CN108417781A - Conducing composite material and its negative material and secondary cell of preparation - Google Patents
Conducing composite material and its negative material and secondary cell of preparation Download PDFInfo
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- CN108417781A CN108417781A CN201710071066.3A CN201710071066A CN108417781A CN 108417781 A CN108417781 A CN 108417781A CN 201710071066 A CN201710071066 A CN 201710071066A CN 108417781 A CN108417781 A CN 108417781A
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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
- H01M4/366—Composites as layered products
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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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
- 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
- H01M4/36—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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- 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
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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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
- H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
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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 invention discloses a kind of conducing composite material and its negative materials and secondary cell of preparation, wherein the conducing composite material includes：One core is formed by being selected from the first material of one of the 4th major element (IVA), metal, metallic compound or alloy composition group；Coating layer in one, be coated on the surface of the core and the group that is made of oxide, nitride or carbide selected from first material prepared by；And an outer coating layer, it is coated on the surface of the interior coating layer and prepared for carbon material and at least one the second material (dopant material) containing halogen or the 5th major element (VA).
Description
Technical field
The present invention provides a kind of composite material of tool electric conductivity and its prepared negative material and secondary cell, and espespecially one
Composite material of the kind with satisfactory electrical conductivity and its negative material and secondary cell to prepare.
Background technology
Recently, taking, being miniaturized in electronic device, information products and communication industry, light and high performance trend are fast
Short-term training is long.Accordingly, heavy-duty battery especially lithium rechargeable battery is used as the energy of these portable electronic devices
And its demand improves rapidly.Secondary cell can be reused by being charged and discharged, and as information and communication, electric bicycle
Or the energy of the portable electronic devices of electric carrier.Two as key component are depended on due to the usage time of these products
Primary cell, so consumer is improved for high power capacity and using the demand of upper safe secondary cell.
The high capacity technological means of secondary cell used in the prior art often has following limitation to be overcome, though such as
Right charge/discharge capacity rises, and energy density is got higher, but cyclicity is insufficient, or reaches the recurring number of an accumulation charge and discharge,
Capacity just declines slowly, and the phenomenon that just tempestuously decline after certain number, or after multiple charge and discharge, secondary cell is made
Material causes structure to generate rupture and integrally-built stability is greatly reduced because of the multiple dilation of its volume.On
The limitation that uses is stated as the commercial value of secondary cell and insufficient, cannot be satisfied the requirement demand in market.
In addition, the fast charging and discharging demand of secondary cell is gradually increased in recent years, but it is fast when promoting battery charging and discharging
When rate, charge/discharge capacity can be substantially reduced, and battery cycle life can be made to be significantly affected, therefore how same secondary cell is
When the problem of having both fast charging and discharging, high initial capacitance and long circulation life, becoming urgent need to resolve currently on the market.
Invention content
For the present invention in view of the deficiency of above-mentioned known technology, its purpose is to provide one kind having superior electrical conductivity, high structure
Stability and safe conducing composite material and prepared negative material and secondary cell.Also, being to provide a kind of same
When with excellent initial capacitance, high capacitance conservation rate, long circulation life, excellent fast charging and discharging performance conductive composite wood
Material and prepared negative material and secondary cell, and preparation method is easy and can be carried out under temperate condition, can be formed
Has the conducing composite material of the high reaction activity nanometer grade of high-specific surface area.
The present invention provides a kind of conducing composite materials, which is characterized in that it includes：
One core constitutes one of group by being selected from the 4th major element (IVA), metal, metallic compound or alloy
First material is formed；
Coating layer in one is coated on the surface of the core and by oxide, nitrogen selected from first material
Prepared by the group of compound or carbide composition；And
One outer coating layer is coated on the surface of the interior coating layer and contains halogen for carbon material and at least one
Or the 5th major element (VA) the second material prepared by.
Preferably, the core is configured as powder.
Preferably, wherein the powder for forming the core is selected from irregular type or ball-shaped.
Preferably, wherein the particle size of the conducing composite material is PS, meet following condition：0.01μm≤PS≤
10μm。
Preferably, the core is configured as sheet or rodlike.
Preferably, the core is made of silicon.
Preferably, the core is made of silicon, and the interior coating layer is made of the oxide of silicon, the outer coating
Second material of the layer by carbon material and containing nitrogen forms, and the conducing composite material is with general formula Si/SiOx/C:N expressions,
Middle x meets following condition：0.3≤x≤1.5.
Preferably, the core is made of silicon, and the interior coating layer is made of the oxide of silicon, the outer coating
Second material of the layer by carbon material and containing fluorine forms, and the conducing composite material is with general formula Si/SiOx/C:F expressions,
Middle x meets following condition：0.3≤x≤1.5.
Preferably, the core is made of silicon, and the interior coating layer is made of the nitride of silicon, the outer coating
Second material of the layer by carbon material and containing nitrogen forms, and the conducing composite material is with general formula Si/SiNx/C:N expressions,
Middle x meets following condition：0.1≤x≤0.8.
Preferably, the core is made of silicon, and the interior coating layer is made of the nitride of silicon, the outer coating
Second material of the layer by carbon material and containing fluorine forms, and the conducing composite material is with general formula Si/SiNx/C:F expressions,
Middle x meets following condition：0.1≤x≤0.8.
Preferably, the core is made of silicon, and the interior coating layer is made of the carbide of silicon, the outer coating
Second material of the layer by carbon material and containing nitrogen forms, and the conducing composite material is with general formula Si/SiC/C:N is indicated.
Preferably, the core is made of silicon, and the interior coating layer is made of the carbide of silicon, the outer coating
Second material of the layer by carbon material and containing fluorine forms, and the conducing composite material is with general formula Si/SiC/C:F is indicated.
Preferably, the specific surface area of the conducing composite material is BET, meets following condition：BET≤60 square metre/
Gram.
Preferably, the electrical conductivity of the conducing composite material is indicated with ED, meets following condition：ED≧1.0x 10- 2S·cm-1。
The present invention additionally provides a kind of negative materials comprising conducing composite material as described in claim 1.
The present invention separately provides a kind of secondary cell comprising：
One contains the cathode of conducing composite material as described in claim 1；
One anode；
One isolated material；And
Electrolyte.
Preferably, the secondary cell is lithium rechargeable battery.
Preferably, the secondary cell is indicated in the initial capacitance of completion charge or discharge in 0.5 hour with IC, is met
Following condition：IC≧1700mAh/g.
Preferably, the capacity retention (%) of the secondary cell is indicated with MC100, when being the 100th charge and discharge
The percentage of capacitance when capacitance divided by the 1st charge and discharge, meets following condition：MC100≤90%.
Description of the drawings
Figure 1A is the TEM figures of the conducing composite material (irregular type) prepared by the embodiment of the present invention 1；
Figure 1B is the TEM figures of the conducing composite material (irregular type) prepared by the embodiment of the present invention 2；
Fig. 1 C are the TEM figures of the conducing composite material (ball-shaped) prepared by the embodiment of the present invention 2.
Fig. 1 D are the TEM figures of the conducing composite material (irregular type) prepared by the embodiment of the present invention 3；
Fig. 1 E are the TEM figures of the conducing composite material (irregular type) prepared by the embodiment of the present invention 4；
The particle diameter distribution numerical value and distribution map that Fig. 2A is measured by the conducing composite material prepared by the embodiment of the present invention 1；
The particle diameter distribution numerical value and distribution map that Fig. 2 B are measured by the conducing composite material prepared by the embodiment of the present invention 2；
The particle diameter distribution numerical value and distribution map that Fig. 2 C are measured by the conducing composite material prepared by the embodiment of the present invention 3；
The particle diameter distribution numerical value and distribution map that Fig. 2 D are measured by the conducing composite material prepared by the embodiment of the present invention 4；
Fig. 3 is that the electrical conductivity of experimental example 3 of the present invention, comparative example 1 and comparative example 2 measures figure；
Fig. 4 is cycle-index of the experimental example 4 of the present invention under different charge-discharge velocities to initial capacitance variation diagram.
Specific implementation mode
The present invention provides a kind of conducing composite material comprising：One core, by be selected from the 4th major element (IVA),
Metal, metallic compound or alloy constitute the first material of one of group and are formed；Coating layer in one, is coated on the core
Prepared by surface and the group being made of oxide, nitride or carbide selected from first material；An and outer coating
Layer is coated on the surface of the interior coating layer and contains halogen or the 5th major element (VA) for carbon material and at least one
The second material prepared by.The invention demonstrates that the conducing composite material has high conductivity and high structural stability, led using this
Negative material prepared by composite and secondary cell also have excellent initial capacitance, high capacitance conservation rate, length
Cycle life, the performance of excellent fast charging and discharging.
When implementing the present invention, no matter carbon source material used in coating layer or outer coating layer in generating, can be selected from it is following it
One can manufacture the material of carbon under heat treatment temperature by pyrolysis：Its independent or any admixture of aliphatic series and clicyclic hydrocarbon
(such as methane, ethane, ethylene, acetylene, propane, butane, butylene, pentane, iso-butane and hexane)；And polyimides
(Polyimide, PI), polyvinyl alcohol (Polyvinyl Alcohol, PVA), polyvinyl chloride (PolyVinyl Chloride,
PVC) etc..
When implementing the present invention, material used in core is generated, the 4th major element (IVA) is can be selected from, including carbon
(C), silicon (Si), germanium (Ge), tin (Sn), lead (Pb) or its alloy formed each other or metallic compound are for example comprising silicon-carbon
Compound, tin carbon compound, silica etc.；Also metal (metal for not including the 4th major element (IVA)) is can be selected from, such as is wrapped
The main group metals such as argentiferous (Ag), zinc (Zn), aluminium (Al), arsenic (As), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu) or transition gold
Category or its alloy or metallic compound for being formed each other.
The configuration in core of the invention portion can be powder, sheet or rodlike.Can be in not advise if core is configured as powder
Then type or ball-shaped.In a preferred embodiment, the particle size of conducing composite material of the present invention is indicated with PS, is met following
Condition：0.01μm≤PS≤10μm.
When implementing the present invention, generate other than outer coating layer institute doped carbon the optional halogen of element (such as fluorine, chlorine, bromine,
Iodine) or the 5th major element (VA) is selected to include nitrogen (N), phosphorus (P), arsenic (As), antimony (Sb), bismuth (Bi).
Implement heating mechanism used in the present invention or reactor, depending on specific object, can carry out continuous or divide
Batch processing, such as fluidized-bed reactor, revolving burner, vertical type moving-burden bed reactor, continuous tunnel furnace, batch stove and rotary kiln etc.,
This is unlimited.
The present invention outside core and interior coating layer in being formed by outer coating layer, since it further includes above-mentioned doping
Electrical conductivity can be substantially improved in material, and contributes to the promotion of initial capacitance.And (it is about due to the use of having high young's modulus
Carbon material 680GPa) can be used as an elastomer, can help to discharge remaining stress, therefore simultaneously through interior coating layer and outside
The double-layer structure body of coating layer can generate core enough compression, can more promote integral material structure multiple
Stability after charge and discharge.
Through disclosed herein core, interior coating layer, the trilaminate material structure of outer coating layer and in outer coating
Layer is doped, and material structure stability can be substantially improved, and materials conductive degree is significantly increased.In addition, the present invention can be directed to how
The core material of rice grade is processed, and since the core material of nanometer grade has high-specific surface area (BET), thus may be used
Promote material reactivity.Therefore, negative material of the invention can not only be substantially improved material initial capacitance and increase material
Cycle life, can also have both excellent fast charging and discharging effect.
In a preferred embodiment, the specific surface area of conducing composite material of the present invention is BET, meets following condition：BET
≤ 60 meters squared per grams.
In another embodiment, the electrical conductivity of conducing composite material of the present invention is indicated with ED, meets following condition：
ED≧1.0x 10-2S·cm-1。
Secondary cell prepared by conducing composite material of the present invention, in a preferred embodiment, the secondary cell are small in 0.5
When complete charge or discharge initial capacitance indicated with IC, IC its meet following condition：IC≧1700mAh/g.It is another compared with
In good embodiment, the capacity retention (%) of the secondary cell prepared by conducing composite material of the present invention is indicated with MC100, is
The percentage of capacitance when capacitance when the 100th charge and discharge divided by the 1st charge and discharge, meets following condition：MC100
≤ 90%.
Please refer to schema and following explanation, purpose therein conducing composite material to illustrate the invention and its to make
The specific embodiment of standby negative material and secondary cell, rather than to limit the scope of the invention.By being specifically embodied
Example illustrates embodiments of the present invention, and the personage for being familiar with this skill can understand this hair easily by content disclosed in the present specification
Other bright advantages and effect.The present invention also can be implemented or be applied by other different specific embodiments, this specification
In every details also can be based on different viewpoints with application, it is without departing from the spirit it is lower carry out it is various modification and change.
Embodiment 1-prepares conducing composite material general formula-core/interior coating layer/outer coating layer (Si/SiOx/C:N, 0.3
≤x≤1.5)
Step 1：It chooses silicon powder (particle diameter distribution is 1nm~10 μm) and is used as core, and being placed on one can
The vacuum degree of the cavity vacuumized, cavity is evacuated to 5x10-4Hold in the palm ear (torr).Above-mentioned cavity can be the reaction of any tool heating
Device, and depending on specific object can be selected from can continuous or batch processing reactor, such as：Fluidized-bed reactor, revolving burner,
Vertical type moving-burden bed reactor, continuous tunnel furnace, batch stove and rotary kiln.Above-mentioned silicon powder can be ball-shaped or irregular type.
Step 2：Then cavity is passed through oxygen and is heated to 800 DEG C, to the core that is formed in silicon powder
On surface, the interior coating layer that is formed of silica is generated, silica general formula is SiOx (0.3≤x≤1.5), wherein when being passed through
Oxygen flow changes from 10 standard cubic centimeters/minute (sccm) to 50 standard cubic centimeters/minute (sccm), silica general formula
The X of SiOx can from 0.3 to 1.5, it is thermally treated reaction 3 hours after, stop supply oxygen, complete in coating layer preparation.
Step 3：It is passed through methane gas (flow 80sccm, as carbon material predecessor) and ammonia again with rear chamber
(flow 20sccm, the source as N doping), and 1000 DEG C are heated to, in the interior coating layer of above-mentioned core
Surface on, generate an outer coating layer.After thermally treated reaction 3 hours, stops supply methane gas and ammonia and closing are anti-
Answer device.Methane gas can be not limited to by generating carbon source used in outer coating layer, can be arbitrary carbon-source gas, rich carbon also can be used
The solid mode of macromolecule powder, such as：Polyimides (Polyimide, PI), polyvinyl alcohol (Polyvinyl Alcohol,
PVA), polyvinyl chloride (PolyVinyl Chloride, PVC) etc., by the core for having generated interior coating layer and rich carbon high score
Sub- powder or slurry are with volume ratio 2:1 is added 500 milliliters of (mL) N- methylpyrroles ketone solvents (NMP), and stirs,
Later carbon is left after high-temp combustion.
Step 4：Argon gas is finally passed through cavity (flow 50sccm), and after making its Temperature fall to room temperature, completes this
The preparation of the conducing composite material of embodiment, it is three layers of concentric structure, general formula Si/SiOx/C to form section:N(0.3≤x
≤ 1.5), TEM figures refer to Figure 1A (irregular type).
Embodiment 2-prepares conducing composite material general formula-core/interior coating layer/outer coating layer (Si/SiOx/C:F, 0.3
≤x≤1.5)；
Step 1：It chooses silicon powder (particle diameter distribution is 1nm~5 μm) and is used as core, and being placed on one can
The vacuum degree of the cavity vacuumized, cavity is evacuated to 5x10-4Hold in the palm ear (torr).Above-mentioned cavity can be the reaction of any tool heating
Device, as the explanation of embodiment 1 repeats no more.Above-mentioned silicon powder can be ball-shaped or irregular type.
Step 2：Then cavity is passed through oxygen and is heated to 800 DEG C, to the core that is formed in silicon powder
On surface, the interior coating layer that is formed of silica is generated, silica general formula is SiOx (0.3≤x≤1.5), wherein when being passed through
Oxygen flow changes from 10 standard cubic centimeters/minute (sccm) to 50 standard cubic centimeters/minute (sccm), silica general formula
The X of SiOx can from 0.3 to 1.5, it is thermally treated reaction 3 hours after, stop supply oxygen, complete in coating layer preparation.
Step 3：It is passed through methane gas (flow 50sccm, as carbon material predecessor) and tetrafluoro again with rear chamber
Change carbon gas (flow 50sccm, the source as Fluorin doped), and be heated to 1000 DEG C, in above-mentioned core
On the surface of interior coating layer, an outer coating layer is generated.Other fluoro-gas, such as perfluor also can be selected in the source of above-mentioned Fluorin doped
Methane.After thermally treated reaction 3 hours, stop supply methane gas and carbon tetrafluoride gas and closing reactor.It generates outer
Carbon source used in coating layer can be not limited to methane gas, can be arbitrary carbon-source gas, rich carbon macromolecule powder also can be used
Solid mode, such as：Polyimides (Polyimide, PI), polyvinyl alcohol (Polyvinyl Alcohol, PVA), polychlorostyrene second
Alkene (PolyVinyl Chloride, PVC) etc. will generate the core and rich carbon macromolecule powder or slurry of interior coating layer
With volume ratio 2:1 500 milliliters of (mL) N- methylpyrroles ketone solvents (NMP) of addition simultaneously stir, later high-temp combustion
After leave carbon.
Step 4：Argon gas is finally passed through cavity (flow 50sccm), and after making its Temperature fall to room temperature, completes this
The preparation of the conducing composite material of embodiment, it is three layers of concentric structure, general formula Si/SiOx/C to form section:F(0.3≤x
≤ 1.5), TEM figures refer to Figure 1B (irregular type) and Fig. 1 C (ball-shaped).
Embodiment 3-prepares conducing composite material general formula-core/interior coating layer/outer coating layer (Si/SiNx/C:N, 0.1
≤x≤0.8)
Step 1：It chooses silicon powder (particle diameter distribution is 1nm~5 μm) and is used as core, and being placed on one can
The vacuum degree of the cavity vacuumized, cavity is evacuated to 5x10-4Hold in the palm ear (torr).Above-mentioned cavity can be the reaction of any tool heating
Device, as the explanation of embodiment 1 repeats no more.Above-mentioned silicon powder can be ball-shaped or irregular type.
Step 2：Then cavity is passed through ammonia and is heated to 800 DEG C, to the core that is formed in silicon powder
On surface, the interior coating layer that is formed of silicon nitride is generated, silicon nitride general formula is SiNx (0.1≤x≤0.8), wherein when being passed through
Ammonia flow changes from 10 standard cubic centimeters/minute (sccm) to 50 standard cubic centimeters/minute (sccm), silicon nitride general formula
The X of SiNx can from 0.1 to 0.8, it is thermally treated reaction 3 hours after, stop supply ammonia, complete in coating layer preparation.
Step 3：It is passed through methane gas (flow 80sccm, as carbon material predecessor) and ammonia again with rear chamber
(flow 20sccm, the source as N doping), and 1000 DEG C are heated to, in the interior coating layer of above-mentioned core
Surface on, generate an outer coating layer.After thermally treated reaction 3 hours, stops supply methane gas and ammonia and closing are anti-
Answer device.Methane gas can be not limited to by generating carbon source used in outer coating layer, can be arbitrary carbon-source gas, rich carbon also can be used
The solid mode of macromolecule powder, such as：Polyimides (Polyimide, PI), polyvinyl alcohol (Polyvinyl Alcohol,
PVA), polyvinyl chloride (PolyVinyl Chloride, PVC) etc., by the core for having generated interior coating layer and rich carbon high score
Sub- powder or slurry are with volume ratio 2:1 500 milliliters of (mL) N- methylpyrroles ketone solvents (NMP) of addition simultaneously stir,
Later carbon is left after high-temp combustion.
Step 4：Argon gas is finally passed through cavity (flow 50sccm), and after making its Temperature fall to room temperature, completes this
The preparation of the conducing composite material of embodiment, it is three layers of concentric structure, general formula Si/SiNx/C to form section:N(0.1≤x
≤ 0.8), TEM figures refer to Fig. 1 D (irregular type).
Embodiment 4-prepares conducing composite material general formula-core/interior coating layer/outer coating layer (Si/SiNx/C:F, 0.1
≤x≤0.8)
Step 1：It chooses silicon powder (particle diameter distribution is 1nm~5 μm) and is used as core, and being placed on one can
The vacuum degree of the cavity vacuumized, cavity is evacuated to 5x10-4Hold in the palm ear (torr).Above-mentioned cavity can be the reaction of any tool heating
Device, as the explanation of embodiment 1 repeats no more.Above-mentioned silicon powder can be ball-shaped or irregular type.
Step 2：Then cavity is passed through ammonia and is heated to 800 DEG C, to the core that is formed in silicon powder
On surface, the interior coating layer that is formed of silicon nitride is generated, silicon nitride general formula is SiNx (0.1≤x≤0.8), wherein when being passed through
Ammonia flow changes from 10 standard cubic centimeters/minute (sccm) to 50 standard cubic centimeters/minute (sccm), silicon nitride general formula
The X of SiNx can from 0.1 to 0.8, it is thermally treated reaction 3 hours after, stop supply ammonia, complete in coating layer preparation.
Step 3：It is passed through methane gas (flow 50sccm, as carbon material predecessor) and tetrafluoro again with rear chamber
Change carbon gas (flow 50sccm, the source as Fluorin doped) and be heated to 1000 DEG C, in above-mentioned core
On the surface of interior coating layer, an outer coating layer is generated.Other fluoro-gas, such as perfluor also can be selected in the source of above-mentioned Fluorin doped
Methane.After thermally treated reaction 3 hours, stop supply methane gas and carbon tetrafluoride gas and closing reactor.It generates outer
Carbon source used in coating layer can be not limited to methane gas, can be arbitrary carbon-source gas, rich carbon macromolecule powder also can be used
Solid mode, such as：Polyimides (Polyimide, PI), polyvinyl alcohol (Polyvinyl Alcohol, PVA), polychlorostyrene second
Alkene (PolyVinyl Chloride, PVC) etc. will generate the core and rich carbon macromolecule powder or slurry of interior coating layer
With volume ratio 2:1 500 milliliters of (mL) N- methylpyrroles ketone solvents (NMP) of addition simultaneously stir, later high-temp combustion
After leave carbon.
Step 4：Argon gas is finally passed through cavity (flow 50sccm), and after making its Temperature fall to room temperature, completes this
The preparation of the conducing composite material of embodiment, it is three layers of concentric structure, general formula Si/SiNx/C to form section:F(0.1≤x
≤ 0.8), TEM figures refer to Fig. 1 E (irregular type).
Embodiment 5-prepares conducing composite material general formula-core/interior coating layer/outer coating layer (Si/SiC/C:N)
Step 1：It chooses silicon powder (particle diameter distribution is 1nm~5 μm) and is used as core, and being placed on one can
The vacuum degree of the cavity vacuumized, cavity is evacuated to 5x10-4Hold in the palm ear (torr).Above-mentioned cavity can be the reactor of any tool heating
As the explanation of embodiment 1 repeats no more.Above-mentioned silicon powder can be ball-shaped or irregular type.
Step 2：Then cavity is passed through methane gas (flow 50sccm), and is heated to 1800 DEG C, in silicon
On the surface for the core that powder is formed, the interior coating layer that silicon carbide is formed is generated, silicon carbide general formula is SiC, at heat
After managing reaction 3 hours, stop supply methane gas, completes the preparation of interior coating layer.
Step 3：It is passed through methane gas (flow 80sccm, as carbon material predecessor) and ammonia again with rear chamber
(flow 20sccm, the source as N doping), and 1000 DEG C are heated to, in the interior coating layer of above-mentioned core
Surface on, generate an outer coating layer.After thermally treated reaction 3 hours, stops supply methane gas and ammonia and closing are anti-
Answer device.Methane gas can be not limited to by generating carbon source used in inside and outside two coating layer, can be arbitrary carbon-source gas, can also be made
With the solid mode of rich carbon macromolecule powder, such as：Polyimides (Polyimide, PI), polyvinyl alcohol (Polyvinyl
Alcohol, PVA), polyvinyl chloride (PolyVinyl Chloride, PVC) etc., will generate the core of interior coating layer with
Rich carbon macromolecule powder or slurry are with volume ratio 2:1 500 milliliters of (mL) N- methylpyrroles ketone solvents (NMP) of addition are simultaneously fully stirred
It mixes uniformly, leaves carbon after high-temp combustion later.
Step 4：Argon gas is finally passed through cavity (flow 50sccm), and after making its Temperature fall to room temperature, completes this
The preparation of the conducing composite material of embodiment, it is three layers of concentric structure, general formula Si/SiC/C to form section:N.
Embodiment 6-prepares conducing composite material general formula-core/interior coating layer/outer coating layer (Si/SiC/C：F)
Step 1：It chooses silicon powder (particle diameter distribution is 1nm~5 μm) and is used as core, and being placed on one can
The vacuum degree of the cavity vacuumized, cavity is evacuated to 5x10-4Hold in the palm ear (torr).Above-mentioned cavity can be the reaction of any tool heating
Device, as the explanation of embodiment 1 repeats no more.Above-mentioned silicon powder can be ball-shaped or irregular type.
Step 2：Then cavity is passed through methane gas (flow 50sccm), and is heated to 1800 DEG C, in silicon
On the surface for the core that powder is formed, the interior coating layer that silicon carbide is formed is generated, silicon carbide general formula is SiC, at heat
After managing reaction 3 hours, stop supply methane gas, completes the preparation of interior coating layer.
Step 3：It is passed through methane gas (flow 50sccm, as carbon material predecessor) and tetrafluoro again with rear chamber
Change carbon gas (flow 50sccm, the source as Fluorin doped) and be heated to 1000 DEG C, in above-mentioned core
On the surface of interior coating layer, an outer coating layer is generated.Other fluoro-gas, such as perfluor also can be selected in the source of above-mentioned Fluorin doped
Methane.After thermally treated reaction 3 hours, stop supply methane gas and carbon tetrafluoride gas and closing reactor.In generating,
Carbon source can be not limited to methane gas used in outer two coating layer, can be arbitrary carbon-source gas, rich carbon macromolecule also can be used
The solid mode of powder, such as：Polyimides (Polyimide, PI), gathers polyvinyl alcohol (Polyvinyl Alcohol, PVA)
Vinyl chloride (PolyVinyl Chloride, PVC) etc., will generate the core of interior coating layer and rich carbon macromolecule powder or
Slurry is with volume ratio 2:1 500 milliliters of (mL) N- methylpyrroles ketone solvents (NMP) of addition simultaneously stir, later high temperature
Carbon is left after burning.
Step 4：Argon gas is finally passed through cavity (flow 50sccm), and after making its Temperature fall to room temperature, completes this
The preparation of the conducing composite material of embodiment, it is three layers of concentric structure, general formula Si/SiC/C to form section：F.
Embodiment 7-- prepares negative electricity pole piece
The present embodiment is that the activity using the conducing composite material selected from one of embodiment 1-6 as battery cathode forms,
Preparation method is described in detail as after, step 1：Slurry needed for negative electricity pole piece is prepared first, and the polyvinylidene fluoride of 1.75g is sticked together
Agent (PVDF) is mixed into 35 milliliters of N- methylpyrroles ketone solvent (NMP), after being sufficiently stirred and being uniformly dispersed, can be formed and is in
The liquid of existing pellucidity.7 g of the conducing composite material according to above-described embodiment 1-6 is added, through being sufficiently stirred and disperseing
The grey mill base material of solid content 30% can be formed after even.Step 2：Negative electricity pole piece is prepared, the slurry that above-mentioned preparation is completed utilizes
Coating machine is coated on the copper clad laminate of 30 μm of thickness, slurry thickness be using scraper gap on the basis of 100 μm and
Slurry is enabled uniformly to be distributed on copper foil with stable promotion rate.Step 3：Negative electricity pole piece will be set after the completion of coating
It is put in high temperature oven, and 50 minutes are toasted to remove organic solvent with 90 DEG C of constant temperature, finally obtains tool high conductivity
Negative electricity pole piece.
Embodiment 8-- prepares the half-cell of lithium rechargeable battery
The glove box that the negative electricity pole piece that embodiment 7 is completed is sent into high purity argon environment carries out secondary battery
Dress, assembling spare part flow sequential be battery lower cover, lithium metal, isolation film (being made of isolated material), negative electricity pole piece,
Metal gasket, spring leaf, cell cover make wherein bubble must be infiltrated into electrolyte and removed when putting isolation film
Ion exchange can be carried out by obtaining between negative electricity pole piece and lithium metal.The group of above-mentioned electrolyte becomes ethylene carbonate (EC)：Diethyl
Base carbonic ether (DEC) is 1:Polyolefin can be selected in lithium hexafluoro phosphate (LiPF6) solution of 1 and concentration 1.2M, isolation membrane material
(Polyolefin), such as polyethylene (PE) or polypropylene (PP), and it is not subject to the limits.
Experimental example 1-- measures conducing composite material particle diameter distribution
The conducing composite material that embodiment 1-4 is completed uses Size Distribution Analyzer (label：Bettersize；
Model：BT-9300H SYSTEM) it is measured, Fig. 2A, 2B, 2C, 2D are please referred to, is respectively the grain that embodiment 1-4 is measured
Diameter distribution values and distribution map, wherein line chart correspond to Count (%), and histogram corresponds to Diff (%), and Count (%) is accumulative
Distribution percentage, Diff (%) are section distribution percentage；The Diff of the right reference axis is：Different destitution
(section percentage composition) refers to the content of each particle size, it obtains relevant distribution values after can integrating.1 (Si/ of embodiment
SiO0.8/C：N particle diameter distribution numerical value) is D3:1.77um D6:2.00um D10:2.22um D16:2.51um D25:
2.92um D50:4.09um D75:5.75um D84:6.66um D90:7.46um D97:8.93um D98:9.40um.Implement
2 (Si/SiO of example0.8/C:F particle diameter distribution numerical value) is D3:0.22um, D6:0.25um, D10:0.28um, D16:0.32um,
D25:0.36um, D50:0.47um, D75:0.62um, D84:0.71um, D90:0.80um, D97:1.03um D98:1.11um.
3 (Si/SiN of embodiment0.8/C:N particle diameter distribution numerical value) is D3:0.10um, D6:0.11um, D10:0.12um, D16:
0.13um, D25:0.14um, D50:0.19um, D75:0.35um, D84:0.43um, D90:0.50um, D97:0.67um, D98:
0.72um.4 (Si/SiN of embodiment0.8/C:F particle diameter distribution numerical value) is D3:0.13um, D6:0.16um, D10:0.21um,
D16:0.26um, D25:0.32um, D50:0.43um, D75:0.56um, D84:0.63um, D90:0.71um, D97:0.89um,
D98:0.95um.As a result it can be seen that the present invention conducing composite material particle diameter distribution can help promoted material initial capacitance,
The material circulation service life shows with fast charging and discharging.
Experimental example 2-- measures the specific surface area (BET) and Average Particle Diameters of conducing composite material
The conducing composite material that embodiment 1-4 is completed uses specific surface area analysis instrument (label：
Micromeritics；Model：ASAP-2020 it) is measured, please refers to table 1, be respectively 1 (Si/SiO of embodiment0.8/C：
N), 2 (Si/SiO of embodiment0.8/C：F), 3 (Si/SiN of embodiment0.8/C：) and 4 (Si/SiN of embodiment N0.8/C：Being averaged F)
Particle size and corresponding BET numerical value, from table 1, it can be seen that, the average grain diameter of conducing composite material of the invention becomes hour, BET
It can become big, can be reacted at this time with more lithium ions, reactivity improves, and helps and promotes material initial capacitance, material circulation longevity
Life is showed with fast charging and discharging.
Table 1
| Embodiment is numbered | Conducing composite material general formula | Average Particle Diameters (nm) | BET surface area (m2/g) |
| 1 | Si/SiOx/C：N (x=0.8) | 100.7 | 59.6 |
| 2 | Si/SiOx/C：F (x=0.8) | 91.4 | 65.7 |
| 3 | Si/SiNx/C：N (x=0.8) | 56.5 | 106.2 |
| 4 | Si/SiNx/C：F (x=0.8) | 67.1 | 89.4 |
Experimental example 3-- measures the electrical conductivity of conducing composite material
Conducing composite material (experimental example 3), (the commercially available negative material of comparative example 1 that embodiment 1 is completed；Manufacturer：
Sigma-Aldrich；Model：633097ALDRICH) and comparative example 2 (preparation method such as embodiment 1 but outer coating layer are not mixed
Composite material obtained by miscellaneous nitrogen), three uses analytical instrument (label：Keithley；Model：2400) it carries out measuring its conduction
Degree, please refers to Fig. 3, the slope in electrical conductivity figure is bigger, and it is higher to represent electrical conductivity.From the experimental results, 3 (Si/ of experimental example
SiO0.8/C：N electrical conductivity) is 1.36x 10-1S·cm-1；The electrical conductivity of comparative example 1 (pure silicon) is 2.21x 10-5S·cm-1；
2 (Si/SiO of comparative example0.8/ C) electrical conductivity be 7.353x 10-5S·cm-1, the electrical conductivity of experimental example 3 of the invention is significantly excellent
It is different, it respectively may be about 6000 times and 2 (Si/SiO of comparative example of comparative example 1 (pure silicon)0.8/ C) 2000 times.
Experimental example 4-measures the fast charging and discharging performance of lithium rechargeable battery
By 1 (Si/SiO of embodiment0.8/C：N conducing composite material) makes lithium ion two according to embodiment 7,8 steps
Primary cell, first by lithium rechargeable battery after 10 hours secondary complete charge/discharge cycles with reach fully loaded capacitance (0.1C, about
0.25 milliampere), is then tested and measured according to following condition：When being between room temperature and voltage 1mV~1.5V for 0.1C；
When for 0.2C, then represents and is tested using 0.5mA, and so on.When testing fast charging and discharging, take with cycle-index
Increase, charge-discharge velocity degree (C is higher) is gradually increased, and judge to show according to initial capacitance and capacity retention.1C represents 1
Hour completes charge or discharge, and 0.5C, which is represented, completes charge or discharge for 2 hours, and 2C is then represented 0.5 hour and completed charge or discharge,
C numerical value is higher, and it is faster to represent charge/discharge rates, shorter the time required to charge and discharge.Use analytical instrument (label：AcuTech
system；Model：BAT-750B it) carries out measuring the performance of its fast charging and discharging, referring to Fig. 4 and table 2, experimental result obtains
To 1 (Si/SiO of embodiment0.8/C：N the cycle-index 1-3 of the lithium rechargeable battery prepared by conducing composite material) is
0.05C, cycle-index 4-6 are 0.1C, and cycle-index 7-9 is 0.2C, and cycle-index 10-12 is 0.5C, and cycle-index 13-15 is
1C, cycle-index 16-18 are 2C, and cycle-index 19-23 is 0.1C, and cycle-index 24 is 0.05C.It can be obtained according to measurement
Know, lithium rechargeable battery of the invention can still have high initial capacitance when cycle-index and the increase of charge-discharge velocity degree
With high capacitance conservation rate, representing has the performance of preferable fast charging and discharging.In addition, last charge-discharge velocity be returned to 0.1C and
0.05C, the lithium rechargeable battery of the further evidence present invention is after fast charging and discharging, when returning to normal charge/discharge rates
When, high initial capacitance and high capacitance conservation rate can be still maintained, there is high stability and high security.
Table 2
Experimental example 5 and 6-measures the cycle life performance of lithium rechargeable battery
By 2 (Si/SiO of embodiment0.8/C：) and 3 (Si/SiN of embodiment F0.8/C：N conducing composite material) is according to implementation
Example 7,8 steps make the experimental example 5 of lithium rechargeable battery and the experimental example 6 of lithium rechargeable battery respectively.It will be real
Test example 5, experimental example 6, (the commercially available negative material of comparative example 3；Manufacturer：Sigma-Aldrich；Model：633097ALDRICH) with
And 4 (general formula of comparative example：Si/C, preparation method such as embodiment 1 but without interior coating layer and undope the lithium prepared by other elements from
Sub- secondary cell) after 10 hours secondary complete charge/discharge cycles to reach fully loaded capacitance (0.1C, about 0.25 milliampere), with
It is tested and is measured according to following condition afterwards：When being between room temperature and voltage 1mV~1.5V for 0.1C.Use analytical instrument
(label：AcuTech system；Model：BAT-750B its other cycle life performance) is measured, please refers to table 3, the present invention
The lithium rechargeable battery of experimental example 5,6 is substantially better than two comparative examples in capacity retention (%), when recycling 100 times, still has
The capacitance conservation rate for having 94% or more has no too big variation, and obvious to stablize relatively, this stability characteristic (quality) can have good cycle
Service life shows.
Table 3
In conclusion the conducing composite material of the present invention confirms there is high conductivity and high structural stability, led using this
Negative material prepared by composite and secondary cell also have excellent initial capacitance, high capacitance conservation rate, length
Cycle life, the performance of excellent fast charging and discharging.
It these are only the preferred embodiment of the present invention, be not intended to restrict the invention, for those skilled in the art
For member, the invention may be variously modified and varied.Any modification made by all within the spirits and principles of the present invention,
Equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (19)
1. a kind of conducing composite material, which is characterized in that it includes：
One core constitutes one of group first by being selected from the 4th major element (IVA), metal, metallic compound or alloy
Material is formed；
Coating layer in one is coated on the surface of the core and by oxide, nitride selected from first material
Or prepared by the group of carbide composition；And
One outer coating layer is coated on the surface of the interior coating layer and for carbon material and at least one containing halogen or the
Prepared by second material of five major elements (VA).
2. conducing composite material as described in claim 1, which is characterized in that the core is configured as powder.
3. conducing composite material as claimed in claim 2, which is characterized in that the powder for wherein forming the core is selected from not
Regular pattern composite or ball-shaped.
4. conducing composite material as claimed in claim 2, which is characterized in that the particle size of the wherein described conducing composite material
For PS, meet following condition：0.01μm≤PS≤10μm.
5. conducing composite material as described in claim 1, which is characterized in that the core is configured as sheet or rodlike.
6. conducing composite material as described in claim 1, which is characterized in that the core is made of silicon.
7. conducing composite material as claimed in claim 6, which is characterized in that the core is made of silicon, it is described in drape over one's shoulders
Coating is made of the oxide of silicon, and second material of the outer coating layer by carbon material and containing nitrogen forms, described to lead
Composite is with general formula Si/SiOx/C:N indicates that wherein x meets following condition：0.3≤x≤1.5.
8. conducing composite material as claimed in claim 6, which is characterized in that the core is made of silicon, it is described in drape over one's shoulders
Coating is made of the oxide of silicon, and second material of the outer coating layer by carbon material and containing fluorine forms, described to lead
Composite is with general formula Si/SiOx/C:F indicates that wherein x meets following condition：0.3≤x≤1.5.
9. conducing composite material as claimed in claim 6, which is characterized in that the core is made of silicon, it is described in drape over one's shoulders
Coating is made of the nitride of silicon, and second material of the outer coating layer by carbon material and containing nitrogen forms, described to lead
Composite is with general formula Si/SiNx/C:N indicates that wherein x meets following condition：0.1≤x≤0.8.
10. conducing composite material as claimed in claim 6, which is characterized in that the core is made of silicon, it is described in drape over one's shoulders
Coating is made of the nitride of silicon, and second material of the outer coating layer by carbon material and containing fluorine forms, described to lead
Composite is with general formula Si/SiNx/C:F indicates that wherein x meets following condition：0.1≤x≤0.8.
11. conducing composite material as claimed in claim 6, which is characterized in that the core is made of silicon, it is described in drape over one's shoulders
Coating is made of the carbide of silicon, and second material of the outer coating layer by carbon material and containing nitrogen forms, described to lead
Composite is with general formula Si/SiC/C:N is indicated.
12. conducing composite material as claimed in claim 6, which is characterized in that the core is made of silicon, it is described in drape over one's shoulders
Coating is made of the carbide of silicon, and second material of the outer coating layer by carbon material and containing fluorine forms, described to lead
Composite is with general formula Si/SiC/C:F is indicated.
13. conducing composite material as claimed in claim 2, which is characterized in that the specific surface area of the conducing composite material is
BET meets following condition：The meters squared per grams of BET≤60.
14. conducing composite material as described in claim 1, which is characterized in that the electrical conductivity of the conducing composite material is with ED
It indicates, meets following condition：ED≧1.0x10-2S·cm-1。
15. a kind of negative material, which is characterized in that it includes conducing composite material as described in claim 1.
16. a kind of secondary cell, which is characterized in that it includes：
One contains the cathode of conducing composite material as described in claim 1；
One anode；
One isolated material；And
Electrolyte.
17. secondary cell as claimed in claim 16, which is characterized in that the secondary cell is lithium rechargeable battery.
18. secondary cell as claimed in claim 16, which is characterized in that the secondary cell in 0.5 hour complete charging or
The initial capacitance of electric discharge is indicated with IC, meets following condition：IC≧1700mAh/g.
19. secondary cell as claimed in claim 16, which is characterized in that the capacity retention (%) of the secondary cell with
MC100 indicates that the percentage of capacitance when being the 100th charge and discharge divided by capacitance when the 1st charge and discharge meets
Following condition：MC100≤90%.
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