CN106784833A - Silicon-carbon cathode material and preparation method thereof - Google Patents
Silicon-carbon cathode material and preparation method thereof Download PDFInfo
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- CN106784833A CN106784833A CN201611218746.5A CN201611218746A CN106784833A CN 106784833 A CN106784833 A CN 106784833A CN 201611218746 A CN201611218746 A CN 201611218746A CN 106784833 A CN106784833 A CN 106784833A
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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
- 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
- H01M4/362—Composites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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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- 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
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- 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
Silicon-carbon cathode material of the present invention and preparation method thereof is related to a kind of silicon-carbon cathode material suitable for lithium ion battery and preparation method thereof.Its purpose is to provide a kind of silicon-carbon cathode material for lithium ion battery negative with and preparation method thereof, the characteristics of the material has first charge-discharge efficiency high, cycle performance and rate charge-discharge excellent performance and relatively low Volumetric expansion；The method is simple to operate, raw material is easy to get, equipment is cheap, it is easy to continuous production.Silicon-carbon cathode material in the present invention, its specific capacity is made up of in 500mAh/g~1200mAh/g nano-silicon, micron graphite and organic cracking carbon, and the mass percent of nano-silicon is 8%~35%.The preparation method of the silicon-carbon cathode material in the present invention, in organic carbon matrix precursor, silicon-carbon cathode material is obtained through drying, compacting, broken, classification, cladding and sintering by by nano-silicon obtained in melten salt electriochemistry method and graphite dispersion.
Description
Technical field
The present invention relates to a kind of silicon-carbon cathode material for lithium ion battery and preparation method thereof, belong to electrochemical energy
Field of material technology.
Background technology
Lithium rechargeable battery extensive use in electronic equipment of various.As the development of electronic equipment is to its dynamical system
The requirement sharp increase of the demand and performance of system-electrochmical power source, most of commercial Li-ion batteries have comprising such as graphite material
The anode of material, the material introduces lithium when charging by inserting mechanism.This insert type anode shows preferable cycle life
And coulombic efficiency, but relatively low theoretical capacity (372mAh/g) is constrained to it is difficult to improve battery by battery preparation technique
Performance.
The Equations of The Second Kind anode material such as Si, Sn and Sb, it introduces lithium when charging by alloying mechanism, is high power capacity anode
The preferable selection of material, wherein silicon have than widely used carbon material more than 10 times theoretical electrochemistry capacity (4200mAh/g),
Low embedding lithium voltage (being less than 0.5V), telescopiny does not exist the common insertion of solvent molecule, in the earth's crust the advantages of rich content.
But silicon materials show relatively poor cycle life and coulombic efficiency as anode, main cause is silicon materials conductive in itself
Poor performance, and the serious bulk effect (volume change produced in electrochemistry removal lithium embedded process：280%~310%), produce
Internal stress cause the destruction of material structure, between causing electrode material, electrode material and conductive agent (such as carbon) and adhesive, electricity
Pole material is separated with collector, and then loses electrical contact, causes the cycle performance of electrode to accelerate to decline.
At present it has been proposed that the method for solving this problem mainly has two kinds：A kind of method is by silicon nanosizing.Because with
The reduction of particle, the Volume Changes of silicon can be reduced to a certain extent, reduce electrode interior stress, but nano material is being followed
Easily reunite during ring, be insufficient to allow the performance improvement of battery to practical.Another method is using materials such as silicon and metals
Compound, the nano-silicon and the good metal material of electric conductivity will with electro-chemical activity are combined.One side metal material can be with
Improve the electric conductivity of silicon materials, another aspect metal material can disperse as " cushioning frame " and buffer silicon materials in deintercalation
Internal stress during lithium produced by Volume Changes, makes silicon metallic composite have good cycle performance.
(the Nano Lett., 2009,9 such as Cui Y:3370-3374, WO2010/138617) use chemical vapour deposition technique
Kernel is prepared for crystalline silicon, outer layer for the silicon nanowires of the nucleocapsid structure of non-crystalline silicon is used for lithium ion battery negative material, should
Crystalline silicon kernel serves as the skeleton in charge and discharge process in nucleocapsid structure silicon materials, amorphous outer silicon as embedding de- lithium activity
Material, cyclical stability of the silicon nanowires with this architectural feature in charge and discharge process is improved.Esmanski
A etc. prepares three-dimensional porous carbon coating silicon composite structure silicon materials (Adv.Funct.Mater., 2009,19 using template:
1999-2010) when as lithium ion battery negative material, carbon coating can suppress the volumetric expansion of silicon materials, while three-dimensional porous
Structure also can bulk effect of the capacity silicon materials during charge and discharge cycles, with good cyclical stability.Yang Juanyu etc. is adopted
Used with silica and carbon common electrolytic preparation nano-silicone wire/carbon composite material (see patent document of ZL201210442906.X)
Do negative material, nano-silicon and carbon In-situ reaction with firm combination, solve what nano-silicon and carbon in cyclic process departed from
Problem, it is ensured that the structural stability of material, but more silica present in material and carborundum are to chemical property shadow
Sound is larger.The studies above shows, these silicon-carbon cathode materials or due to being all that nano-silicon is deposited on carbon base body, between silicon and carbon
Combination be only a kind of physical bond, due to silicon materials bulk effect in itself, with the carrying out of circulation, between silicon and carbon
Physical bond can become worse and worse, and the separation for ultimately resulting in silicon and carbon material loses electrical contact so that the stable circulation of material
Property be deteriorated, or because nano-silicon is exposed in electrolyte, the huge specific surface area of nano-silicon and electrolysis during circulating battery
Liquid contact and sustained response, cause the loss of electrolyte and active material, ultimately result in the decline of cycle performance.In addition, at present
Preparing these silicon-carbon cathode material methods mainly includes chemical vapour deposition technique, thermal vapor deposition method, Pintsch process, high-energy ball milling
Etc. method.
Although researcher is combined by nanosizing and silicon-carbon and solves the penalty that the Volume Changes of silicon materials bring and ask
Topic, but insertion of the lithium ion in silicon materials necessarily causes volumetric expansion, i.e. high power capacity to bring highly expanded, and this highly expanded is special
Property cause that height ratio capacity silica-base material cannot meet requirement prepared by existing lithium ion battery, the battery that such as volumetric expansion high brings
Volumetric expansion, such as meets the electrolyte storage problem that the high porosity of silicon expansion brings.
The content of the invention
It is an object of the invention to provide a kind of silicon-carbon cathode material for lithium ion battery negative, the material has head
Secondary efficiency for charge-discharge is high, cycle performance and the characteristics of rate charge-discharge excellent performance and relatively low Volumetric expansion.The present invention
Another object be that a kind of preparation method of the silicon-carbon cathode material is provided, the method is simple to operate, raw material is easy to get, equipment
Cheaply, it is easy to continuous production.
Silicon-carbon cathode material in the present invention, the silicon-carbon cathode material specific capacity 500mAh/g to 1200mAh/g it
Between, the silicon-carbon cathode material is made up of nano-silicon, micron graphite and organic cracking carbon, and the mass percent of the nano-silicon exists
Between 8% to 35%, nano-silicon is that nano silicon is obtained by melten salt electriochemistry reduction, and organic cracking carbon is by being added with
Machine carbon matrix precursor is obtained by Pintsch process again.
Silicon-carbon cathode material in the present invention, wherein the specific capacity of the silicon-carbon cathode material is arrived for 600mAh/g
Between 1000mAh/g, the mass percent of nano-silicon is 12-28%.
Silicon-carbon cathode material in the present invention, wherein the silicon-carbon cathode material has nano-silicon, graphite and organic cracking
The interior three-dimensional loose structure of carbon composition and the outside densification clad structure of organic cracking carbon composition.
Silicon-carbon cathode material in the present invention, wherein organic carbon matrix precursor needed for the interior three-dimensional loose structure is phenolic aldehyde
Resin, furfural resin, epoxy resin, hydroxyethyl cellulose, polyvinyl butyral resin, polyvinylpyrrolidone, polyethylene glycol, sugarcane
At least one in sugar, glucose.
Silicon-carbon cathode material in the present invention, wherein organic carbon matrix precursor needed for the outside densification clad structure is dripped for coal
At least one in blue or green, asphalt.
Silicon-carbon cathode material in the present invention, wherein the nano-silicon is nano silicon being reduced by melten salt electriochemistry
The method for obtaining is as follows：Porous blocks using nano grade silica particles composition as negative electrode, using graphite or inert anode as
Anode, with CaCl2Or with CaCl2Based on mixed salt melt constitute electrolytic cell as electrolyte, apply straight between a cathode and an anode
Stream voltage, controls electrolytic current density and electrolysis electricity so that the silica negative electrode in-situ electrolysis reduction in porous blocks, system
Obtain the nano-silicon.
Silicon-carbon cathode material in the present invention, wherein the SiO 2 powder particle diameter is 10nm to 1 μm.
The preparation method of the silicon-carbon cathode material in the present invention, comprises the following steps：
(1) in the organic carbon matrix precursor for building organic cracking carbon of three-dimensional porous structure being dissolved in into water or organic solvent；
(2) the specific capacity requirement according to material, determines that silicon-carbon cathode material is constituted, according to result of calculation by certain mass
The graphite dispersion of nano-silicon and certain mass by stirring, is then dried in the solution of step (1), obtains being produced in the middle of first
Thing；
(3) the first intermediate product that step (2) is obtained is carried out into isostatic cool pressing compacting；
(4) the isostatic cool pressing compacting block for obtaining step (3) is crushed and is classified, and obtains the second intermediate product；
(5) the second intermediate product is well mixed with cladding with organic carbon matrix precursor, is placed in solid phase reactor and is wrapped
Cover, obtain the 3rd intermediate product；
(6) the 3rd intermediate product is placed in sintering furnace, under protective atmosphere, roasting, insulation, cooling obtains described
Silicon-carbon cathode material.
In above-mentioned preparation method, in the step (3), the pressure of isostatic cool pressing compacting is 100-200MPA.
In above-mentioned preparation method, in the step (6), the temperature of roasting is 800~1100 DEG C.
In above-mentioned preparation method, in the step (6), the time of insulation is 1~10 hour.
It is phenolic resin, furfural tree as the organic carbon matrix precursor for building three-dimensional porous structure in above-mentioned preparation method
In fat, epoxy resin, hydroxyethyl cellulose, polyvinyl butyral resin, polyvinylpyrrolidone, polyethylene glycol, sucrose, glucose
At least one.
With organic carbon matrix precursor it is at least one in pitch, acetylene, ethene as cladding in above-mentioned preparation method.
Pitch is at least one in selected from coal tar pitch and petroleum asphalt.
Lithium ion battery in the present invention, the battery includes positive pole, negative pole and nonaqueous electrolytic solution, and the negative pole includes above-mentioned
Silicon-carbon cathode material.
The advantage of the invention is that：
Silicon-carbon cathode material in the present invention obtains the controllable silicon-carbon cathode material of specific capacity by controlling silicone content, protects
The volumetric expansion for demonstrate,proving silicon-carbon cathode material meets lithium ion battery preparation demand, and with high specific capacity and excellent cycle
Energy.The silicon-carbon cathode material is made up of organic cracking carbon, nano-silicon and graphite, and cracking carbon is formed closely between graphite and silicon
With reference to both having maintained the electrical contact that the bulk effect of silicon in turn ensure that between silicon and graphite, and formed between silicon/carbon graphite
Three-dimensional porous structure can effectively absorb the silicon impact of Volume Changes to electrode structure during removal lithium embedded, outside densification
Clad has effectively completely cut off infiltration of the electrolyte to internal void, that is, avoid silicon and meet again with the directly contact reaction of electrolyte
The demand of battery preparation technique, so as to improving the performance of battery.
The invention will be further described below in conjunction with the accompanying drawings.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of the nano-silicon that the embodiment of the present invention 1 is obtained；
Fig. 2 is the scanning electron microscope (SEM) photograph of the silicon-carbon cathode material that the embodiment of the present invention 1 is obtained；
Fig. 3 is the X ray diffracting spectrum of the silicon-carbon cathode material that the embodiment of the present invention 1 is obtained.
Specific embodiment
Silicon-carbon cathode material in the present invention, the silicon-carbon cathode material specific capacity 500mAh/g to 1200mAh/g it
Between, the silicon-carbon cathode material is made up of nano-silicon, micron graphite and organic cracking carbon, and the mass percent of the nano-silicon exists
Between 8% to 35%, remaining is micron graphite and organic cracking carbon, and micron graphite and organic cracking carbon can match somebody with somebody for any quality
Than nano-silicon is that nano silicon is obtained by melten salt electriochemistry reduction, and organic cracking carbon is by adding organic carbon matrix precursor
Obtained by Pintsch process again.
Silicon-carbon cathode material in the present invention, wherein the specific capacity of the silicon-carbon cathode material is arrived for 600mAh/g
Between 1000mAh/g, the mass percent of nano-silicon is 12-28%.
Silicon-carbon cathode material in the present invention, wherein the silicon-carbon cathode material has nano-silicon, graphite and organic cracking
The interior three-dimensional loose structure of carbon composition and the outside densification clad structure of organic cracking carbon composition.
Silicon-carbon cathode material in the present invention, wherein organic carbon matrix precursor needed for the interior three-dimensional loose structure is phenolic aldehyde
Resin, furfural resin, epoxy resin, hydroxyethyl cellulose, polyvinyl butyral resin, polyvinylpyrrolidone, polyethylene glycol, sugarcane
At least one in sugar, glucose.
Silicon-carbon cathode material in the present invention, wherein organic carbon matrix precursor needed for the outside densification clad structure is dripped for coal
At least one in blue or green, asphalt.
Silicon-carbon cathode material in the present invention, wherein the nano-silicon is nano silicon being reduced by melten salt electriochemistry
The method for obtaining is as follows：Porous blocks using nano grade silica particles composition as negative electrode, using graphite or inert anode as
Anode, with CaCl2Or with CaCl2Based on mixed salt melt constitute electrolytic cell as electrolyte, apply straight between a cathode and an anode
Stream voltage, controls electrolytic current density and electrolysis electricity so that the silica negative electrode in-situ electrolysis reduction in porous blocks, system
Obtain the nano-silicon.
Silicon-carbon cathode material in the present invention, wherein the SiO 2 powder particle diameter is 10nm to 1 μm.
The preparation method of the silicon-carbon cathode material in the present invention, comprises the following steps：
(1) in the organic carbon matrix precursor for building organic cracking carbon of three-dimensional porous structure being dissolved in into water or organic solvent；
(2) the specific capacity requirement according to material, determines that silicon-carbon cathode material is constituted, according to result of calculation by certain mass
The graphite dispersion of nano-silicon and certain mass by stirring, is then dried in the solution of step (1), obtains being produced in the middle of first
Thing；
(3) the first intermediate product that step (2) is obtained is carried out into isostatic cool pressing compacting；
(4) the isostatic cool pressing compacting block for obtaining step (3) is crushed and is classified, and obtains the second intermediate product；
(5) the second intermediate product is well mixed with cladding with organic carbon matrix precursor, is placed in solid phase reactor and is wrapped
Cover, obtain the 3rd intermediate product；
(6) the 3rd intermediate product is placed in sintering furnace, under protective atmosphere, roasting, insulation, cooling obtains described
Silicon-carbon cathode material.
In above-mentioned preparation method, the addition of nano-silicon is calculated according to silicone content 12-28% in final product and added.
It is phenolic resin, furfural tree as the organic carbon matrix precursor for building three-dimensional porous structure in above-mentioned preparation method
In fat, epoxy resin, hydroxyethyl cellulose, polyvinyl butyral resin, polyvinylpyrrolidone, polyethylene glycol, sucrose, glucose
At least one.
With organic carbon matrix precursor it is at least one in pitch, acetylene, ethene as cladding in above-mentioned preparation method.
Pitch is at least one in selected from coal tar pitch and petroleum asphalt.
The group of one or more in ethanol, ethylene glycol, isopropanol, acetone, hexamethylene can be selected as organic solvent
Close.
Natural flake graphite, micro crystal graphite, spherical natural graphite, Delanium or intermediate-phase carbon can be selected as graphite
The combination of one or more in microballoon.In the step (2), nano-silicon passes through melten salt electriochemistry method reduced nano dioxy
SiClx is obtained.
In the step (2), drying means can select one or two the group in convection drying or spray drying
Close.
In the step (3), the pressure of isostatic cool pressing compacting is 100-200MPA.
In the step (6), protective atmosphere can select in nitrogen, argon gas, helium, neon, Krypton, xenon
Plant or several combinations, preferably nitrogen, argon gas or the mixed gas of the two.
In the step (6), the temperature of roasting is 800~1100 DEG C, preferably 800~1000 DEG C.
In the step (6), the time of insulation is 1~10 hour.
Lithium ion battery in the present invention, the battery includes positive pole, negative pole and nonaqueous electrolytic solution, and the negative pole includes above-mentioned
Silicon-carbon cathode material.
Silicon-carbon cathode material in the present invention obtains the controllable silicon-carbon cathode material of specific capacity by controlling silicone content, protects
The volumetric expansion for demonstrate,proving silicon-carbon cathode material meets lithium ion battery preparation demand, and with high specific capacity and excellent cycle
Energy.The silicon-carbon cathode material is made up of organic cracking carbon, nano-silicon and graphite, and cracking carbon is formed closely between graphite and silicon
With reference to both having maintained the electrical contact that the bulk effect of silicon in turn ensure that between silicon and graphite, and formed between silicon/carbon graphite
Three-dimensional porous structure can effectively absorb the silicon impact of Volume Changes to electrode structure during removal lithium embedded, outside densification
Clad has effectively completely cut off infiltration of the electrolyte to internal void, that is, avoid silicon and meet again with the directly contact reaction of electrolyte
The demand of battery preparation technique, so as to improving the performance of battery.
The invention will be further described by the following examples, but the present invention is not limited to following examples.
Embodiment 1
10g polyvinylpyrrolidones are dissolved in 50mL ethanol, 30min is stirred；Weigh the line that 4g average diameters are 100nm
Shape nano-silicon, is slowly added in above-mentioned solution, stirs 1h；The crystalline flake graphite that 10g average grain diameters are 2 μm is weighed, is slowly added to
State in solution, stir 3h；Above-mentioned solution is placed in 70 DEG C of blast dry ovens and dries 2h, obtain the first intermediate product.
By above-mentioned first intermediate product loaded in sealing silica gel sheath, it is placed in cold isostatic press, pressure 150MPa, pressurize 5
Minute.
The block of compacting is placed in mechanical crusher and is crushed, and be classified using air current classifying, obtain D50=
10-20 μm of the second intermediate product.
Second intermediate product about 14g is well mixed with asphalt 6g, is placed in solid phase reactor, entered under 500 degree
Row cladding, reaction time 6h obtains the 3rd intermediate product after cooling.
3rd intermediate product is placed in tube furnace flat-temperature zone, argon gas is passed through, gas flow is 200mL/min, according to 10 DEG C/
Min speed is warmed up to 900 DEG C, and sample is taken out in constant temperature 2h, furnace cooling to room temperature.The sieving of above-mentioned sample is lithium-ion electric
Pond silicon-carbon cathode material.
Silicon is wire nano-silicon as can see from Figure 1, Fig. 2 and shows that the carbon coating layer for having one layer of densification is placed in three-dimensional
Outside loose structure, Fig. 3 is the X ray diffracting spectrum of the silicon-carbon cathode material for obtaining.
Gained negative material prepares lithium ion cell electrode as follows：With obtained electrolysate nano-silicone wire/carbon negative pole
Material is active material, and Super-P carbon blacks are conductive agent, and CMC/SBR is binding agent, after in mass ratio 8: 1: 1 is well mixed, is used
Deionized water is sized mixing for solvent, and slurry is coated on the Copper Foil of 8 μ m-thicks the pole piece for being made 1.0cm × 1.5cm, in 60 DEG C of dryings
Back roller is depressed into thickness needed for pole piece, and 12h is dried under 120 DEG C of vacuum, standby.It is to electrode, Celgard with metal lithium sheet
2300 films are barrier film, and 1mol/L LiPF6/EC+DEC+DMC (volume ratio 1: 1: 1) (voluntarily set for electrolyte assembling experimental cell
Meter, diameter of phi=30mm, L=100mm long).With the charge and discharge of blue electricity battery test system CT2001A tester test experiments batteries
Electrical property.Charging/discharging voltage scope is 0.005~2.0V, charging and discharging currents density 80mA/g, tests the circulating battery appearance of 100 weeks
Amount conservation rate C100/C1.
Embodiment 2
10g polyvinylpyrrolidones are dissolved in 50mL ethanol, 30min is stirred；Weigh the line that 2g average diameters are 100nm
Shape nano-silicon, is slowly added in above-mentioned solution, stirs 1h；The crystalline flake graphite that 10g average grain diameters are 2 μm is weighed, is slowly added to
State in solution, stir 3h；Above-mentioned solution is placed in 70 DEG C of blast dry ovens and dries 2h, obtain the first intermediate product.
By above-mentioned first intermediate product loaded in sealing silica gel sheath, it is placed in cold isostatic press, pressure 180MPa, pressurize 5
Minute.
The block of compacting is placed in mechanical crusher and is crushed, and be classified using air current classifying, obtain D50=
10-20 μm of the second intermediate product.
Second intermediate product about 13g is well mixed with medium temperature coal pitch 6g, is placed in solid phase reactor, under 500 degree
Coated, reaction time 6h obtains the 3rd intermediate product after cooling.
3rd intermediate product is placed in tube furnace flat-temperature zone, argon gas is passed through, gas flow is 200mL/min, according to 10 DEG C/
Min speed is warmed up to 1000 DEG C, and sample is taken out in constant temperature 2h, furnace cooling to room temperature.The sieving of above-mentioned sample is lithium-ion electric
Pond silicon-carbon cathode material.
Gained negative material prepares electrode according to method same as Example 1, carries out electrochemical property test.
Embodiment 3
20g polyvinylpyrrolidones are dissolved in 50mL ethanol, 30min is stirred；Weigh the line that 3g average diameters are 100nm
Shape nano-silicon, is slowly added in above-mentioned solution, stirs 1h；The MCMB graphite that 10g average grain diameters are 2 μm is weighed, is delayed
Slowly add in above-mentioned solution, stir 3h；Above-mentioned solution is placed in 70 DEG C of blast dry ovens and dries 2h, obtain being produced in the middle of first
Thing.
By above-mentioned first intermediate product loaded in sealing silica gel sheath, it is placed in cold isostatic press, pressure 200MPa, pressurize 5
Minute.
The block of compacting is placed in mechanical crusher and is crushed, and be classified using air current classifying, obtain D50=
10-20 μm of the second intermediate product.
Second intermediate product about 17g is well mixed with high temperature asphalt 6g, is placed in solid phase reactor, at 500 degree
Under coated, reaction time 6h obtains the 3rd intermediate product after cooling.
3rd intermediate product is placed in tube furnace flat-temperature zone, argon gas is passed through, gas flow is 200mL/min, according to 10 DEG C/
Min speed is warmed up to 1000 DEG C, and sample is taken out in constant temperature 2h, furnace cooling to room temperature.The sieving of above-mentioned sample is lithium-ion electric
Pond silicon-carbon cathode material.
Gained negative material prepares electrode according to method same as Example 1, carries out electrochemical property test.
Embodiment 4
20g polyvinylpyrrolidones are dissolved in 50mL ethanol, 30min is stirred；Weigh the line that 4g average diameters are 100nm
Shape nano-silicon, is slowly added in above-mentioned solution, stirs 1h；The crystalline flake graphite that 10g average grain diameters are 3 μm is weighed, is slowly added to
State in solution, stir 3h；Above-mentioned solution is placed in 70 DEG C of blast dry ovens and dries 2h, obtain the first intermediate product.
By above-mentioned first intermediate product loaded in sealing silica gel sheath, it is placed in cold isostatic press, pressure 120MPa, pressurize 5
Minute.
The block of compacting is placed in mechanical crusher and is crushed, and be classified using air current classifying, obtain D50=
10-20 μm of the second intermediate product.
Second intermediate product about 18g is well mixed with coal tar pitch 6g, is placed in solid phase reactor, under 550 degree
Coated, reaction time 6h obtains the 3rd intermediate product after cooling.
3rd intermediate product is placed in tube furnace flat-temperature zone, argon gas is passed through, gas flow is 200mL/min, according to 10 DEG C/
Min speed is warmed up to 1000 DEG C, and sample is taken out in constant temperature 2h, furnace cooling to room temperature.The sieving of above-mentioned sample is lithium-ion electric
Pond silicon-carbon cathode material.
Gained negative material prepares electrode according to method same as Example 1, carries out electrochemical property test.
Embodiment 5
20g polyvinylpyrrolidones are dissolved in 50mL ethanol, 30min is stirred；It is 100nm's to weigh 2.5g average diameters
Wire nano-silicon, is slowly added in above-mentioned solution, stirs 1h；The Delanium that 10g average grain diameters are 5 μm is weighed, is slowly added to
In above-mentioned solution, 3h is stirred；Above-mentioned solution is placed in 70 DEG C of blast dry ovens and dries 2h, obtain the first intermediate product.
By above-mentioned first intermediate product loaded in sealing silica gel sheath, it is placed in cold isostatic press, pressure 180MPa, pressurize 5
Minute.
The block of compacting is placed in mechanical crusher and is crushed, and be classified using air current classifying, obtain D50=
10-20 μm of the second intermediate product.
Second intermediate product about 20g is well mixed with middle fire stons oil asphalt 6g, is placed in solid phase reactor, at 550 degree
Under coated, reaction time 6h obtains the 3rd intermediate product after cooling.
3rd intermediate product is placed in tube furnace flat-temperature zone, argon gas is passed through, gas flow is 200mL/min, according to 10 DEG C/
Min speed is warmed up to 900 DEG C, and sample is taken out in constant temperature 2h, furnace cooling to room temperature.The sieving of above-mentioned sample is lithium-ion electric
Pond silicon-carbon cathode material.
Gained negative material prepares electrode according to method same as Example 1, carries out electrochemical property test.
The electrochemical property test result of embodiment is contrasted, as a result as shown in table 1.Be can be seen that from following table
Silicon-carbon cathode material for lithium ion battery negative disclosed by the invention has good chemical property, specific capacity and efficiency
All reach the international most advanced level of like product.
The chemical property of the nano-silicone wire/carbon negative material of table 1
Embodiment described above is only that the preferred embodiment of the present invention is described, not to model of the invention
Enclose and be defined, on the premise of design spirit of the present invention is not departed from, those of ordinary skill in the art are to technical side of the invention
Various modifications and improvement that case is made, all should fall into the protection domain of claims of the present invention determination.
Claims (12)
1. a kind of silicon-carbon cathode material, it is characterised in that：The silicon-carbon cathode material specific capacity is in 500mAh/g to 1200mAh/g
Between, the silicon-carbon cathode material is made up of nano-silicon, micron graphite and organic cracking carbon, the mass percent of the nano-silicon
Between 8% to 35%, nano-silicon is that nano silicon is obtained by melten salt electriochemistry reduction, and organic cracking carbon is by addition
Organic carbon matrix precursor is obtained by Pintsch process again.
2. silicon-carbon cathode material according to claim 1, it is characterised in that：The specific capacity of the silicon-carbon cathode material is
Between 600mAh/g to 1000mAh/g, the mass percent of nano-silicon is 12-28%.
3. silicon-carbon cathode material according to claim 1 and 2, it is characterised in that：The silicon-carbon cathode material has nanometer
The interior three-dimensional loose structure of silicon, graphite and organic cracking carbon composition and the outside fine and close cladding knot of organic cracking carbon composition
Structure.
4. silicon-carbon cathode material according to claim 3, it is characterised in that：It is organic needed for the interior three-dimensional loose structure
Carbon matrix precursor is phenolic resin, furfural resin, epoxy resin, hydroxyethyl cellulose, polyvinyl butyral resin, polyvinylpyrrolidine
At least one in ketone, polyethylene glycol, sucrose, glucose.
5. silicon-carbon cathode material according to claim 3, it is characterised in that：It is organic needed for the outside densification clad structure
Carbon matrix precursor is at least one in selected from coal tar pitch and petroleum asphalt.
6. the silicon-carbon cathode material according to any one of Claims 1 to 5, it is characterised in that：The nano-silicon is nanometer two
Silica is as follows by the method that melten salt electriochemistry reduction is obtained：Porous blocks using nano grade silica particles composition are used as the moon
Pole, using graphite or inert anode as anode, with CaCl2Or with CaCl2Based on mixed salt melt as electrolyte constitute be electrolysed
Groove, applies DC voltage between a cathode and an anode, controls electrolytic current density and electrolysis electricity so that in porous blocks two
Silica negative electrode in-situ electrolysis is reduced, and the nano-silicon is obtained.
7. silicon-carbon cathode material according to claim 6, it is characterised in that：The SiO 2 powder particle diameter be 10nm extremely
1μm。
8. the preparation method of silicon-carbon cathode material any one of a kind of claim 1~7, it is characterised in that including as follows
Step：
(1) in the organic carbon matrix precursor described in claim 4 being dissolved in into water or organic solvent；
(2) the specific capacity requirement according to material, determines that silicon-carbon cathode material is constituted, according to result of calculation by the nanometer of certain mass
The graphite dispersion of silicon and certain mass by stirring, is then dried in the solution of step (1), obtains the first intermediate product；
(3) the first intermediate product that step (2) is obtained is carried out into isostatic cool pressing compacting；
(4) the isostatic cool pressing compacting block for obtaining step (3) is crushed and is classified, and obtains the second intermediate product；
(5) the second intermediate product is well mixed with the organic carbon matrix precursor described in claim 5, is placed in solid phase reactor
Coated, obtained the 3rd intermediate product；
(6) the 3rd intermediate product is placed in sintering furnace, under protective atmosphere, roasting, insulation, cooling obtains the silicon-carbon
Negative material.
9. the preparation method of silicon-carbon cathode material according to claim 8, it is characterised in that：It is cold etc. in the step (3)
The pressure of static pressure compacting is 100-200MPA.
10. the preparation method of silicon-carbon cathode material according to claim 9, it is characterised in that：In the step (6), roasting
The temperature of burning is 800~1100 DEG C.
The preparation method of 11. silicon-carbon cathode materials according to claim 10, it is characterised in that：In the step (6), protect
The time of temperature is 1~10 hour.
A kind of 12. lithium ion batteries, the battery includes positive pole, negative pole and nonaqueous electrolytic solution, it is characterised in that：The negative pole includes
Silicon-carbon cathode material any one of claim 1-7.
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