CN109686960A - A kind of carbon coating silicon nanometer sheet and silicon based composite material and preparation method thereof - Google Patents
A kind of carbon coating silicon nanometer sheet and silicon based composite material and preparation method thereof Download PDFInfo
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- CN109686960A CN109686960A CN201910041404.8A CN201910041404A CN109686960A CN 109686960 A CN109686960 A CN 109686960A CN 201910041404 A CN201910041404 A CN 201910041404A CN 109686960 A CN109686960 A CN 109686960A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of carbon coating silicon nanometer piece preparation method and carbon coating silicon nanometer sheets, by the way that stirring and ultrasonic disperse 10-30min in 5-20mL water is added in 0.1-1g carbon source；The silicon powder ultrasonic disperse 10-30min of 0.1-1g D50 partial size 10-500nm is added；It is centrifuged after 100-200 DEG C of hydro-thermal reaction 10-24h, is dried in vacuo to obtain carbon coating silicon nanometer sheet.The carbon coating silicon nanometer sheet is by silicon nanometer sheet and is coated on the carbon-coating of surrounding and forms.The invention discloses the silicon based composite material prepared with above-mentioned carbon coating silicon nanometer sheet and preparation methods, by being warming up to carbon coating silicon nanometer sheet, carbon material, carbon source 5-12%:78-85%:10% mixing and ball milling in mass ratio 500-1000 DEG C of calcining 5-12h with 3-10 DEG C/min and obtaining silicon based composite material.The silicon based composite material includes carbon coating silicon nanometer sheet, carbon material and cladding carbon-coating.The carbon coating layer of carbon coating silicon nanometer sheet and silicon based composite material of the invention has buffered the volume expansion of silicon, enhances electric conductivity, and the expansion that carbon-coating further suppresses silicon is covered in the double-contracting of silicon based composite material, improves first charge-discharge efficiency and circulation volume conservation rate.
Description
Technical field
The present invention relates to a kind of preparation method of carbon coating silicon nanometer sheet and carbon coating silicon nanometer sheets, further relate to a kind of silicon substrate
The preparation method and silicon based composite material of composite material.
Background technique
Lithium ion battery because of its memory-less effect, energy density is high and the advantages such as self-discharge rate is low make it in industrial circle
It grows rapidly.With its application in portable device and power vehicle, people propose the negative electrode material of lithium ion battery
Higher requirement is gone out.Graphite is most common lithium ion battery negative material at present, with it is cheap, resourceful,
The advantages that with good dynamics.However, it is lower than 0.2V (vs.Li/Li+) to lithium voltage, and especially under high magnification, this electricity
The deposition potential for crimping nearly lithium can generate Li dendrite, cause very big safety issue.In addition, its theoretical specific capacity only has
372mAh/g can no longer meet all kinds of electronic equipment for consumption, especially energy storage device and electric car to energy density
It is required that.Therefore, new negative electrode material is researched and developed as Study on Li-ion batteries field hot spot.
Silica-base material theoretical specific capacity is 4200mAh/g, is one of highest material of specific capacity, silicon abundance is inexpensive
It is easy to get, this makes silicon become one of next-generation lithium ion battery negative material the most popular.But silicon have the shortcomings that it is obvious,
Volume expansion variation is huge in cyclic process, leads to electrode dusting, or even remove from collector, so that capacity be made to decline rapidly
Subtract.Researcher through a variety of ways improves silicon at present, including by silicon nanosizing, alloying and with other materials it is compound
Etc..These methods improve the cycle performance of silicon materials and silicon composite to a certain extent, but capacity attenuation is still
Obviously, modified poor circulation.
Summary of the invention
The technical problem to be solved by the present invention is to provide a kind of first charge-discharge efficiency height, the good lithium ion silicon of cycle performance
Base negative electrode material.
In order to solve the above-mentioned technical problem, basic conception of the invention is: in the coated with carbon bed of silicon, utilizing cladding
The volume expansion of carbon-coating buffering silicon；Silicon uses laminated structure simultaneously, delay silicon wafer also can in the volume expansion of longitudinal direction
Punching, to improve the first charge-discharge efficiency and circulation volume conservation rate of silicium cathode material, and then improves its cycle performance.
Make the first string to realize the present invention, the present invention provides a kind of first charge-discharge efficiency height, circulation volume
The preparation method of the high carbon in lithium ion battery coated Si nanometer sheet negative electrode material of conservation rate and the carbon coating prepared using this method
Silicon nanometer sheet.
The preparation method of carbon coating silicon nanometer sheet provided by the invention a kind of the following steps are included:
Step 1: 0.1-1g carbon source is added in 5-20mL water, stirs simultaneously ultrasonic disperse 10-30min；0.1-1g is added
D50 partial size is the silicon powder of 10-500nm, ultrasonic disperse 10-30min；
Step 2: carrying out hydro-thermal reaction for mixture obtained by step 1 in closed container, and 100-200 DEG C of reaction temperature,
Reaction time is 10-24 hours；
Step 3: by hydro-thermal reaction product centrifugal treating, obtained solid substance is in 40 DEG C of -80 DEG C of vacuum drying；
Step 4: by the solid abrasive after drying, calcining, heating rate is 3-10 DEG C/min when calcining, and calcination temperature is
500-1000 DEG C, calcination time is 5-12 hour to get to carbon coating silicon nanometer sheet.
Preferably, the carbon source is one or more of sucrose, glucose, pitch, polythiophene, polypyrrole, polyaniline.
Preferably, the calcination temperature is 750-800 DEG C.
The present invention provides a kind of carbon coating silicon nanometer sheet, and the carbon coating silicon nanometer sheet is by silicon nanometer sheet and to be coated on it
The carbon-coating composition of surrounding.
Second scheme of the invention, there is provided the high lithiums of a kind of first charge-discharge efficiency height, circulation volume conservation rate
The preparation method of ion battery silicon based composite material and the silicon based composite material prepared using this method.
The present invention provides a kind of method for preparing silicon based composite material, comprising the following steps:
Step 1: by carbon coating silicon nanometer sheet produced by the present invention, D50 partial size be 1-40 μm carbon material, carbon source according to
Mass ratio 5-12%:78-85%:10% mixing, obtains uniformly mixed powder after being put into ball mill ball milling；
Wherein, the carbon material is one of graphite, soft carbon, hard carbon or several mixtures.
Step 2: by the powder calcination after ball milling, calcining heating rate is 3-10 DEG C/min, calcination temperature 500-1000
DEG C, calcination time is 5-12 hour to get to silicon based composite material.
Preferably, ratio of grinding media to material is 10:1 in the ball mill, and Ball-milling Time is 0.5-24 hours, and drum's speed of rotation is
600r/min。
Preferably, the carbon source is one or more of sucrose, glucose, pitch, polythiophene, polypyrrole, polyaniline.
Preferably, the calcination temperature is 750-800 DEG C.
The present invention also provides a kind of silicon based composite material, the silicon based composite material prepares silicon based composite material with above-mentioned
Method be made, the silicon based composite material include carbon coating silicon nanometer sheet, carbon material and cladding carbon-coating；Wherein, the carbon packet
The surface that silicon nanometer sheet is uniformly attached to the carbon material is covered, outside the carbon material for being attached with carbon coating silicon nanometer sheet
It is even to be coated with carbon-coating.
Preferably, the carbon material is one of graphite, soft carbon, hard carbon or several mixtures.
Beneficial effects of the present invention:
Carbon coating silicon nanometer sheet is made by being centrifuged, grinding after hydro-thermal reaction in silicon and carbon source, calcine in the present invention, utilizes
The volume expansion of the carbon-coating buffering silicon of cladding；Laminated structure buffer silicon also can in the volume expansion of longitudinal direction, thus
Improve the first charge-discharge efficiency and circulation volume conservation rate of silicium cathode material.The present invention is received using carbon coating silicon obtained above
Rice piece is reacted with carbon material, carbon source, silicon based composite material is further made, which includes carbon coating silicon nanometer
Piece, carbon material and cladding carbon-coating；Wherein, the carbon coating silicon nanometer sheet is uniformly attached to the surface of the carbon material, described
It is attached with outside the carbon material of carbon coating silicon nanometer sheet and is uniformly coated with carbon-coating.The silicon nanometer sheet surface of the silicon based composite material
Carbon-coating is coated as first layer buffer layer, carbon coating silicon nanometer sheet is adhered on the carbon material, carbon material surface after secondary cladding
Carbon material and carbon coating silicon nanometer sheet are bundled together by cladding carbon-coating, have both effectively been buffered swollen in carbon material cyclic process
It is swollen, the cycle performance of carbon material is improved, also as the second layer buffer layer of silicon nanometer sheet, effectively inhibits silicon in cyclic process
Expansion, to play the effect for making composite material entirety stable cycle performance.
Detailed description of the invention
Fig. 1 is the XRD diagram of carbon coating silicon nanometer sheet obtained by embodiment 1.
Fig. 2 is the scanning electron microscope (SEM) photograph of carbon coating silicon nanometer sheet obtained by embodiment 1.
Fig. 3 is the XRD diagram of silicon based composite material obtained by embodiment 1.
Fig. 4 is the scanning electron microscope (SEM) photograph of silicon based composite material obtained by embodiment 1.
Specific embodiment
It elaborates below with reference to embodiment to the present invention.It should be noted that for these embodiments
Illustrate to be used to help understand the present invention, but and does not constitute a limitation of the invention.In addition, each reality of invention described below
Applying technical characteristic involved in mode can be combined with each other as long as they do not conflict with each other.In addition following is only this hair
Bright section Example, rather than whole embodiments, based on the embodiments of the present invention, those of ordinary skill in the art are not having
Every other embodiment obtained under the premise of creative work is made, shall fall within the protection scope of the present invention.
Embodiment 1:
Prepare carbon coating silicon nanometer sheet:
Step 1: 0.1g sucrose is added in 5mL water, and simultaneously ultrasonic disperse 10min is sufficiently stirred；0.1g D50 partial size is added
For the silicon powder of 10nm, ultrasonic disperse 10min；
Step 2: mixture obtained by step 1 is subjected to hydro-thermal reaction in closed container, 100 DEG C of reaction temperature, is reacted
Time is 10 hours；
Step 3: by hydro-thermal reaction product centrifugal treating, obtained solid substance is dried in vacuo at 60 DEG C；
Step 4: by the solid abrasive after drying, calcining, heating rate is 10 DEG C/min, calcination temperature 500 when calcining
DEG C, calcination time be 5 hours to get arrive carbon coating silicon nanometer sheet.
Fig. 1 is the XRD diagram of carbon coating silicon nanometer sheet obtained by the present embodiment, from Fig. 1 XRD result it was determined that preparation
Obtained carbon coating silicon nanometer sheet main component is silicon.
The scanning electron microscope (SEM) photograph of carbon coating silicon nanometer sheet obtained by Fig. 2 the present embodiment.As seen from Figure 2, after carbon coating
Silicon nanometer sheet be uniformly dispersed, there is not agglomeration.In conjunction with Fig. 1 and Fig. 2 it is found that carbon coating silicon obtained by the present embodiment
Nanometer sheet is by silicon nanometer sheet and is coated on surrounding cladding carbon-coating and forms.
Prepare silicon based composite material:
Step 1: by carbon coating silicon nanometer sheet obtained above, the graphite that D50 partial size is 20 μm, glucose according to quality
It is mixed than 5%:85%:10%, is put into ball mill ball milling 5 hours (ratio of grinding media to material 10:1), drum's speed of rotation 600r/min, ball milling
Uniformly mixed powder is obtained afterwards.
Step 2: the powder after ball milling being transferred in porcelain boat, is put into tube furnace and calcines, and calcining heating rate is 10
DEG C/min, calcination temperature be 500 DEG C, calcination time be 5 hours to get arrive silicon based composite material.
Fig. 3 is the XRD diagram of silicon based composite material obtained by the present embodiment, in terms of the XRD result of Fig. 3, silicon substrate composite wood
The main component of material is graphite and silicon.
Fig. 4 is the scanning electron microscope (SEM) photograph of silicon based composite material obtained by the present embodiment, as seen from Figure 4, the composite wood
Material includes carbon coating silicon nanometer sheet, graphite and cladding carbon-coating；Wherein, the carbon coating silicon nanometer sheet is uniformly attached to the graphite
The surface of particle is uniformly coated with carbon-coating outside the graphite for being attached with carbon coating silicon nanometer sheet.
Embodiment 2:
Prepare carbon coating silicon nanometer sheet:
Step 1: 0.5g pitch is added in 15mL water, and simultaneously ultrasonic disperse 20min is sufficiently stirred；It is added 0.5g D50
Diameter is the silicon powder of 50nm, ultrasonic disperse 20min；
Step 2: mixture obtained by step 1 is subjected to hydro-thermal reaction in closed container, 150 DEG C of reaction temperature, is reacted
Time is 16 hours；
Step 3: by hydro-thermal reaction product centrifugal treating, obtained solid substance is dried in vacuo at 40 DEG C；
Step 4: by the solid abrasive after drying, calcining, heating rate is 5 DEG C/min, calcination temperature 750 when calcining
DEG C, calcination time be 8 hours to get arrive carbon coating silicon nanometer sheet.
Prepare silicon based composite material:
Step 1: carbon coating silicon nanometer sheet obtained above, the graphite that D50 partial size is 40 μm, polyaniline are according to mass ratio
7.5%:82.5%:10% mixing, is put into ball mill ball milling 10 hours (ratio of grinding media to material 10:1), drum's speed of rotation 600r/min,
Uniformly mixed powder is obtained after ball milling.
Step 2: the powder after ball milling being transferred in porcelain boat, is put into tube furnace and calcines, and heating rate is 5 DEG C/min,
Calcination temperature be 750 DEG C, calcination time be 8 hours to get arrive silicon based composite material.
Embodiment 3:
Prepare carbon coating silicon nanometer sheet:
Step 1: 1g glucose is added in 20mL water, and simultaneously ultrasonic disperse 30min is sufficiently stirred；1g D50 partial size is added
For the silicon powder of 200nm, ultrasonic disperse 30min；
Step 2: mixture obtained by step 1 is subjected to hydro-thermal reaction in closed container, 200 DEG C of reaction temperature, is reacted
Time is 24 hours；
Step 3: by hydro-thermal reaction product centrifugal treating, obtained solid substance is dried in vacuo at 80 DEG C；
Step 4: by the solid abrasive after drying, calcining, heating rate is 3 DEG C/min, calcination temperature 1000 when calcining
DEG C, calcination time be 8 hours to get arrive carbon coating silicon nanometer sheet.
Prepare silicon based composite material::
Step 1: by carbon coating silicon nanometer sheet obtained above, the hard carbon that D50 partial size is 1 μm, pitch according to mass ratio
10%:80%:10% mixing, is put into ball mill ball milling 24 hours (ratio of grinding media to material 10:1), drum's speed of rotation 600r/min, ball milling
Uniformly mixed powder is obtained afterwards.
Step 2: the powder after ball milling being transferred in porcelain boat, is put into tube furnace and calcines, and heating rate is 3 DEG C/min,
Calcination temperature be 1000 DEG C, calcination time be 12 hours to get arrive silicon based composite material.
Embodiment 4:
Prepare carbon coating silicon nanometer sheet:
Step 1: 0.5g polypyrrole is added in 20mL water, and simultaneously ultrasonic disperse 20min is sufficiently stirred；0.5g D50 is added
Partial size is the silicon powder of 200nm, ultrasonic disperse 30min；
Step 2: mixture obtained by step 1 is subjected to hydro-thermal reaction in closed container, 200 DEG C of reaction temperature, is reacted
Time is 18 hours；
Step 3: by hydro-thermal reaction product centrifugal treating, obtained solid substance is dried in vacuo at 40 DEG C；
Step 4: by the solid abrasive after drying, calcining, heating rate is 5 DEG C/min, calcination temperature 800 when calcining
DEG C, calcination time be 12 hours to get arrive carbon coating silicon nanometer sheet.
Prepare silicon based composite material:
Step 1: by carbon coating silicon nanometer sheet obtained above, the hard carbon that D50 partial size is 5 μm, polythiophene according to mass ratio
10%:80%:10% mixing, is put into ball mill ball milling 12 hours (ratio of grinding media to material 10:1), drum's speed of rotation 600r/min, ball milling
Uniformly mixed powder is obtained afterwards.
Step 2: the powder after ball milling being transferred in porcelain boat, is put into tube furnace and calcines, and heating rate is 5 DEG C/min,
Calcination temperature be 800 DEG C, calcination time be 12 hours to get arrive silicon based composite material.
Embodiment 5:
Prepare carbon coating silicon nanometer sheet:
Step 1: 0.5g polythiophene is added in 20mL water, and simultaneously ultrasonic disperse 20min is sufficiently stirred；0.5g D50 is added
Partial size is the silicon powder of 100nm, ultrasonic disperse 30min；
Step 2: mixture obtained by step 1 is subjected to hydro-thermal reaction in closed container, 200 DEG C of reaction temperature, is reacted
Time is 18 hours；
Step 3: by hydro-thermal reaction product centrifugal treating, obtained solid substance is dried in vacuo at 60 DEG C；
Step 4: by the solid abrasive after drying, calcining, heating rate is 10 DEG C/min, calcination temperature 800 when calcining
DEG C, calcination time be 12 hours to get arrive carbon coating silicon nanometer sheet,
Prepare silicon based composite material:
Step 1: being 8 μm of soft carbons, polypyrroles according to mass ratio by carbon coating silicon nanometer sheet obtained above, D50 partial size
12%:78%:10% mixing, is put into ball mill ball milling 0.5 hour (ratio of grinding media to material 10:1), drum's speed of rotation 600r/min, ball
Uniformly mixed powder is obtained after mill.
Step 2: the powder after ball milling being transferred in porcelain boat, is put into tube furnace and calcines, heating rate be 10 DEG C/
Min, calcination temperature be 800 DEG C, calcination time be 12 hours to get arrive silicon based composite material.
Embodiment 6:
Prepare carbon coating silicon nanometer sheet:
Step 1: 0.5g polyaniline is added in 20mL water, and simultaneously ultrasonic disperse 20min is sufficiently stirred；0.5g D50 is added
Partial size is the silicon powder of 500nm, ultrasonic disperse 30min；
Step 2: mixture obtained by step 1 is subjected to hydro-thermal reaction in closed container, 200 DEG C of reaction temperature, is reacted
Time is 18 hours；
Step 3: by hydro-thermal reaction product centrifugal treating, obtained solid substance is dried in vacuo at 60 DEG C；
Step 4: by the solid abrasive after drying, calcining, heating rate is 10 DEG C/min, calcination temperature 800 when calcining
DEG C, calcination time be 12 hours to get arrive carbon coating silicon nanometer sheet.
Prepare silicon based composite material:
Step 1: by carbon coating silicon nanometer sheet obtained above, the soft carbon that D50 partial size is 10 μm, sucrose according to mass ratio
10%:80%:10% mixing, is put into ball mill ball milling 10 hours (ratio of grinding media to material 10:1), drum's speed of rotation 600r/min, ball milling
Uniformly mixed powder is obtained afterwards
Step 2: the powder after ball milling being transferred in porcelain boat, is put into tube furnace and calcines, heating rate be 10 DEG C/
Min, calcination temperature be 800 DEG C, calcination time be 12 hours to get arrive silicon based composite material.
Embodiment 7:
Prepare carbon coating silicon nanometer sheet:
Step 1: the mixture (wherein the mass ratio of dextrose and saccharose is 1:1) of 0.5g dextrose and saccharose is added
In 20mL water, simultaneously ultrasonic disperse 20min is sufficiently stirred；The silicon powder that 0.5g D50 partial size is 100nm, ultrasonic disperse 30min is added；
Step 2: mixture obtained by step 1 is subjected to hydro-thermal reaction in closed container, 200 DEG C of reaction temperature, is reacted
Time is 18 hours；
Step 3: by hydro-thermal reaction product centrifugal treating, obtained solid substance is dried in vacuo at 60 DEG C；
Step 4: by the solid abrasive after drying, calcining, heating rate is 10 DEG C/min, calcination temperature 800 when calcining
DEG C, calcination time be 12 hours to get arrive carbon coating silicon nanometer sheet.
Prepare silicon based composite material:
Step 1: by carbon coating silicon nanometer sheet obtained above, graphite and soft carbon mixture, pitch and polyaniline mixture
It is mixed according to mass ratio 10%:80%:10%, is put into ball mill ball milling 8 hours (ratio of grinding media to material 10:1), drum's speed of rotation is
600r/min obtains uniformly mixed powder after ball milling；
Wherein, in the graphite and soft carbon mixture, the graphite D50 partial size is 20 μm, and the soft carbon D50 partial size is 10
μm, the graphite and the soft carbon mass ratio are 1:1；The mass ratio of pitch and polyaniline in the pitch and polyaniline mixture
For 1:1.
Step 2: the powder after ball milling being transferred in porcelain boat, is put into tube furnace and calcines, heating rate be 10 DEG C/
Min, calcination temperature be 800 DEG C, calcination time be 12 hours to get arrive silicon based composite material.
Embodiment 8:
Prepare carbon coating silicon nanometer sheet:
Step 1: the mixture (mass ratio 1:1) of 0.5g polypyrrole and polythiophene is added in 20mL water, is sufficiently stirred
And ultrasonic disperse 20min；The silicon powder that 0.5g D50 partial size is 100nm, ultrasonic disperse 30min is added；
Step 2: mixture obtained by step 1 is subjected to hydro-thermal reaction in closed container, 200 DEG C of reaction temperature, is reacted
Time is 18 hours；
Step 3: by hydro-thermal reaction product centrifugal treating, obtained solid substance is dried in vacuo at 60 DEG C；
Step 4: by the solid abrasive after drying, calcining, heating rate is 10 DEG C/min, calcination temperature 800 when calcining
DEG C, calcination time be 12 hours to get arrive carbon coating silicon nanometer sheet.
Prepare silicon based composite material:
Step 1: by carbon coating silicon nanometer sheet, graphite and hard carbon mixture obtained above, dextrose and saccharose mixture
It is mixed according to mass ratio 10%:80%:10%, is put into ball mill ball milling 5 hours (ratio of grinding media to material 10:1), drum's speed of rotation is
600r/min obtains uniformly mixed powder after ball milling；
Wherein, in the graphite and hard carbon mixture, the graphite D50 partial size is 20 μm, and the hard carbon D50 partial size is 5 μ
M, the graphite and the hard carbon mass ratio are 1:1；The mass ratio of dextrose and saccharose in the dextrose and saccharose mixture
For 1:1.
Step 2: the powder after ball milling being transferred in porcelain boat, is put into tube furnace and calcines, heating rate be 10 DEG C/
Min, calcination temperature be 800 DEG C, calcination time be 12 hours to get arrive silicon based composite material.
Embodiment 9:
Prepare carbon coating silicon nanometer sheet:
Step 1: 0.5g pitch and polyaniline mixture (wherein the mass ratio of pitch and polyaniline is 1:1) are added
In 20mL water, simultaneously ultrasonic disperse 20min is sufficiently stirred；The silicon powder that 0.5g D50 partial size is 500nm, ultrasonic disperse 30min is added；
Step 2: mixture obtained by step 1 is subjected to hydro-thermal reaction in closed container, 200 DEG C of reaction temperature, is reacted
Time is 18 hours；
Step 3: by hydro-thermal reaction product centrifugal treating, obtained solid substance is dried in vacuo at 60 DEG C；
Step 4: by the solid abrasive after drying, calcining, heating rate is 10 DEG C/min, calcination temperature 800 when calcining
DEG C, calcination time be 12 hours to get arrive carbon coating silicon nanometer sheet.
Prepare silicon based composite material:
Step 1: carbon coating silicon nanometer sheet, soft carbon and hard carbon mixture obtained above, polypyrrole and polythiophene are mixed
Object is mixed according to mass ratio 10%:80%:10%, is put into ball mill ball milling 5 hours (ratio of grinding media to material 10:1), drum's speed of rotation is
600r/min obtains uniformly mixed powder after ball milling.
Wherein, in the soft carbon and hard carbon mixture, the soft carbon D50 partial size is 10 μm, and the hard carbon D50 partial size is 5 μ
M, the soft carbon and the hard carbon mass ratio are 1:1；The matter of polypyrrole and polythiophene in the polypyrrole and polythiophene mixture
Amount is than being 1:1.
Step 2: the powder after ball milling being transferred in porcelain boat, is put into tube furnace and calcines, heating rate be 10 DEG C/
Min, calcination temperature be 800 DEG C, calcination time be 12 hours to get arrive silicon based composite material.
Electric performance test
(1) negative electrode material prepares
Using carbon coating silicon nanometer sheet prepared by the above various embodiments and silicon based composite material as negative electrode material system
Standby battery testing electrical property.
Comparative example 1:
The silicon powder that the D50 partial size of the non-modified processing of purchase is 200nm is directly used as negative electrode material, is prepared into battery
Test electrical property.
Comparative example 2:
The silicon powder that D50 partial size by the D50 partial size graphite for being 20 μm and non-modified processing is 200nm is according to 95:5 machinery
Graphite silicon base complex is obtained after mixing as negative electrode material, is prepared into battery testing electrical property.
(2) battery preparation and electric performance test
It is straight as silicon powder described in negative electrode material and comparative example 1 by carbon coating silicon nanometer sheet is made in the above various embodiments
It connects and does negative electrode material and make battery respectively, and made battery is carried out to the test of electrical property respectively.The specific method is as follows:
By negative electrode material, acetylene black and polyacrylic acid according to the uniform mixed grinding 30min of mass ratio of 70:15:15 after,
It is even to be coated on copper foil, it is cut into the disk that diameter is 12cm after dry, carries out assembled battery.Assembled battery in glove box into
Row is to electrode with metal lithium sheet, and polypropylene screen is diaphragm, 1M lithium hexafluoro phosphate (propene carbonate+dimethyl carbonate, quality
Than 1:1) it is electrolyte, it is assembled into button cell.By assembled button cell at 0.1C, in 0.05V-2V voltage range into
Row charge and discharge.Test reversible specific capacity for the first time (mAh/g), first charge-discharge efficiency (%), the 100 weeks reversible specific capacities of battery
(mAh/g) and 100 weeks capacity retention ratios (%), it the results are shown in Table 1.
Silicon based composite material and the resulting graphite silicon base complex of comparative example 2 will be made in the above various embodiments as cathode
Material makes battery respectively, and made battery is carried out to the test of electrical property respectively.The specific method is as follows:
By negative electrode material, acetylene black and polyacrylic acid according to the uniform mixed grinding 30min of mass ratio of 90:5:5 after, uniformly
Coated in the disk that diameter is 12cm on copper foil, is cut into after dry, assembled battery is carried out.Assembled battery carries out in glove box,
It is to electrode with metal lithium sheet, polypropylene screen is diaphragm, 1M lithium hexafluoro phosphate (propene carbonate+dimethyl carbonate, mass ratio 1:
1) it is electrolyte, is assembled into button cell.By assembled button cell under 0.1C multiplying power, in 0.05V-2V voltage range into
Row charge and discharge.Test reversible specific capacity for the first time (mAh/g), first charge-discharge efficiency (%), the 100 weeks reversible specific capacities of battery
(mAh/g) and 100 weeks capacity retention ratios (%), it the results are shown in Table 1.
As can be seen from Table 1, it compared with comparative example 1 and comparative example 2, is received using carbon coating silicon prepared by method of the invention
Rice piece directly does negative electrode material first charge-discharge efficiency than silicon powder and 100 weeks capacity retention ratios improve very much；Using of the invention
The silicon based composite material of method preparation than graphite and commercialization silicon powder according to after 95:5 mechanical mixture graphite silicon base complex
First charge-discharge efficiency and 100 weeks capacity retention ratios improve very much.
In carbon coating silicon nanometer sheet of the invention, the presence for coating carbon-coating has effectively buffered the volume expansion of silicon, to mention
High circulation performance, and laminated structure makes silicon also play the effect that buffering expands in the volume expansion of longitudinal direction.
In silicon based composite material of the invention, including carbon coating silicon nanometer sheet, carbon material and cladding carbon-coating；Wherein, described
Carbon coating silicon nanometer sheet is uniformly attached to the surface of the carbon material, outside the carbon material for being attached with carbon coating silicon nanometer sheet
Face is uniformly coated with carbon-coating.The cladding carbon-coating on the silicon nanometer sheet surface of the silicon based composite material is as first layer buffer layer, carbon packet
Cover the attachment of silicon nanometer sheet on the carbon material, the cladding carbon-coating of carbon material surface is by carbon material and carbon coating silicon nanometer after secondary cladding
Piece is bundled together, and has both effectively been buffered the expansion in carbon material cyclic process, has been improved the cycle performance of carbon material, and silicon is also used as
The second layer buffer layer of nanometer sheet effectively inhibits expansion of the silicon in cyclic process, so that playing follows composite material integrally
The stable effect of ring performance.
Table 1
The test result of battery is made in each embodiment, each comparative example negative electrode material
Claims (10)
1. a kind of preparation method of carbon coating silicon nanometer sheet, which comprises the following steps:
Step 1: 0.1-1g carbon source is added in 5-20mL water, stirs simultaneously ultrasonic disperse 10-30min；It is added 0.1-1g D50
Diameter is the silicon powder of 10-500nm, ultrasonic disperse 10-30min；
Step 2: mixture obtained by step 1 is subjected to hydro-thermal reaction in closed container, 100-200 DEG C of reaction temperature, is reacted
Time is 10-24 hours；
Step 3: by hydro-thermal reaction product centrifugal treating, obtained solid substance is in 40 DEG C of -80 DEG C of vacuum drying；
Step 4: by the solid abrasive after drying, calcining, heating rate is 3-10 DEG C/min, calcination temperature 500- when calcining
1000 DEG C, calcination time is 5-12 hour to get to carbon coating silicon nanometer sheet.
2. the preparation method of carbon coating silicon nanometer sheet as described in claim 1, which is characterized in that the carbon source is sucrose, Portugal
One or more of grape sugar, pitch, polythiophene, polypyrrole, polyaniline.
3. the preparation method of carbon coating silicon nanometer sheet as described in claim 1, which is characterized in that the calcination temperature is 750-
800℃。
4. a kind of carbon coating silicon nanometer sheet, which is characterized in that the silicon nanometer sheet is used such as one of claims 1 to 3 the method
It is made, the carbon coating silicon nanometer sheet is by silicon nanometer sheet and is coated on surrounding carbon-coating and forms.
5. a kind of method for preparing silicon based composite material using carbon coating silicon nanometer sheet as claimed in claim 4, feature exist
In, comprising the following steps:
Step 1: by carbon coating silicon nanometer sheet, D50 partial size obtained by one of claims 1 to 3 be 1-40 μm carbon material,
Carbon source is mixed according to mass ratio 5-12%:78-85%:10%, obtains uniformly mixed powder after being put into ball mill ball milling；
Wherein, the carbon material is one of graphite, soft carbon, hard carbon or several mixtures；
Step 2: by the powder calcination after ball milling, calcining heating rate is 3-10 DEG C/min, and calcination temperature is 500-1000 DEG C,
Calcination time is 5-12 hour to get to silicon based composite material.
6. a kind of preparation method of silicon based composite material as claimed in claim 5, which is characterized in that ball material in the ball mill
Than for 10:1, Ball-milling Time is 0.5-24 hours, drum's speed of rotation 600r/min.
7. a kind of preparation method of such as silicon based composite material described in claim 5 or 6, which is characterized in that the carbon source is sugarcane
One or more of sugar, glucose, pitch, polythiophene, polypyrrole, polyaniline.
8. a kind of preparation method of silicon based composite material as claimed in claim 7, which is characterized in that the calcination temperature is
750-800℃。
9. a kind of silicon based composite material, which is characterized in that the silicon based composite material is used as described in one of claim 5 to 8
Method is made, and the silicon based composite material includes carbon coating silicon nanometer sheet, carbon material and cladding carbon-coating；Wherein, the carbon coating
Silicon nanometer sheet is uniformly attached to the surface of the carbon material, outside the carbon material for being attached with carbon coating silicon nanometer sheet uniformly
It is coated with carbon-coating.
10. a kind of silicon based composite material as claimed in claim 9, which is characterized in that the carbon material is graphite, soft carbon, hard
One of carbon or several mixtures.
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