements,
Graphite is continuously orientated along vertical and horizontal direction when screw rod rotates, shear and peel off so as to the Graphene for obtaining；
Described dispersion orientation section conveys the engagement spiral shell that screwing element, two groups of teeth shape disk, four groups of oblique angles are 60 ° by two group 56/56
Texel part, four groups of reverse 56/56 conveying screwing element compositions；
It is first that the engagement screw thread that the engagement screwing element that Duan Yousi groups oblique angle is 30 °, four groups of oblique angles are 45 ° is peeled off in described shearing
Part, four groups reverse 45 ° of engagement screwing element group, four groups 90 ° of right angle engagement screwing element, four groups reverse 60 ° of engagement spiral shell
Texel part is constituted.
8. a kind of silene/graphene composite material, it is characterised in that the preparation method described in any one of right 1-7 is prepared from
Silene/graphene composite material, structure resets on graphene layer for silicon atom and is composited.
9. a kind of application of silene/graphene composite material, is characterized in that being applied to the negative material of lithium battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610934738.4A CN106532047A (en) | 2016-11-01 | 2016-11-01 | Silylene/graphene composite material, and preparation method and applications thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610934738.4A CN106532047A (en) | 2016-11-01 | 2016-11-01 | Silylene/graphene composite material, and preparation method and applications thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106532047A true CN106532047A (en) | 2017-03-22 |
Family
ID=58291806
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610934738.4A Pending CN106532047A (en) | 2016-11-01 | 2016-11-01 | Silylene/graphene composite material, and preparation method and applications thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106532047A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111554910A (en) * | 2020-05-19 | 2020-08-18 | 溧阳天目先导电池材料科技有限公司 | Lithium battery negative electrode material containing pre-lithiated silylene material, preparation method thereof and lithium battery |
| CN113972362A (en) * | 2021-09-09 | 2022-01-25 | 宁波二黑科技有限公司 | Active composite material for lithium ion battery and preparation method thereof |
| CN114368743A (en) * | 2020-10-15 | 2022-04-19 | 佛山市佳汇科技有限公司 | Preparation method of graphene coated with silicon |
-
2016
- 2016-11-01 CN CN201610934738.4A patent/CN106532047A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111554910A (en) * | 2020-05-19 | 2020-08-18 | 溧阳天目先导电池材料科技有限公司 | Lithium battery negative electrode material containing pre-lithiated silylene material, preparation method thereof and lithium battery |
| CN114368743A (en) * | 2020-10-15 | 2022-04-19 | 佛山市佳汇科技有限公司 | Preparation method of graphene coated with silicon |
| CN113972362A (en) * | 2021-09-09 | 2022-01-25 | 宁波二黑科技有限公司 | Active composite material for lithium ion battery and preparation method thereof |
| CN113972362B (en) * | 2021-09-09 | 2023-02-24 | 宁波二黑科技有限公司 | Active composite material for lithium ion battery and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yuan et al. | Si-based materials derived from biomass: synthesis and applications in electrochemical energy storage | |
| CN105492126B (en) | Ultrasonic spray coating of conducting and transparent films from combined graphene and conductive nano filaments | |
| CN105293483B (en) | A kind of method that original position prepares transient metal doped porous graphene | |
| CN105271170B (en) | Preparation method of nano carbon and composite material of nano carbon | |
| CN106410155B (en) | A kind of preparation method of graphene silica carbon negative pole material | |
| CN103183334A (en) | Preparation method of size controllable grapheme | |
| CN107565115A (en) | Preparation method, silicon-carbon cathode material and the lithium ion battery of silicon-carbon cathode material | |
| CN103922330A (en) | Method for preparing graphene powder by using dry process | |
| CN109686952A (en) | A kind of silicon-carbon cathode material and coating preparation method | |
| CN106876665A (en) | Silicon carbide composite particles, its preparation method and application | |
| CN106532047A (en) | Silylene/graphene composite material, and preparation method and applications thereof | |
| CN103553030A (en) | Preparation method of few-layer graphene | |
| CN107324319B (en) | A kind of big lamella graphene and preparation method thereof | |
| CN106276881B (en) | A kind of preparation method of graphene | |
| CN102515151A (en) | Porous graphene with stratified columnar support structure and its preparation method | |
| CN110170648A (en) | Graphene coated nickel alloy composite granule and preparation method thereof | |
| CN104386676A (en) | Preparation method of graphene | |
| CN105417534A (en) | Method for preparation of biomass graphene material by screw machine | |
| CN106145064A (en) | The Tellurobismuthite. nano material of a kind of different-shape and synthetic method thereof | |
| CN105731440A (en) | Method for achieving stripping preparation of graphene nanoplatelets by means of phase change material | |
| CN106882795A (en) | A kind of scale ultrasound stripping prepares the application of the method and Graphene of Graphene | |
| CN111559743B (en) | Preparation method and application of graphene powder | |
| CN110600688A (en) | Silene-copper-silylene composite material, preparation method, application and lithium ion battery | |
| CN106395768A (en) | Ultrathin boron nitride nanosheet synthesis method | |
| CN106744835A (en) | A kind of method that utilization maize straw prepares Graphene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170322 |
|
| RJ01 | Rejection of invention patent application after publication |