CN107317006A - Aoxidize silicon substrate carbon compound cathode materials, its preparation method and lithium ion battery - Google Patents
Aoxidize silicon substrate carbon compound cathode materials, its preparation method and lithium ion battery Download PDFInfo
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- CN107317006A CN107317006A CN201710475669.XA CN201710475669A CN107317006A CN 107317006 A CN107317006 A CN 107317006A CN 201710475669 A CN201710475669 A CN 201710475669A CN 107317006 A CN107317006 A CN 107317006A
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- 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
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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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- 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
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- H01M2220/00—Batteries for particular applications
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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
- H01M2220/00—Batteries for particular applications
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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 provides a kind of preparation method for aoxidizing silicon substrate carbon compound cathode materials, including：A silica) is subjected to heat treatment 10min~20h at 800~1200 DEG C；B) by step A) obtained silica cooled, and the scope of the cooling is 0~400 DEG C；Or by step A) obtained silica is first cooled to room temperature, then it is warming up to 800~1000 DEG C；C carbon-source gas) are passed through, in step B) chemical vapor deposition is carried out on obtained silica, obtain aoxidizing silicon substrate carbon compound cathode materials.This method generates one-dimensional carbon material without additionally addition catalyst, but by being heat-treated to silica after, its surface is set to have the avtive spot of catalytic action, catalysis carbon-source gas grow into agraphitic carbon and one-dimensional carbon material naturally, are coated on silicon oxide surface formation oxidation silicon substrate carbon compound cathode materials.This method is simple and easy to apply, and obtained composite negative pole material specific capacity and cycle performance are higher.
Description
Technical field
The present invention relates to technical field of lithium ion, more particularly to a kind of oxidation silicon substrate carbon compound cathode materials, its system
Preparation Method and lithium ion battery.
Background technology
To solve energy problem and problem of environmental pollution, exploitation Large Copacity and high-power energy storage material have become research
Focus.Lithium ion battery because its voltage is high, have extended cycle life and receive significant attention the features such as environmental protection, and be applied to each
Mobile device is planted, such as smart mobile phone, notebook computer, what is had is even applied to electric automobile field.But, current business
Requirement of the market development to energy storage device is all extremely difficult to the energy density and power density of lithium ion battery.Therefore, develop
The electrode material of high power capacity is extremely urgent.
In existing non-carbons negative material, Si oxide has obvious advantage compared to other negative materials.Such as body
Silica is much smaller than silicon in terms of product bulking effect；Furthermore, the oxygen that silica is generated in cyclic process first with lithium reaction in-situ
Change lithium and lithium metasilicate serves as preferable decentralized medium, the volumetric expansion of silicon is not only inhibited, while being also prevented from the group of nano-silicon
Cluster is assembled.Importantly, compared with other negative materials in addition to silicon, silica has higher specific capacity and relatively low
Removal lithium embedded potential.Therefore, silica negative material is considered as a kind of high-capacity cathode material for having very much a potentiality to be exploited.But,
Simple silica material is as lithium cell cathode material, and its electric conductivity is poor, polarizes more serious.
To solve the above problems, silica and carbonaceous material are combined by researcher, the obtained side of composite construction one
Face can improve the conductance of silica material, improve its high rate performance；On the other hand can be with buffer silicon oxide volumetric expansion/receipts
Bulk effect caused by contracting, improves cycle life.Such as：Chinese patent CN201610125508.3 reports a kind of lithium-ion electric
The preparation method of the SiOx-C-CNT composites of pond negative material, by adding CNT conductive networks and directly pouring into culture dish
The method of film forming, prepares SiOx-C-CNT composites.Chinese patent CN201480003402.5 reports a kind of secondary electricity of lithium
Pond and the method for preparing the negative active core-shell material, receive silica (SiOx) with carbon by using sodium carboxymethylcellulose (CMC)
Mitron (CNT) combines preparation SiOx-CMC-CNT composites.Also there are some to need addition Ni as catalyst, then pass through
CVD mode prepares SiOx-CNT composites.Answered however, the shortcoming of above-mentioned prior art generally existing is exactly preparation technology
Miscellaneous, last handling process trouble, repeatability is poor, extensive use of the influence silicon-carbon cathode material in lithium ion battery, meanwhile, system
The specific capacity and cycle performance of the silicon-carbon cathode material obtained need to improve.Therefore, exploitation excellent performance and preparation process letter
Single Si-C composite material to be preferably applied for the preparation of lithium ion battery, this become for those skilled in the art it is of interest
Focus.
The content of the invention
In view of this, the technical problem to be solved in the present invention be to provide a kind of oxidation silicon substrate carbon compound cathode materials, its
Preparation method and lithium ion battery, preparation method disclosed by the invention need not use catalyst, and operation is simple；Using this hair
The obtained oxidation silicon substrate carbon compound cathode materials specific capacity of bright preparation method and cycle performance are higher.
The invention provides a kind of preparation method for aoxidizing silicon substrate carbon compound cathode materials, including：
A silica) is subjected to heat treatment 10min~20h at 800~1200 DEG C；
B) by step A) obtained silica cooled, and the scope of the cooling is 0~400 DEG C；Or by step A)
To silica be first cooled to room temperature, then be warming up to 800~1000 DEG C；
C carbon-source gas) are passed through, in step B) chemical vapor deposition is carried out on obtained silica, obtain aoxidizing silicon substrate carbon
Composite negative pole material.
It is preferred that, the silica is SiOx, wherein 0 ＜ x≤2.
It is preferred that, step A) in, the temperature of the heat treatment is 900~1100 DEG C；The time of the heat treatment is 30min
~10h.
It is preferred that, step A) and step B) carry out under an inert atmosphere.
It is preferred that, the carbon-source gas are hydrocarbon compound gas or alcohol compound gas.
It is preferred that, the carbon-source gas are ethene, methane or acetylene.
It is preferred that, step C) in, the time of the chemical vapor deposition is 10min~10h.
It is preferred that, step C) in, the time of the chemical vapor deposition is 30min~5h.
The invention provides oxidation silicon substrate carbon compound cathode materials prepared by a kind of preparation method described above.
Present invention also offers a kind of lithium ion battery, including positive pole, negative pole, barrier film and electrolyte, the negative pole includes
Above-mentioned oxidation silicon substrate carbon compound cathode materials.
The invention provides a kind of preparation method for aoxidizing silicon substrate carbon compound cathode materials, including：A) by silica 800
Heat treatment 10min~20h is carried out at~1200 DEG C；B) by step A) obtained silica cooled, the scope of the cooling
For 0~400 DEG C；Or by step A) obtained silica is first cooled to room temperature, then it is warming up to 800~1000 DEG C；C) it is passed through carbon source
Gas, in step B) chemical vapor deposition is carried out on obtained silica, obtain aoxidizing silicon substrate carbon compound cathode materials.Above-mentioned
In heat treatment process, disproportionated reaction occurs for silica, its surface is produced the avtive spot of certain catalytic action, is catalyzed carbon source gas
Body grows into agraphitic carbon and one-dimensional carbon material naturally, and then is coated on silicon oxide surface formation oxidation silicon substrate carbon compound cathode material
Material, preparation method is simple and easy to apply.Meanwhile, using oxidation silicon substrate carbon compound cathode materials specific volume made from the preparation method of the present invention
Amount and cycle performance are higher.
Brief description of the drawings
Fig. 1 is the SEM figures of oxidation silicon substrate carbon compound cathode materials prepared by the embodiment of the present invention 1；
Fig. 2 is prepared by the XRD and comparative example 1 of oxidation silicon substrate carbon compound cathode materials prepared by the embodiment of the present invention 1
Silicon oxide/carbon composite negative material XRD；
Fig. 3 is the Raman collection of illustrative plates and comparative example 1 of oxidation silicon substrate carbon compound cathode materials prepared by the embodiment of the present invention 1
The Raman collection of illustrative plates of the silicon oxide/carbon composite negative material of preparation；
Fig. 4 is the cycle performance curve and coulomb effect of oxidation silicon substrate carbon compound cathode materials prepared by the embodiment of the present invention 1
The cycle performance curve and coulombic efficiency curve map of silicon oxide/carbon composite negative material prepared by rate curve map and comparative example 1；
Fig. 5 is the SEM figures of oxidation silicon substrate carbon compound cathode materials prepared by the embodiment of the present invention 6；
Fig. 6 is the XRD of oxidation silicon substrate carbon compound cathode materials prepared by the embodiment of the present invention 6；
Fig. 7 is the Raman collection of illustrative plates of oxidation silicon substrate carbon compound cathode materials prepared by the embodiment of the present invention 6；
Fig. 8 is the cycle performance curve and coulomb effect of oxidation silicon substrate carbon compound cathode materials prepared by the embodiment of the present invention 6
Rate curve map；
Fig. 9 is the SEM figures of silicon oxide/carbon composite negative material prepared by comparative example 1 of the present invention.
Embodiment
Below in conjunction with the embodiment of the present invention, technical scheme is clearly and completely described, it is clear that institute
The embodiment of description is only a part of embodiment of the invention, rather than whole embodiments.Based on the embodiment in the present invention,
The every other embodiment that those of ordinary skill in the art are obtained under the premise of creative work is not made, belongs to this hair
The scope of bright protection.
The invention provides a kind of preparation method for aoxidizing silicon substrate carbon compound cathode materials, including：
A silica) is subjected to heat treatment 10min~20h at 800~1200 DEG C；
B) by step A) obtained silica cooled, and the scope of the cooling is 0~400 DEG C；Or by step A)
To silica be first cooled to room temperature, then be warming up to 800~1000 DEG C；
C carbon-source gas) are passed through, in step B) chemical vapor deposition is carried out on obtained silica, obtain aoxidizing silicon substrate carbon
Composite negative pole material.
Step A) in, silica is first carried out heat treatment 10min~20h by the present invention at 800~1200 DEG C.Specifically,
Preferably：Silica is warming up to the temperature of heat treatment, heat treatment 10min~20h is then carried out at 800~1200 DEG C.
In the present invention, the silica is preferably expressed as SiOx, wherein 0 ＜ x≤2.The silica is preferably oxidation
Silicon grain, is more preferably commercialized unformed silicon oxide particle.The particle diameter of the silicon oxide particle is preferably 0.1~100 μm, more
Preferably 1~20 μm.In certain embodiments of the present invention, the particle diameter of the silicon oxide particle is 5 μm.
The present invention has no special limitation to the speed of the heating, using heating rate well known to those skilled in the art
.The present invention has no special limitation to the mode of the heat treatment, using heat treatment side well known to those skilled in the art
Formula.The present invention is preferably to heat.The temperature of the heat treatment is preferably 900~1100 DEG C；The time of the heat treatment is excellent
Elect 0.5h~10h as.In certain embodiments of the present invention, the temperature of the heat treatment is 900 DEG C, 1000 DEG C or 1100 DEG C；
The time of the heat treatment is 5h.
The step A) terminate after, carry out step B), i.e., to the step A) obtained silica cools, the drop
The scope of temperature is 0~400 DEG C；Preferably 0~200 DEG C.In certain embodiments of the present invention, the scope of the cooling be 0 DEG C,
100 DEG C or 200 DEG C.Or, by the step A) obtained silica is first cooled to room temperature, then it is warming up to 800~1000 DEG C.
In certain embodiments of the present invention, by the step A) obtained silica is first cooled to room temperature, then it is warming up to 900 DEG C.This hair
The bright speed to the cooling has no special limitation, using rate of temperature fall well known to those skilled in the art.The present invention
Speed to the heating has no special limitation, using heating rate well known to those skilled in the art.
In the present invention, above-mentioned steps A) and step B) preferably carried out under conditions of protection gas.The present invention is protected to described
The species of shield gas has no special limitation, using protection gas well known to those skilled in the art.The present invention is preferably inertia
Gas, more preferably argon gas.
By above-mentioned steps A) and step B) processing after, silicon oxide surface produces the active sites of certain catalytic action
Point, in chemical vapor deposition processes below, can be catalyzed carbon-source gas and grow into agraphitic carbon and one-dimensional carbon material naturally,
And then it is coated on silicon oxide surface formation oxidation silicon substrate carbon compound cathode materials.
The step B) terminate after, carry out step C), that is, carbon-source gas are passed through, in step B) carry out on obtained silica
Chemical vapor deposition (CVD), obtains aoxidizing silicon substrate carbon compound cathode materials.Carbon-source gas are in step B) the obtained work of silica
Under the catalytic action in property site, agraphitic carbon and one-dimensional carbon material are grown into naturally, and then be coated on step B) obtained oxidation
Silicon face formation oxidation silicon substrate carbon compound cathode materials.
The present invention method of the chemical vapor deposition is had no it is specifically limited, using well known to those skilled in the artization
CVD method is learned, the present invention is preferably normal atmosphere vapor deposition.In the present invention, the carbon-source gas are preferably hydro carbons
Chemical compound gas or alcohol compound gas；More preferably ethene, methane or acetylene.The present invention to the carbon-source gas with it is described
The volume mass of the silica limitation more special than having no, as long as meeting the requirement of chemical vapor deposition.In the present invention, institute
Carbon-source gas are stated with the volume mass of the silica than preferably 0.2L~10L：0.5g~10g, more preferably 0.2L~5L：
0.5g~5g, most preferably 0.5L~2L：1g~2g.In certain embodiments of the present invention, the carbon-source gas and the oxygen
The volume mass ratio of SiClx is 0.6L：1.5g.
The time that the carbon-source gas are passed through is the time of chemical vapor deposition, and the time of the chemical vapor deposition is excellent
Elect 10min~10h as；More preferably 30min~5h.The temperature of the chemical vapor deposition be step B) at the end of temperature.
In certain embodiments of the present invention, the temperature of the chemical vapor deposition is 900 DEG C；The time of the chemical vapor deposition is
1h。
After the chemical vapor deposition terminates, preferably also include：The product of the chemical vapor deposition is cooled down, so that
To oxidation silicon substrate carbon compound cathode materials.The present invention has no special limitation to the mode of the cooling, using art technology
The type of cooling known to personnel.The present invention is preferably to naturally cool to room temperature.
In the present invention, above-mentioned all steps are carried out preferably in atmosphere furnace.
The present invention has no special limitation to the source of above-mentioned used raw material components, can be general commercially available.
The invention provides oxidation silicon substrate carbon compound cathode materials prepared by a kind of preparation method described above.
The oxidation silicon substrate carbon compound cathode materials include：Silica and carbon material；The carbon material includes amorphous carbon
With one-dimensional carbon material.The one-dimensional carbon material is the one or more in carbon nanocoils, CNT and one-dimensional carbon nano chain.
In certain embodiments of the present invention, the one-dimensional carbon material is CNT.
In the present invention, the agraphitic carbon and one-dimensional carbon material are carbon-source gas in the silica activity through Overheating Treatment
Under the catalytic action in site, grow and form naturally by chemical vapor deposition.The agraphitic carbon and one-dimensional carbon material are coated on
Silicon oxide surface, forms oxidation silicon substrate carbon compound cathode materials.
The silica is preferably expressed as SiOx, wherein 0 ＜ x≤2.The silica is preferably silicon oxide particle, more excellent
Elect the unformed silicon oxide particle of commercialization as.The particle diameter of the silicon oxide particle is preferably 1~10 μm.In some realities of the present invention
Apply in example, the particle diameter of the silicon oxide particle is 5 μm.
The oxidation silicon substrate carbon compound cathode materials are expressed as：SiOx@a-C, wherein, 0 ＜ x≤2.
Present invention also offers a kind of lithium ion battery, including positive pole, negative pole, barrier film and electrolyte, the negative pole includes
Oxidation silicon substrate carbon compound cathode materials described above.
The present invention does not have special limitation to the species of the positive pole, barrier film and electrolyte, and e.g., the positive pole can use lithium
Piece；The barrier film can use microporous polypropylene membrane；The electrolyte can use ethylene carbonate (EC) and dimethyl carbonate (DMC)
Mixed liquor.Specifically, of the invention by above-mentioned silica/carbon/CNT composite negative pole material and binding agent (butadiene-styrene rubber
(SBR)：Sodium carboxymethylcellulose (CMC)=3：7 mass ratioes), conductive agent Super P are according to 80：10：10 weight ratio mixing,
Suitable quantity of water is added as dispersant and is tuned into slurry, is then coated uniformly in copper foil current collector, and vacuum dried, roll-in, system
It is standby into negative plate；Using lithium metal as to electrode, 1mol/L LiPF6Mixed solvent (EC: DMC=1:1 volume ratio) it is electrolysis
Liquid, microporous polypropylene membrane (Celgard 2400) is barrier film, and simulated battery is assembled into the glove box that argon gas is protected.
The present invention carries out permanent rate charge-discharge to obtained simulated battery and tested, and tests the cyclicity of the lithium ion battery
Can, charging/discharging voltage is limited in 0.005~1.5 volt, and the multiplying power of discharge and recharge is 0.5C.The electricity of battery is tested using Land testers
Chemical property, test condition is room temperature.Test result indicates that, the stable discharging specific capacity of lithium ion battery produced by the present invention exists
More than 800mAh/g, coulombic efficiency is more than 99% after circulating 5 times, and coulombic efficiency reaches more than 99.5% after circulating 20 times；Follow
After ring 140 times, stable discharging specific capacity almost without obvious decay, coulombic efficiency also substantially without significant change, thus, with higher
Specific capacity and cycle performance.
The invention provides a kind of preparation method for aoxidizing silicon substrate carbon compound cathode materials, including：A) by silica 800
Heat treatment 10min~20h is carried out at~1200 DEG C；B) by step A) obtained silica cooled, the scope of the cooling
For 0~400 DEG C；Or by step A) obtained silica is first cooled to room temperature, then it is warming up to 800~1000 DEG C；C) it is passed through carbon source
Gas, in step B) chemical vapor deposition is carried out on obtained silica, obtain aoxidizing silicon substrate carbon compound cathode materials.The present invention
In the preparation method of the oxidation silicon substrate carbon compound cathode materials of offer, one-dimensional carbon materials are generated without extra addition catalyst
Material, but by being carried out to silica after a certain degree of heat treatment, its surface is produced the avtive spot of certain catalytic action,
Catalysis carbon-source gas grow into agraphitic carbon and one-dimensional carbon material naturally, and then are coated on silicon oxide surface formation oxidation silicon substrate carbon
Composite negative pole material, preparation method is simple and easy to apply.Meanwhile, using oxidation silicon substrate carbon Compound Negative made from the preparation method of the present invention
Pole material specific capacity and cycle performance are higher
In order to further illustrate the present invention, a kind of oxidation silicon substrate carbon Compound Negative provided with reference to embodiments the present invention
Pole material, its preparation method and lithium ion battery are described in detail, but can not be understood as to the scope of the present invention
Limit.
Embodiment 1
1.5g particle diameters are put into atmosphere furnace for 5 μm of silicon oxide sio x (0 ＜ x≤2), are warming up under an inert atmosphere
1000 DEG C, be incubated 5h, be then cooled to 900 DEG C, be passed through 0.6L ethylene gas carry out chemical vapor deposition, sustained response 1h,
Obtain oxidation silicon substrate carbon compound cathode materials (SiOx a-C).
Obtained oxidation silicon substrate carbon compound cathode materials are scanned electron-microscope scanning analysis by the present invention, as a result such as Fig. 1 institutes
Show, Fig. 1 is the SEM figures of oxidation silicon substrate carbon compound cathode materials prepared by the embodiment of the present invention 1.As seen from Figure 1, silica
Surface coating have one layer of carbon, and also substantial amounts of CNT is attached to the surface of silica there is provided good conduction
Network, while serving the effect of buffering substrate.
Obtained oxidation silicon substrate carbon compound cathode materials are analyzed using X-ray diffractometer, implementation of the present invention is obtained
The XRD of silicon substrate carbon compound cathode materials is aoxidized in example 1, as shown in the SiOx a-C curves in Fig. 2.Fig. 2 is implemented for the present invention
Oxidation silicon substrate carbon compound cathode materials prepared by the XRD and comparative example 1 of oxidation silicon substrate carbon compound cathode materials prepared by example 1
XRD.The oxidation silicon substrate carbon compound cathode material that it can be seen from SiOx a-C curves in Fig. 2 prepared by the embodiment of the present invention 1
The diffraction maximum of material is mainly unformed SiO after disproportionation2With Si diffraction maximum.
The oxidation silicon substrate carbon compound cathode materials obtained to the present embodiment carry out Raman atlas analysis, as a result as in Fig. 3
Shown in SiOx a-C curves, Fig. 3 be the embodiment of the present invention 1 prepare oxidation silicon substrate carbon compound cathode materials Raman collection of illustrative plates with
And the Raman collection of illustrative plates of the oxidation silicon substrate carbon compound cathode materials of the preparation of comparative example 1.It can be seen by the SiOx@a-C curves in Fig. 3
Go out, D peaks and G peaks show that SiOx material surfaces are coated with carbon material.
The present invention is by above-mentioned oxidation silicon substrate carbon compound cathode materials and binding agent (butadiene-styrene rubber (SBR)：Carboxymethyl cellulose
Sodium (CMC)=3：7 mass ratioes), conductive agent Super P are according to 80：10：10 weight adds suitable quantity of water as scattered than mixing
Agent is tuned into slurry, is then coated uniformly in copper foil current collector, and vacuum dried, roll-in, is prepared into negative plate；With lithium metal
For to electrode, 1mol/L LiPF6Mixed solvent (EC: DMC=1:1 volume ratio) it is electrolyte, microporous polypropylene membrane
(Celgard 2400) is barrier film, and simulated battery is assembled into the glove box that argon gas is protected.
The simulated battery being assembled into is carried out to permanent multiplying power charge and discharge on Land testers (Wuhan Xin Nuo Electronics Co., Ltd.s)
Electrical testing, charging/discharging voltage is limited in after 0.005~1.5 volt, the circle of 0.05C activation 2,0.5C rate charge-discharges (nominal specific capacity
It is set as 1500mA/g), its cycle performance curve and coulombic efficiency curve are obtained as shown in the SiOx@a-C curves in Fig. 4.Fig. 4
The cycle performance curve and coulombic efficiency curve map and ratio of the SiOx@a-C composite negative pole materials prepared for the embodiment of the present invention 1
The cycle performance curve and coulombic efficiency curve map of the SiOx@C composite negative pole materials prepared compared with example 1.
Test result indicates that, the stable discharging specific capacity of lithium ion battery made from the present embodiment in more than 1000mAh/g,
Coulombic efficiency is more than 99% after circulating 5 times, and coulombic efficiency reaches more than 99.5% after circulating 20 times；It is stable after circulation 140 times
Specific discharge capacity almost without obvious decay, coulombic efficiency also substantially without significant change, thus, with higher specific capacity and circulation
Performance.
Embodiment 2
1.5g particle diameters are put into atmosphere furnace for 5 μm of silicon oxide sio x (0 ＜ x≤2), argon gas is passed through, temperature is risen to
900 DEG C, 5h is incubated, at the end of 900 DEG C are incubated 5h, the ethylene gas for being passed through 0.6L carries out chemical vapor deposition, sustained response
1h, obtains aoxidizing silicon substrate carbon compound cathode materials.
The present invention is by above-mentioned oxidation silicon substrate carbon compound cathode materials and binding agent (butadiene-styrene rubber (SBR)：Carboxymethyl cellulose
Sodium (CMC)=3：7 mass ratioes), conductive agent Super P are according to 80：10：10 weight adds suitable quantity of water as scattered than mixing
Agent is tuned into slurry, is then coated uniformly in copper foil current collector, and vacuum dried, roll-in, is prepared into negative plate；With lithium metal
For to electrode, 1mol/L LiPF6Mixed solvent (EC: DMC=1:1 volume ratio) it is electrolyte, microporous polypropylene membrane
(Celgard 2400) is barrier film, and simulated battery is assembled into the glove box that argon gas is protected.
The simulated battery being assembled into is carried out to permanent multiplying power charge and discharge on Land testers (Wuhan Xin Nuo Electronics Co., Ltd.s)
Electrical testing, charging/discharging voltage is limited in after 0.005~1.5 volt, the circle of 0.05C activation 2,0.5C rate charge-discharges (nominal specific capacity
It is set as 1500mA/g).Test result indicates that, the stable discharging specific capacity of lithium ion battery made from the present embodiment exists
More than 800mAh/g, coulombic efficiency is more than 99% after circulating 5 times, and coulombic efficiency reaches more than 99.5% after circulating 20 times；Follow
After ring 140 times, stable discharging specific capacity almost without obvious decay, coulombic efficiency also substantially without significant change, thus, with higher
Specific capacity and cycle performance.
Embodiment 3
1.5g particle diameters are put into atmosphere furnace for 5 μm of silicon oxide sio x (0 ＜ x≤2), argon gas is passed through, temperature is risen to
1100 DEG C, be incubated 5h, be then cooled to 900 DEG C, be passed through 0.6L ethylene gas carry out chemical vapor deposition, sustained response 1h,
Obtain aoxidizing silicon substrate carbon compound cathode materials.
The present invention is by above-mentioned oxidation silicon substrate carbon compound cathode materials and binding agent (butadiene-styrene rubber (SBR)：Carboxymethyl cellulose
Sodium (CMC)=3：7 mass ratioes), conductive agent Super P are according to 80：10：10 weight adds suitable quantity of water as scattered than mixing
Agent is tuned into slurry, is then coated uniformly in copper foil current collector, and vacuum dried, roll-in, is prepared into negative plate；With lithium metal
For to electrode, 1mol/L LiPF6Mixed solvent (EC: DMC=1:1 volume ratio) it is electrolyte, microporous polypropylene membrane
(Celgard 2400) is barrier film, and simulated battery is assembled into the glove box that argon gas is protected.
The simulated battery being assembled into is carried out to permanent multiplying power charge and discharge on Land testers (Wuhan Xin Nuo Electronics Co., Ltd.s)
Electrical testing, charging/discharging voltage is limited in after 0.005~1.5 volt, the circle of 0.05C activation 2,0.5C rate charge-discharges (nominal specific capacity
It is set as 1500mA/g).Test result indicates that, the stable discharging specific capacity of lithium ion battery made from the present embodiment exists
More than 800mAh/g, coulombic efficiency is more than 99% after circulating 5 times, and coulombic efficiency reaches more than 99.5% after circulating 20 times；Follow
After ring 140 times, stable discharging specific capacity almost without obvious decay, coulombic efficiency also substantially without significant change, thus, with higher
Specific capacity and cycle performance.
Embodiment 4
1.5g particle diameters are put into atmosphere furnace for 5 μm of silicon oxide sio x (0 ＜ x≤2), argon gas is passed through, temperature is risen to
1000 DEG C, 5h is incubated, 900 DEG C are then cooled the temperature to, the ethylene gas for being passed through 0.6L carries out chemical vapor deposition, sustained response
1h, obtains aoxidizing silicon substrate carbon compound cathode materials.
The present invention is by above-mentioned oxidation silicon substrate carbon compound cathode materials and binding agent (butadiene-styrene rubber (SBR)：Carboxymethyl cellulose
Sodium (CMC)=3：7 mass ratioes), conductive agent Super P are according to 80：10：10 weight adds suitable quantity of water as scattered than mixing
Agent is tuned into slurry, is then coated uniformly in copper foil current collector, and vacuum dried, roll-in, is prepared into negative plate；With lithium metal
For to electrode, 1mol/L LiPF6Mixed solvent (EC: DMC=1:1 volume ratio) it is electrolyte, microporous polypropylene membrane
(Celgard 2400) is barrier film, and simulated battery is assembled into the glove box that argon gas is protected.
The simulated battery being assembled into is carried out to permanent multiplying power charge and discharge on Land testers (Wuhan Xin Nuo Electronics Co., Ltd.s)
Electrical testing, charging/discharging voltage is limited in after 0.005~1.5 volt, the circle of 0.05C activation 2,0.5C rate charge-discharges (nominal specific capacity
It is set as 1500mA/g).Test result indicates that, the stable discharging specific capacity of lithium ion battery made from the present embodiment exists
More than 800mAh/g, coulombic efficiency is more than 99% after circulating 5 times, and coulombic efficiency reaches more than 99.5% after circulating 20 times；Follow
After ring 140 times, stable discharging specific capacity almost without obvious decay, coulombic efficiency also substantially without significant change, thus, with higher
Specific capacity and cycle performance.
Embodiment 5
1.5g particle diameters are put into atmosphere furnace for 5 μm of silicon oxide sio x (0 ＜ x≤2), argon gas is passed through, temperature is risen to
1000 DEG C, be incubated 5h, be then cooled to 900 DEG C, be passed through 0.6L ethylene gas carry out chemical vapor deposition, sustained response 1h,
Obtain aoxidizing silicon substrate carbon compound cathode materials.
The present invention is by above-mentioned oxidation silicon substrate carbon compound cathode materials and binding agent (butadiene-styrene rubber (SBR)：Carboxymethyl cellulose
Sodium (CMC)=3：7 mass ratioes), conductive agent Super P are according to 80：10：10 weight adds suitable quantity of water as scattered than mixing
Agent is tuned into slurry, is then coated uniformly in copper foil current collector, and vacuum dried, roll-in, is prepared into negative plate；With lithium metal
For to electrode, 1mol/L LiPF6Mixed solvent (EC: DMC=1:1 volume ratio) it is electrolyte, microporous polypropylene membrane
(Celgard 2400) is barrier film, and simulated battery is assembled into the glove box that argon gas is protected.
The simulated battery being assembled into is carried out to permanent multiplying power charge and discharge on Land testers (Wuhan Xin Nuo Electronics Co., Ltd.s)
Electrical testing, charging/discharging voltage is limited in after 0.005~1.5 volt, the circle of 0.05C activation 2,0.5C rate charge-discharges (nominal specific capacity
It is set as 1500mA/g).Test result indicates that, the stable discharging specific capacity of lithium ion battery made from the present embodiment exists
More than 700mAh/g, coulombic efficiency is more than 99% after circulating 5 times；After circulation 140 times, stable discharging specific capacity is almost without obvious
Decay, coulombic efficiency also substantially without significant change, thus, with higher specific capacity and cycle performance.
Embodiment 6
1.5g particle diameters are put into atmosphere furnace for 5 μm of silicon oxide sio x (0 ＜ x≤2), argon gas is passed through, temperature is risen to
1000 DEG C, 5h is incubated, room temperature is then cooled to, then temperature is risen to 900 DEG C, be passed through 0.6L ethylene gas and carry out chemical vapor deposition
Product, sustained response 1h, natural cooling obtains aoxidizing silicon substrate carbon compound cathode materials.
Obtained oxidation silicon substrate carbon compound cathode materials are scanned electronic microscope photos by the present invention, as a result as shown in figure 5, figure
5 be the SEM figures of oxidation silicon substrate carbon compound cathode materials prepared by the embodiment of the present invention 6.As seen from Figure 5, the table of silica
Bread is covered with one layer of carbon, and also substantial amounts of carbon nano-fiber is attached to the surface of silica there is provided good conductive mesh
Network, while serving the effect of buffering substrate.
Obtained silicon oxide/carbon composite negative material is analyzed using X-ray diffractometer, the embodiment of the present invention is obtained
The XRD of silicon substrate carbon compound cathode materials is aoxidized in 6, as shown in Figure 6.Fig. 6 is oxidation silicon substrate carbon prepared by the embodiment of the present invention 6
The XRD of composite negative pole material.As seen from Figure 6, the diffraction maximum of prepared oxidation silicon substrate carbon compound cathode materials is main
For unformed SiO after disproportionation2With Si diffraction maximum.
The oxidation silicon substrate carbon compound cathode materials obtained to the present embodiment carry out Raman atlas analysis, as a result such as Fig. 7 institutes
Show, Fig. 7 is the Raman collection of illustrative plates of oxidation silicon substrate carbon compound cathode materials prepared by the embodiment of the present invention 6.As seen from Figure 7, D
Peak and G peaks show that SiOx material surfaces are coated with carbon material.
The present invention is by above-mentioned oxidation silicon substrate carbon compound cathode materials and binding agent (butadiene-styrene rubber (SBR)：Carboxymethyl cellulose
Sodium (CMC)=3：7 mass ratioes), conductive agent Super P are according to 80：10：10 weight adds suitable quantity of water as scattered than mixing
Agent is tuned into slurry, is then coated uniformly in copper foil current collector, and vacuum dried, roll-in, is prepared into negative plate；With lithium metal
For to electrode, 1mol/L LiPF6Mixed solvent (EC: DMC=1:1 volume ratio) it is electrolyte, microporous polypropylene membrane
(Celgard 2400) is barrier film, and simulated battery is assembled into the glove box that argon gas is protected.
The simulated battery being assembled into is carried out to permanent multiplying power charge and discharge on Land testers (Wuhan Xin Nuo Electronics Co., Ltd.s)
Electrical testing, charging/discharging voltage is limited in after 0.005~1.5 volt, the circle of 0.05C activation 2,0.5C rate charge-discharges (nominal specific capacity
It is set as 1500mA/g), obtain its cycle performance curve and coulombic efficiency curve is as shown in Figure 8.Fig. 8 is the embodiment of the present invention 6
The cycle performance curve and coulombic efficiency curve map of the oxidation silicon substrate carbon compound cathode materials of preparation.
Test result indicates that, the stable discharging specific capacity of lithium ion battery made from the present embodiment in more than 900mAh/g,
Coulombic efficiency is more than 99% after circulating 6 times；After circulation 55 times, stable discharging specific capacity is almost without obvious decay, coulombic efficiency
Also substantially without significant change, thus, with higher specific capacity and cycle performance.
Embodiment 7
1.5g particle diameters are put into atmosphere furnace for 5 μm of silicon oxide sio x (0 ＜ x≤2), argon gas is passed through, temperature is risen to
1100 DEG C, 5h is incubated, room temperature is then cooled to, then temperature is risen to 900 DEG C, the ethylene gas for being passed through 0.6L carries out chemical gaseous phase
Deposition, sustained response 1h obtains aoxidizing silicon substrate carbon compound cathode materials.
The present invention is by above-mentioned oxidation silicon substrate carbon compound cathode materials and binding agent (butadiene-styrene rubber (SBR)：Carboxymethyl cellulose
Sodium (CMC)=3：7 mass ratioes), conductive agent Super P are according to 80：10：10 weight adds suitable quantity of water as scattered than mixing
Agent is tuned into slurry, is then coated uniformly in copper foil current collector, and vacuum dried, roll-in, is prepared into negative plate；With lithium metal
For to electrode, 1mol/L LiPF6Mixed solvent (EC: DMC=1:1 volume ratio) it is electrolyte, microporous polypropylene membrane
(Celgard 2400) is barrier film, and simulated battery is assembled into the glove box that argon gas is protected.
The simulated battery being assembled into is carried out to permanent multiplying power charge and discharge on Land testers (Wuhan Xin Nuo Electronics Co., Ltd.s)
Electrical testing, charging/discharging voltage is limited in after 0.005~1.5 volt, the circle of 0.05C activation 2,0.5C rate charge-discharges (nominal specific capacity
It is set as 1500mA/g).Test result indicates that, the stable discharging specific capacity of lithium ion battery made from the present embodiment exists
More than 800mAh/g, coulombic efficiency is more than 99% after circulating 7 times；After circulation 100 times, stable discharging specific capacity is almost without obvious
Decay, coulombic efficiency also substantially without significant change, thus, with higher specific capacity and cycle performance.
Embodiment 8
1.5g particle diameters are put into atmosphere furnace for 5 μm of silicon oxide sio x (0 ＜ x≤2), argon gas is passed through, temperature is risen to
900 DEG C, 5h is incubated, room temperature is then cooled to, then temperature is risen to 900 DEG C, the ethylene gas for being passed through 0.6L carries out chemical gaseous phase
Deposition, sustained response 1h obtains aoxidizing silicon substrate carbon compound cathode materials.
The present invention is by above-mentioned oxidation silicon substrate carbon compound cathode materials and binding agent (butadiene-styrene rubber (SBR)：Carboxymethyl cellulose
Sodium (CMC)=3：7 mass ratioes), conductive agent Super P are according to 80：10：10 weight adds suitable quantity of water as scattered than mixing
Agent is tuned into slurry, is then coated uniformly in copper foil current collector, and vacuum dried, roll-in, is prepared into negative plate；With lithium metal
For to electrode, 1mol/L LiPF6Mixed solvent (EC: DMC=1:1 volume ratio) it is electrolyte, microporous polypropylene membrane
(Celgard 2400) is barrier film, and simulated battery is assembled into the glove box that argon gas is protected.
The simulated battery being assembled into is carried out to permanent multiplying power charge and discharge on Land testers (Wuhan Xin Nuo Electronics Co., Ltd.s)
Electrical testing, charging/discharging voltage is limited in after 0.005~1.5 volt, the circle of 0.05C activation 2,0.5C rate charge-discharges (nominal specific capacity
It is set as 1500mA/g).Test result indicates that, the stable discharging specific capacity of lithium ion battery made from the present embodiment exists
More than 800mAh/g, coulombic efficiency is more than 99% after circulating 7 times；After circulation 80 times, stable discharging specific capacity is almost without obvious
Decay, coulombic efficiency also substantially without significant change, thus, with higher specific capacity and cycle performance.
Comparative example 1
1.5g particle diameters are put into atmosphere furnace for 5 μm of silicon oxide sio x (0 ＜ x≤2), argon gas is passed through, is passed through 0.6L's
Ethylene gas, chemical vapor deposition 1h is carried out at 900 DEG C, silicon oxide/carbon composite negative material (SiOx@C) is obtained.
Obtained silicon oxide/carbon composite negative material is scanned electron-microscope scanning analysis by the present invention, as a result such as Fig. 9 institutes
Show, Fig. 9 is the SEM figures of silicon oxide/carbon composite negative material prepared by comparative example 1 of the present invention.As seen from Figure 9, silica
Surface be only coated with one layer of carbon.
Obtained silicon oxide/carbon composite negative material (SiOx@C) is analyzed using X-ray diffractometer, this hair is obtained
The XRD of silicon oxide/carbon composite negative material in bright comparative example 1, as shown in the SiOx@C curves in Fig. 2.In Fig. 2
The diffraction maximum that SiOx@C curves can be seen that prepared silicon oxide/carbon composite negative material is mainly unformed after being disproportionated
SiO2With Si diffraction maximum.
The silicon oxide/carbon composite negative material obtained to this comparative example 1 carries out Raman atlas analysis, as a result as in Fig. 3
Shown in SiOx@C curves, D peaks and G peaks show that SiOx material surfaces are coated with carbon materials it can be seen from the SiOx@C curves in Fig. 3
Material.
The present invention is by above-mentioned silicon oxide/carbon composite negative material and binding agent (butadiene-styrene rubber (SBR)：Carboxymethyl cellulose
Sodium (CMC)=3：7 mass ratioes), conductive agent Super P are according to 80：10：10 weight adds suitable quantity of water as scattered than mixing
Agent is tuned into slurry, is then coated uniformly in copper foil current collector, and vacuum dried, roll-in, is prepared into negative plate；With lithium metal
For to electrode, 1mol/L LiPF6Mixed solvent (EC: DMC=1:1 volume ratio) it is electrolyte, microporous polypropylene membrane
(Celgard 2400) is barrier film, and simulated battery is assembled into the glove box that argon gas is protected.
The simulated battery being assembled into is carried out to permanent multiplying power charge and discharge on Land testers (Wuhan Xin Nuo Electronics Co., Ltd.s)
Electrical testing, charging/discharging voltage is limited in after 0.005~1.5 volt, the circle of 0.05C activation 2,0.5C rate charge-discharges (nominal specific capacity
It is set as 1500mA/g), its cycle performance curve and coulombic efficiency curve are obtained as shown in the SiOx@C curves in Fig. 4.
Test result indicates that, the specific discharge capacity of lithium ion battery made from comparative example 1 declines comparatively fast, after circulating 40 times,
Specific capacity is less than 500mAn/g, and coulombic efficiency reaches 99% by 40 circulations；After circulation 140 times, specific discharge capacity is reduced to not
Sufficient 250mAh/g, coulombic efficiency is 99.5%.Thus, specific capacity and cycle performance are poor.
The foregoing description of the disclosed embodiments, enables professional and technical personnel in the field to realize or using the present invention.
A variety of modifications to these embodiments will be apparent for those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, it is of the invention
The embodiments shown herein is not intended to be limited to, and is to fit to and principles disclosed herein and features of novelty phase one
The most wide scope caused.
Claims (10)
1. a kind of preparation method for aoxidizing silicon substrate carbon compound cathode materials, it is characterised in that including：
A silica) is subjected to heat treatment 10min~20h at 800~1200 DEG C；
B) by step A) obtained silica cooled, and the scope of the cooling is 0~400 DEG C；Or by step A) obtain
Silica is first cooled to room temperature, then is warming up to 800~1000 DEG C；
C carbon-source gas) are passed through, in step B) chemical vapor deposition is carried out on obtained silica, obtain oxidation silicon substrate carbon and be combined
Negative material.
2. preparation method according to claim 1, it is characterised in that the silica is SiOx, wherein 0 ＜ x≤2.
3. preparation method according to claim 1, it is characterised in that step A) in, the temperature of the heat treatment for 900~
1100℃；The time of the heat treatment is 30min~10h.
4. preparation method according to claim 1, it is characterised in that step A) with step B) be to carry out under an inert atmosphere
's.
5. preparation method according to claim 1, it is characterised in that the carbon-source gas are hydrocarbon compound gas or alcohol
Class chemical compound gas.
6. preparation method according to claim 5, it is characterised in that the carbon-source gas are ethene, methane or acetylene.
7. preparation method according to claim 1, it is characterised in that step C) in, the time of the chemical vapor deposition
For 10min~10h.
8. preparation method according to claim 7, it is characterised in that step C) in, the time of the chemical vapor deposition
For 30min~5h.
9. oxidation silicon substrate carbon compound cathode materials prepared by claim 1~8 any one preparation method.
10. a kind of lithium ion battery, including positive pole, negative pole, barrier film and electrolyte, it is characterised in that the negative pole includes right
It is required that the oxidation silicon substrate carbon compound cathode materials described in 9.
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