CN109346685A - A kind of SiOxThe preparation method and applications of/C spherical powder - Google Patents
A kind of SiOxThe preparation method and applications of/C spherical powder Download PDFInfo
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- CN109346685A CN109346685A CN201811042162.6A CN201811042162A CN109346685A CN 109346685 A CN109346685 A CN 109346685A CN 201811042162 A CN201811042162 A CN 201811042162A CN 109346685 A CN109346685 A CN 109346685A
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- oxygen carbon
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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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- 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
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- 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 present invention relates to a kind of SiOxThe preparation method and applications of/C spherical powder, belong to new material technology field.The present invention uses that the low temperature of siliceous oxygen carbon easily evaporates or labile solid or liquid substance is precursors; it places it in reaction unit and seals; then reaction unit is put into suitable heating furnace the proper temperature heating under protective atmosphere makes forerunner's evacuator body or decomposes to generate high pressure, and silicon oxygen carbon ball is successfully prepared under the action of high pressure.The silicon oxygen carbon ball of acquisition is heat-treated, silicon oxygen carbon ball ingredient is changed after heat treatment, has obtained nanoscale evenly dispersed ground SiOx/ C spherical structure, and by SiOx/ C ball is applied in lithium ion battery as negative electrode material.This method work skill letter list ﹑ raw material Feng Fu ﹑ is low in cost, the SiO prepared using this programmex/ C ball can improve cycle performance of battery and high rate performance as lithium ion battery negative material, be suitable for large-scale promotion, have a good application prospect.
Description
Technical field
The present invention relates to new technology Material Field more particularly to a kind of SiOxIt the preparation method of/C spherical powder and its answers
With.
Background technique
Since the 1990s, rechargeable lithium ion batteries are successfully developed, and have been realized in the life of business
It produces and is widely used in different types of small portable electronic device, such as laptop, mobile phone and camera etc..Due to
Its high-energy density and long circulation life, lithium ion battery are with important application prospects in terms of electric car.However, graphite
(LiC6:372mAh g-1) be used as commercialized negative electrode of lithium ion battery since its theoretical capacity and high rate performance are lower, be not suitable for
Applied to high-power electric automobile.Therefore, in order to meet the demand of growing heavy-duty battery, such as electric car requirement
The lithium ion battery of high reversible capacity, high power density and high circulation stability, there is an urgent need to research and develop excellent high-performance
Negative electrode material.The negative electrode material studied at present is many kinds of, such as transition metal oxide, graphene, tin, black phosphorus and silicon substrate
Material, wherein silica-base material has high theoretical capacity, low discharge voltage, source abundant and preferable safety, thus
With very big application potential.However, silica-base material poorly conductive, and volume expansion is larger in charge and discharge process, to lead
The electro-chemical activity for causing its low includes the cyclical stability of low coulombic efficiency and difference.15The present invention is prepared for for these problems
A kind of SiOx/ C ball, establishes its preparation process, and be used for lithium ion battery negative material, obtains good performance.
Low temperature is easily evaporated first or the precursors of labile siliceous oxygen carbon are placed in confined reaction device, and places it in conjunction
Heating makes presoma decompose generation high pressure under protective atmosphere in suitable heating furnace, so that silicon oxygen carbon ball is formed, then to acquisition
Silicon oxygen carbon ball be heat-treated to obtain SiOx/ C ball.This SiOx/ C ball has the circulation of superelevation steady in lithium cell negative pole material application
Qualitative and good high rate performance, the method being capable of large scale preparation SiOx/ C ball, has a good application prospect.
Summary of the invention
The purpose of the present invention is prepare a kind of SiOx/ C spherical powder material, prepared SiOx/ C spherical powder can be used as
Lithium ion battery negative material, and there is superior chemical property.
To achieve the goals above, the technical scheme adopted by the invention is as follows:
Use that low temperature easily evaporates or labile siliceous oxygen carbon is as precursors, places it in high-strength using high-melting-point
It spends in confined reaction device made of metal or special alloy, then reaction unit is put into heating furnace, protected in inert gas
It is heated to 600-950 DEG C under shield when making forerunner's evacuator body or being decomposed into gas and generates the high pressure of 1-10MPa, under the action of high pressure
Silicon oxygen carbon ball is formed, control reaction temperature is the quality of 600-950 DEG C ﹑ presoma and the volumetric ratio of reaction cavity is 0.018-
Under the reaction condition that 0.5g/ml ﹑ heating rate is 1-80 DEG C/min and soaking time is 0-5h, 1.6-15 μm of silicon oxygen carbon is obtained
Then ball is heat-treated to obtain SiO to silicon oxygen carbon ball obtainedx/ C ball.It should be noted that reaction temperature is being lower than
At 600 DEG C, when being lower than 0.018g/ml, heating rate is being lower than 1 DEG C/min for the quality of presoma and the volumetric ratio of reaction cavity
When all cannot get silicon oxygen carbon ball.
As a further improvement of the present invention, the low temperature refers to 100-600 DEG C.
As a further improvement of the present invention, the precursors of siliceous oxygen carbon are Ju bis- Jia base Gui Yang Wan ﹑ dimethoxy
107 glue ﹑ of diformazan base silane ﹑, 108 glue, eight methyl rings, four ten methyl of silicon oxygen alkane ﹑ silica gel rubber circle ﹑, four silicon oxygen alkane ﹑ 1,3- divinyl
Any one of tetramethyl Er Gui Yang Wan ﹑ octamethyltrisiloxane and hexamethyldisilane.
As a further improvement of the present invention, the high-melting-point high duty metal is any one of molybdenum, tungsten metal；
The special alloy is any one of alloy tool steel, heat resisting steel and special property steel.
As a further improvement of the present invention, the heating furnace is any one of tube furnace and batch-type furnace.
As a further improvement of the present invention, the heat treatment is heat treatment temperature 1000- under inert gas atmosphere
1200 DEG C, soaking time 3-5h, heating rate is 1-10 DEG C/min, ventilation flow rate 50-400sccm.If heat treatment temperature
Degree is lower than 1000 DEG C, and reaction rate is not reacted even slowly excessively, if temperature, which is higher than 1200 DEG C, is likely to form silicon carbide, deteriorates
Lithium performance is stored up, so temperature selection is at 1000-1200 DEG C.Heat treatment time is less than 3h and reacts insufficient, and 5h reaction is completed, and is greater than
5h product structure is not further change in, so suitable heat treatment time range is 3-5h.
As a further improvement of the present invention, the inert gas is any one of argon gas, nitrogen and helium.
The present invention also provides SiO made from the above methodx/ C spherical powder is in as lithium ion battery negative material
Application.
It is above-mentioned using the lithium ion battery negative material the preparation method comprises the following steps: the SiO that will be obtainedx/ C ball respectively with acetylene
Black and binder is stirred for 24 hours in deionized water with mass ratio 7:1.5:1.5 mixing, is then evenly coated on copper foil of affluxion body,
First dry 1h removes macromolecular water at 50 DEG C of normal pressure, is then placed in 70 DEG C of vacuum oven dry 12h, is finally cut into diameter
The disk of 11mm.
Preferably, the binder is that butadiene-styrene rubber and sodium carboxymethylcellulose 1:3 in mass ratio are mixed.
In a particularly preferred scheme of the invention, the further detailed protocol of the present invention includes:
1. preparing silicon oxygen carbon ball
(1) presoma of the quality of suitable presoma and the volumetric ratio of reaction cavity is put into reaction unit；
(2) then reaction unit is in the glove box (flowing water molecule and oxygen concentration are no more than 1ppm) of argon atmosphere
Sealing；
(3) device, which is taken out, is placed in heating furnace appropriate, from room temperature with appropriate under protective atmosphere appropriate
The rate of heat addition is heated to proper temperature, keeps appropriate time, device is naturally cooled room temperature later.Obtained loess color or
Dark tan powder is carefully collected and is put into sample bottle.It should be noted that gas, operator can be released in device for opening
It need to be operated with corresponding safeguard procedures, and in draught cupboard.
2. heat treatment obtains SiOx/ C ball
Sample obtained in 1 is taken and is put into aluminium oxide ceramics boat on a small quantity, respectively in indifferent gas such as the Ar of 50-400sccm
Heat treatment 3-5h is carried out for 1000-1200 DEG C in atmosphere.
3. the preparation of negative electrode material
The SiO that will be obtainedx/ C ball respectively with acetylene black and binder (butadiene-styrene rubber and sodium carboxymethylcellulose, mass ratio
It 1:3) is stirred for 24 hours, is then evenly coated on copper foil (collector) in deionized water with mass ratio 7:1.5:1.5 mixing, first existed
Dry 1h removes macromolecular water at 50 DEG C of normal pressure, is then placed in 70 DEG C of vacuum oven dry 12h, is then cut into diameter 11mm's
Disk is put into glove box after weighing quality.
4. the assembling and performance test of lithium battery
It in the glove box of argon atmosphere, is assembled using 2032 button half-cells, the disk that 3 are prepared is as negative
Pole material, lithium foil are used as to electrode and reference electrode, and diaphragm is Celgard 2400, and electrolyte is the hexafluoro phosphorus lithium of 1mol in body
Product than be 1:1 ethylene carbonate and diethyl carbonate in, in addition plus the additive of the fluoro ethylene carbonate of 5vol%.Other
Unfilled space is filled with the nickel foam that diameter 16mm, thickness are respectively 1mm and 1.5mm, plays the conductive effect of support.?
The blue electric battery test system of CT2001A carries out cycle performance and high rate performance test, voltage range 0.005-2V, and current density is
0.1-2A/g。
Advantage of the invention is as follows: method is simple, and without complicated equipment and process flow, whole preparation process only needs
Presoma is put into be sealed in device heating Ji this Di of Ke ﹑ Cheng Lian ﹑ generated time Duan ﹑ production Shuai Gao ﹑ can largely prepare SiOx/C
Ball can be effectively reduced production cost compared to other methods.SiOx/ C ball has preferable mobility, therefore prepares in electrode
SiO in the processx/ C ball can be preferably dispersed in the substrate of conductive agent and binder, can preferably be contacted with conductive substrates
Improve the electric conductivity of entire electrode.Because of SiOx/ C ball has anisotropy, so having in all directions in cyclic process
Uniform volume change can make the stress as caused by volume change be uniformly dispersed in entire electrode, to improve
The stability of entire electrode structure.Due to spherical structure possess more than advantage, so SiOx/ C ball has good lithium ion
Battery performance.The present invention is successfully to prepare SiO using the method for high pressure for the first time both at home and abroadx/ C ball.
SiOx/ C ball has good cycle performance and high rate performance, active material carrying capacity about 0.3mg/cm2When, SiOx/C
Ball after 400 circulations, has obtained reversible capacity and has been up to 1603.1mAh/g, corresponding capacity is kept under 0.2A/g current density
Rate is 96.2%, SiOx/ C ball after 3000 circulations, has obtained reversible capacity and has been up to 757.6mAh/g under 1A/g current density,
Corresponding capacity retention ratio is 84.9%, SiOx/ C ball after 3000 circulations, has obtained reversible capacity under 2A/g current density
Up to 474.6mAh/g, corresponding capacity retention ratio are 77.9%.And SiOx/ C ball 3.02mg/cm under high carrying capacity2When, it obtains
It obtained reversible face amount and is up to 2.6mAh/cm2, and outstanding cyclical stability is shown, capacity is kept after 400 circulations
Rate is 87.3%.
Detailed description of the invention
Fig. 1 is the SEM photograph for the silicon oxygen carbon ball that the embodiment of the present invention 1 obtains in molybdenum reaction cavity.
Fig. 2 is the SEM photograph for the silicon oxygen carbon ball that the embodiment of the present invention 2 obtains at 600 DEG C.
Fig. 3 is that the embodiment of the present invention 3 is obtained when the quality of presoma and the volumetric ratio of reaction cavity are 0.018g/ml
The SEM photograph of silicon oxygen carbon ball.
Fig. 4 is SEM photograph of the embodiment of the present invention 4 in the obtained silicon oxygen carbon ball of 1 DEG C/min of the rate of heat addition.
Fig. 5 is SEM photograph of the embodiment of the present invention 5 in the obtained silicon oxygen carbon ball of soaking time 0h.
Fig. 6 is SEM photograph of the embodiment of the present invention 6 in the obtained silicon oxygen carbon ball of soaking time 5h.
Fig. 7 is the embodiment of the present invention 7, the SEM photograph for the silicon oxygen carbon ball that silicon rubber loop is obtained as presoma.
Fig. 8 is the embodiment of the present invention 8, the SEM photograph for the silicon oxygen carbon ball that decamethyl tetrasiloxane is obtained as presoma.
Fig. 9 is the embodiment of the present invention 9, the SEM photograph for the silicon oxygen carbon ball that octamethyltrisiloxane is obtained as presoma.
Figure 10 is the embodiment of the present invention 10, SiOxThe SEM photograph of/C ball is under protection of argon gas at 1000 DEG C to 800
DEG C silicon oxygen carbon ball obtained obtains after being heat-treated.
Figure 11 is the SiO that the embodiment of the present invention 10 obtainsxThe XPS spectrum of the Si 2p of/C ball.
Figure 12 is the SiO that the embodiment of the present invention 10 obtainsxThe XPS spectrum of the C 1s of/C ball.
Figure 13 is the SiO that the embodiment of the present invention 10 obtainsxThe Raman spectrogram of/C ball.
Figure 14 is the SiO that the embodiment of the present invention 10 obtainsxCharging and discharging curve of/C the ball as lithium cell negative pole material.
Figure 15 is the SiO that the embodiment of the present invention 10 obtainsx/ C ball is as lithium cell negative pole material under 0.2A/g current density
Stable circulation linearity curve.
Figure 16 is the SiO that the embodiment of the present invention 10 obtainsx/ C ball follows under 1A/g current density as lithium cell negative pole material
Ring stability curve.
Figure 17 is the SiO that the embodiment of the present invention 10 obtainsx/ C ball follows under 2A/g current density as lithium cell negative pole material
Ring stability curve.
Figure 18 is the SiO that the embodiment of the present invention 10 obtainsxCirculation of/C the ball as lithium cell negative pole material under different carrying capacity
Curve.
Specific embodiment
The present invention is further described for explanation and specific embodiment with reference to the accompanying drawing.
1 molybdenum reaction cavity of embodiment prepares silicon oxygen carbon ball
It is reaction cavity that this example, which illustrates molybdenum, and protective atmosphere is that argon gas prepares silicon oxygen carbon ball, is specifically prepared
Journey is as follows:
Precursors are dimethyl silicone polymer, are 0.3g/ml in the quality of presoma and the volumetric ratio of reaction cavity,
Heating rate 10 DEG C/min, soaking time 0.5h under conditions of 800 DEG C of reaction temperature, selects copper sealing ring, molybdenum screw
Fastening, prepares silicon oxygen carbon ball.
Fig. 1 is the SEM figure of the silicon oxygen carbon ball obtained in molybdenum reaction cavity.
It will be seen from figure 1 that silicon oxygen carbon ball has been formed, and size is distributed in 1.6-10 μm.
2 600 DEG C of embodiment prepare silicon oxygen carbon ball
This example illustrates 600 DEG C of reaction temperature and prepares to silicon oxygen carbon ball, reaction cavity and protective atmosphere with embodiment 1,
Specific preparation process is as follows:
Precursors are dimethyl silicone polymer, are 0.3g/ml in the quality of presoma and the volumetric ratio of reaction cavity,
Heating rate 10 DEG C/min, soaking time 1h under conditions of 600 DEG C of reaction temperature, selects copper metal sealing ring, molybdenum spiral shell
It clenches admittedly, prepares silicon oxygen carbon ball.
Fig. 2 is the SEM photograph of the silicon oxygen carbon ball obtained in 600 DEG C.
Figure it is seen that silicon oxygen carbon ball has been formed, and size is distributed in 3-15 μm.
The quality of 3 presoma of embodiment and the volumetric ratio of reaction cavity are that 0.018g/ml prepares silicon oxygen carbon ball
Embodiment shows the volumetric ratios of the quality of the presoma of 0.018g/ml and reaction cavity to prepare silicon oxygen carbon ball,
With embodiment 1, specific preparation process is as follows for reaction cavity and protective atmosphere:
Precursors are dimethyl silicone polymer, at 800 DEG C, under conditions of heating rate is 10 DEG C/min, when heat preservation
Between 2h, molybdenum is reaction cavity, select copper metal sealing ring, molybdenum is fastening screw, prepares silicon oxygen carbon ball.
Fig. 3 is that the SEM for the silicon oxygen carbon ball that the quality of the presoma of 0.018g/ml and the volumetric ratio of reaction cavity obtain shines
Piece.Silicon oxygen carbon ball has been formed as can be seen from Figure 3, and size is distributed in 1.6-8 μm.
4 rate of heat addition of embodiment is that 1 DEG C/min prepares silicon oxygen carbon ball
It is that 1 DEG C/min prepares silicon oxygen carbon ball, reaction cavity and protective atmosphere with implementation embodiment shows the rate of heat addition
Example 1, specific preparation process are as follows: precursors are dimethyl silicone polymer, 800 DEG C of reaction temperature, the presoma of 0.3g/ml
Quality and reaction cavity volumetric ratio and soaking time be 0.5h, molybdenum is reaction cavity, select copper metal sealing ring, molybdenum
Metal is fastening screw, prepares silicon oxygen carbon ball.
Fig. 4 is the SEM photograph for the silicon oxygen carbon ball that 1 DEG C/min of the rate of heat addition is obtained.From fig. 4, it can be seen that silicon oxygen carbon ball is
Through being formed, size range is at 2-13 μm.
5 soaking time 0h of embodiment prepares silicon oxygen carbon ball
Embodiment shows soaking time 0h to prepare silicon oxygen carbon ball, and reaction cavity and protective atmosphere are with embodiment 1, specifically
Preparation process is as follows: precursors are dimethyl silicone polymer, 800 DEG C of holding temperature, the quality of the presoma of 0.3g/ml with
The volumetric ratio and the rate of heat addition of reaction cavity are 10 DEG C/min, and molybdenum is reaction cavity, select copper metal sealing ring, molybdenum
For fastening screw, silicon oxygen carbon ball is prepared.
Fig. 5 is the SEM photograph for the silicon oxygen carbon ball that soaking time 0h is obtained.
From fig. 5, it can be seen that silicon oxygen carbon ball has been formed, size range is at 1.8-10 μm.
6 soaking time 5h of embodiment prepares silicon oxygen carbon ball
Embodiment shows soaking time 5h to prepare silicon oxygen carbon ball, and reaction cavity and protective atmosphere are with embodiment 1, specifically
Preparation process is as follows: precursors are dimethyl silicone polymer, 800 DEG C of holding temperature, the quality of the presoma of 0.3g/ml with
The volumetric ratio and the rate of heat addition of reaction cavity are 10 DEG C/min, and molybdenum is reaction cavity, select copper metal sealing ring, molybdenum
For fastening screw, silicon oxygen carbon ball is prepared.
Fig. 6 is the SEM photograph for the silicon oxygen carbon ball that soaking time 5h is obtained.
From fig. 6, it can be seen that silicon oxygen carbon ball has been formed and size is distributed in 1.6-10 μm.
7 silicon rubber loop of embodiment is prepared silicon oxygen carbon ball as presoma
This example illustrates silicon rubber loop and prepares to silicon oxygen carbon ball, and specific preparation process is as follows: precursors are silicon rubber
Glue, presoma quality and reaction cavity volumetric ratio be 0.2g/ml, heating rate 10 DEG C/min, soaking time 0.5h,
Under conditions of 800 DEG C of reaction temperature, reaction cavity and protective atmosphere select copper sealing ring, molybdenum screw is tight with embodiment 1
Gu preparing silicon oxygen carbon ball.
Fig. 7 is the SEM figure of the silicon oxygen carbon ball obtained when silicon rubber is as presoma.
From figure 7 it can be seen that silicon oxygen carbon ball has been formed, and size is distributed in 2-13 μm.
Preparation of 8 decamethyl tetrasiloxane of embodiment as presoma to silicon oxygen carbon ball
This example illustrates decamethyl tetrasiloxane and prepares to silicon oxygen carbon ball, reaction cavity and protective atmosphere with embodiment 1,
Specific preparation process is as follows:
Precursors are decamethyl tetrasiloxane, are 0.3g/ml in the quality of presoma and the volumetric ratio of reaction cavity,
Heating rate 10 DEG C/min, soaking time 0.5h under conditions of 800 DEG C of reaction temperature, selects nickel metal as sealing ring, molybdenum
Metallic screw fastening, prepares silicon oxygen carbon ball.
Fig. 8 is the SEM figure of the silicon oxygen carbon ball obtained when decamethyl tetrasiloxane is as presoma.
From figure 8, it is seen that silicon oxygen carbon ball has been formed, and size is distributed in 1.6-13 μm.
Preparation of 9 octamethyltrisiloxane of embodiment as presoma to silicon oxygen carbon ball
This example illustrates octamethyltrisiloxane and prepares to silicon oxygen carbon ball, reaction cavity and protective atmosphere with embodiment 1,
Specific preparation process is as follows:
Precursors are octamethyltrisiloxane, are 0.3g/ml in the quality of presoma and the volumetric ratio of reaction cavity,
Heating rate 10 DEG C/min, soaking time 0.5h under conditions of 800 DEG C of reaction temperature, selects copper sealing ring, molybdenum screw
Fastening, prepares silicon oxygen carbon ball.
Fig. 9 is the SEM figure of the silicon oxygen carbon ball obtained when octamethyltrisiloxane is as presoma.
From fig. 9, it can be seen that silicon oxygen carbon ball has been formed, and size is distributed in 1.5-10 μm.
Embodiment 10SiOxThe SEM photograph of/C ball.
Embodiment shows under argon atmosphere, the silicon oxygen carbon ball of synthesis is heat-treated to obtain SiOx/ C ball, specifically
Heat treatment process is as follows: the silicon oxygen carbon ball that embodiment 2 obtains being weighed 0.5g and is put into aluminium oxide ceramics boat, horizontal tube is placed on
The argon gas for leading to 200sccm in furnace is heat-treated, and heating rate is 3 DEG C/min, and heat treatment temperature is 1000 DEG C, keeps 3h.
Figure 10 is SiOxThe SEM photograph of/C ball.
The spherical morphology of the silicon oxygen carbon ball in argon atmosphere illustrates 800 DEG C there is no variation as can be seen from Figure 10
The silicon oxygen carbon ball of acquisition is relatively stable.
Embodiment 11SiOxThe XPS spectrum of the Si 2p of/C ball.
Figure 11 is the SiO that embodiment 10 obtainsxThe XPS spectrum of the Si 2p of/C ball.
It can be seen from figure 11 that the center at the peak of Si 2p is located at 102.43eV, this is typical SiOxThe XPS of (0 < x < 2)
Peak illustrates to contain SiO in this samplex。
Embodiment 12SiOxThe XPS spectrum of the C 1s of/C ball.
Figure 12 is the SiO that embodiment 10 obtainsxThe XPS spectrum of the C 1s of/C ball.
It can be recognized from fig. 12 that the center at the peak of C 1s is located at 284.76eV, this is the peak XPS of typical C-C key, illustrates this
Contain free carbon in sample.
Embodiment 13SiOxThe Raman spectrum of/C ball
Figure 13 is the SiO that embodiment 10 obtainsxThe Raman spectrogram of/C ball.
As can be seen from Figure 13, SiOxThere is the peak D of typical carbon material and the peak G in the Raman spectrogram of/C ball, this into
One step illustrates SiOx/ C ball contains free carbon.From Figure 11-13, it can be concluded that, the sample after heat treatment contains SiOxAnd C, therefore will
This sample is known as SiOx/C。
Embodiment 14SiOxElectrochemical property test of/the C as lithium cell negative pole material
Embodiment shows to SiOx/ C ball carries out lithium electric performance test, and detailed process is as follows: embodiment 10 is obtained
SiOx/ C ball and acetylene black and binder (butadiene-styrene rubber and sodium carboxymethylcellulose, mass ratio 1:3) are with mass ratio 7:
1.5:1.5 mixing is stirred for 24 hours in deionized water, is then evenly coated on copper foil, and first the dry 1h at 50 DEG C of normal pressure, then puts
Enter 70 DEG C of vacuum oven dry 12h, the disk for being then cut into diameter 11mm fills button half-cell then in indigo plant glove box
Electrical measurement test system carries out lithium electric performance test.
Figure 14 is the SiO obtained after embodiment 10 is heat-treatedxCharging and discharging curve of/C the ball as lithium cell negative pole material.
It is seen from figure 14 that first electric discharge and charging capacity are respectively 2276.7 and 1667.3mAh/g, corresponding library for the first time
Human relations efficiency is 73.2%.
Figure 15 is the SiO under 0.2A/g current densityxThe stable circulation linearity curve of/C ball, wherein SiOxThe carrying capacity of/C is
0.3mg/cm2.It is shown in lower 400 circulations of 0.2A/g current density in figure and has obtained the reversible quality of 1603.1mAh/g later
Specific capacity, corresponding circulation volume conservation rate are 96.2%, and the average coulomb effect of the 400th circulation is recycled to from the 2nd time
Rate is 99.83%.
Figure 16 is the SiO under 1A/g current densityxThe stable circulation linearity curve of/C ball, wherein SiOxThe carrying capacity of/C is
0.3mg/cm2.It is shown in lower 3000 circulations of 1A/g current density in figure and has obtained the reversible mass ratio of 757.6mAh/g later
Capacity, corresponding circulation volume conservation rate are 84.9%, and the average coulombic efficiency of the 3000th circulation is recycled to from the 2nd time
It is 99.66%.
Figure 17 is the SiO under 2A/g current densityxThe stable circulation linearity curve of/C ball, wherein SiOxThe carrying capacity of/C is
0.3mg/cm2.It is shown in lower 3000 circulations of 2A/g current density in figure and has obtained the reversible mass ratio of 474.6mAh/g later
Capacity, corresponding circulation volume conservation rate are 77.9%, and the average coulombic efficiency of the 3000th circulation is recycled to from the 2nd time
It is 99.38%.
Figure 18 is the SiO obtained after embodiment 10 is heat-treatedx/ C ball following under different carrying capacity as lithium cell negative pole material
Ring curve.As can be seen that being 3.02mg/cm in carrying capacity in figure2With current density be 0.1A/g when 400 times circulation after can obtain
2.0mAh/cm2Face amount, recycle that start capacity retention ratio be 87.1% since third time, the average coulombic efficiency of acquisition is
99.60%.
The above content is a further detailed description of the present invention in conjunction with specific preferred embodiments, and it cannot be said that
Specific implementation of the invention is only limited to these instructions.For those of ordinary skill in the art to which the present invention belongs, exist
Under the premise of not departing from present inventive concept, a number of simple deductions or replacements can also be made, all shall be regarded as belonging to of the invention
Protection scope.
Claims (10)
1. a kind of SiOxThe preparation method of/C spherical powder, which is characterized in that easily evaporated or labile siliceous oxygen carbon using low temperature
As precursors, place it in using in confined reaction device made of high-melting-point high duty metal or special alloy, so
Reaction unit is put into heating furnace afterwards, being heated to 600-950 DEG C under inert gas protection makes forerunner's evacuator body or be decomposed into
The high pressure that 1-10MPa is generated when gas forms silicon oxygen carbon ball, before control reaction temperature is 600-950 DEG C ﹑ under the action of high pressure
The volumetric ratio of the quality and reaction cavity of driving body is that 0.018-0.5g/ml ﹑ heating rate is 1-80 DEG C/min and soaking time is
Under the reaction condition of 0-5h, 1.6-15 μm of silicon oxygen carbon ball is obtained, then silicon oxygen carbon ball obtained is heat-treated to obtain
SiOx/ C ball.
2. SiO according to claim 1xThe preparation method of/C spherical powder, which is characterized in that the low temperature refers to
100-600℃。
3. SiO according to claim 2xThe preparation method of/C spherical powder, it is characterised in that: siliceous oxygen carbon is poly- diformazan
107 glue ﹑ of base silicon oxygen alkane ﹑ dimethoxy diformazan base silane ﹑, 108 glue, eight methyl rings, four silicon oxygen alkane ﹑ silica gel rubber circle ﹑ decamethyl, four silicon
Any one of Yang Wan ﹑ 1,3- divinyl tetramethyl Er Gui Yang Wan ﹑ octamethyltrisiloxane and hexamethyldisilane.
4. SiO according to claim 1xThe preparation method of/C spherical powder, which is characterized in that the high-melting-point is high-intensitive
Metal is any one of molybdenum, tungsten metal；The special alloy is in alloy tool steel, heat resisting steel and special property steel
It is any.
5. SiO according to claim 1xThe preparation method of/C spherical powder, which is characterized in that the heating furnace is tubular type
Any one of furnace and batch-type furnace.
6. SiO according to claim 1xThe preparation method of/C spherical powder, which is characterized in that the heat treatment is lazy
Property gas atmosphere under, heat treatment temperature be 1000-1200 DEG C, soaking time 3-5h, heating rate be 1-10 DEG C/min, ventilation
Flow is 50-400sccm.
7. SiO according to claim 6xThe preparation method of/C spherical powder, which is characterized in that the inert gas is argon
Any one of gas, nitrogen and helium.
8. SiO made from a kind of preparation method as claimed in claim 1xThe application of/C spherical powder, feature exist
In the SiOx/ C spherical powder is used to prepare lithium ion battery negative material.
9. SiO according to claim 8xThe application of/C spherical powder, which is characterized in that the negative electrode of lithium ion battery material
Material the preparation method comprises the following steps: the SiO that will be obtainedx/ C ball is blended in respectively with acetylene black and binder with mass ratio 7:1.5:1.5
It stirs in ionized water for 24 hours, is then evenly coated on copper foil of affluxion body, first dry 1h removes macromolecular water at 50 DEG C of normal pressure, so
After be put into 70 DEG C of vacuum oven dry 12h, be finally cut into the disk of diameter 11mm.
10. SiO according to claim 9xThe application of/C spherical powder, which is characterized in that the binder is butadiene-styrene rubber
It is mixed with sodium carboxymethylcellulose 1:3 in mass ratio.
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