CN108682829A - A kind of preparation method of nitrogen-doped carbon coated Si composite graphite material - Google Patents

A kind of preparation method of nitrogen-doped carbon coated Si composite graphite material Download PDF

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CN108682829A
CN108682829A CN201810592149.1A CN201810592149A CN108682829A CN 108682829 A CN108682829 A CN 108682829A CN 201810592149 A CN201810592149 A CN 201810592149A CN 108682829 A CN108682829 A CN 108682829A
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nitrogen
doped carbon
organic acid
preparation
carbon coated
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CN108682829B (en
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康飞宇
谌芳园
贺艳兵
何中林
王鹏
武洪彬
李宝华
程光春
林平
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Hubei Rongtong High Tech Advanced Materials Group Co ltd
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Hubei Rong Tong Hi Tech Advanced Materials Co Ltd
Shenzhen Graduate School Tsinghua University
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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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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 belongs to technical field of lithium ion, are related to a kind of preparation method of nitrogen-doped carbon coated Si composite graphite material, include the following steps：Using melamine as nitrogen source, organic acid is carbon source, and modified graphene is conductive bridge, and melamine, organic acid, modified graphene are uniformly mixed with nano-silicon suspension, then add graphite, is uniformly mixed, dry；The dried material mixed is ground up, sieved, is then transferred the material into rotary furnace, inert atmosphere is passed through, is heated to 100 ~ 500 DEG C, silicon nanoparticle be embedded in melamine in generated in-situ functional structure component after organic acid, modified graphite alkene reaction；Then proceed to heating carbonization.Compared with the existing technology, the present invention uses situ Nitrogen Doping carbon coating silicon composite graphite material, and to obtain Si-C composite material, the cycle performance of the material promotes apparent, good rate capability.And this method is simple, and it is at low cost, it is very suitable for large-scale production and uses.

Description

A kind of preparation method of nitrogen-doped carbon coated Si composite graphite material
Technical field
The invention belongs to technical field of lithium ion, are related to a kind of preparation of nitrogen-doped carbon coated Si composite graphite material Method.
Background technology
In recent years, due to the continuous development in electric vehicle field, four ministries and commissions such as Ministry of Industry and Information exist at present《Promote automobile power electricity Pond industry development action scheme》Middle proposition requires single battery energy density to reach 300wh/kg in the year two thousand twenty object of planning, this For as the conventional lithium ion battery of cathode being a huge challenge using graphite (theoretical gram volume 372mAh/g).And silicon Theoretical capacity with 4200mAh/g, and low (the ＜ 0.5V Vs Li/Li of deintercalation platform+), silica-base material is to be expected to become next The material of one of mainstream for ion cathode material lithium.However there are one fatal disadvantages for silica-base material：In lithium ion from silicon material During expecting deintercalation, volume change is very big, easily leads to the dusting of electrode material and the deterioration of electrode performance, so that battery follows Ring performance is poor.
In view of this, the present invention is intended to provide a kind of preparation method of nitrogen-doped carbon coated Si composite graphite material, is adopted With situ Nitrogen Doping carbon coating silicon composite graphite material, to obtain Si-C composite material, the cycle performance promotion of the material is bright It is aobvious, good rate capability.And this method is simple, and it is at low cost, it is very suitable for large-scale production and uses.
Invention content
It is an object of the invention to：In view of the deficiencies of the prior art, a kind of nitrogen-doped carbon coated Si composite graphite is provided The preparation method of material uses situ Nitrogen Doping carbon coating silicon composite graphite material, to obtain Si-C composite material, the material The cycle performance of material promotes apparent, good rate capability.And this method is simple, and it is at low cost, it is very suitable for large-scale production and uses.
In order to achieve the above object, the present invention adopts the following technical scheme that：
A kind of preparation method of nitrogen-doped carbon coated Si composite graphite material includes at least following steps：
Step 1, using, as nitrogen source, organic acid is carbon source, and modified graphene is conducting bridge with the high melamine of nitrogen content Melamine, organic acid, modified graphene are uniformly mixed by beam with nano-silicon suspension, then add graphite, and mixing is equal It is even, it is dry；
The dried material mixed in step 1 is ground up, sieved, then transfers the material into rotary furnace by step 2, leads to Enter inert atmosphere, be heated to 100~500 DEG C, keep the temperature 0.1~5h, the amino of melamine respectively with organic acid, modified graphene In carboxyl reaction, generate key containing C-N, the functional structure group of the hydroxyl generation esters in the carboxyl and modified graphene of organic acid Point.After silicon nanoparticle insertion melamine and organic acid, modified graphite alkene reaction in generated in-situ functional structure component；So After be continuously heating to 500~1000 DEG C, the oxygen and hydrogen in functional structure are sloughed in functional structure component carbonization 0.5~for 24 hours, cooling After break up, be sieved, obtain fine and close nitrogen-doped carbon coated Si composite graphite material.
A kind of improvement of preparation method as nitrogen-doped carbon coated Si composite graphite material of the present invention, what step 2 obtained Nitrogen-doped carbon coated Si composite graphite material has nucleocapsid, and shell is the N doping carbon-coating for being embedded with nano-silicon, and stratum nucleare is Graphite, the N doping carbon-coating are by generated in-situ functional structure group after melamine and organic acid, modified graphite alkene reaction Carbonization is divided to obtain.The shell thickness is in 500nm~5 μm, good conductivity, and, package effect good in graphite surface spreading property Fruit is excellent, and in addition graphene is flexible, provides space for silicon electrochemical expansion, maintains material structure stability.Function knot Structure component is uniformly coated on graphite surface.
A kind of improvement of preparation method as nitrogen-doped carbon coated Si composite graphite material of the present invention, the quality of shell are The 5~30% of stratum nucleare quality.
A kind of improvement of preparation method as nitrogen-doped carbon coated Si composite graphite material of the present invention, described in step 1 Modified graphene is to be grafted with-OOH, and the graphene of-OH functional groups, modified graphene can be anti-with organic acid and melamine It answers.
A kind of improvement of preparation method as nitrogen-doped carbon coated Si composite graphite material of the present invention, described in step 1 Organic acid is the organic matter containing-COOH, so as to be reacted with melamine and modified graphene heating, systematic function structure group Point.And the number of-COOH functional groups is 1~5, and carbon atom number is 2~20.Preferably, organic acid be citric acid, stearic acid, At least one of ethanedioic acid.
A kind of improvement of preparation method as nitrogen-doped carbon coated Si composite graphite material of the present invention, described in step 1 Silicone content in nano-silicon suspension is 5~50%, and the grain size of silicon is 30~100nm, the liquid in nano-silicon suspension be water, At least one of ethyl alcohol, acetone, isopropanol, n-butanol, tetrahydrofuran and espeleton.
A kind of improvement of preparation method as nitrogen-doped carbon coated Si composite graphite material of the present invention, stone described in step 1 Ink is at least one of artificial graphite, natural graphite and carbonaceous mesophase spherules.
A kind of improvement of preparation method as nitrogen-doped carbon coated Si composite graphite material of the present invention, described in step 1 60~200 DEG C of dry temperature.
A kind of improvement of preparation method as nitrogen-doped carbon coated Si composite graphite material of the present invention in step 1, has Machine acid, modified graphene, melamine, silicon nanoparticle, graphite mass ratio be (10~30)：(0.1~1)：(10~30)： (0.1~5)：100.
A kind of improvement of preparation method as nitrogen-doped carbon coated Si composite graphite material of the present invention is returned described in step 2 The rotating speed of converter is 0.1rpm~1000rpm；The inert atmosphere includes at least one in helium, nitrogen, argon gas, carbon dioxide Kind.
Compared with the existing technology, it is to be embedded with the nitrogen of nano-silicon to mix that the material that prepared by the present invention, which has nucleocapsid, shell, Miscellaneous carbon-coating, stratum nucleare are graphite, wherein N doping carbon-coating is by being given birth in situ after melamine and organic acid, modified graphite alkene reaction At functional structure component be carbonized.The N-C functional groups that melamine, organic acid and modified graphene reaction in-situ generate Divide the shell that carbonization obtains conductive good, in the good advantage of graphite surface spreadability, and the flexibility of graphene can give Silicon expand reserved space, to the present invention material circulation performance and high rate performance it is excellent, can better meet power lithium from The demand of sub- battery.In addition, present invention process is simple, and it is easy to operate, it is suitable for large-scale production and prepares.
Specific implementation mode
Embodiment 1
A kind of preparation method of nitrogen-doped carbon coated Si composite graphite material is present embodiments provided, following step is included at least Suddenly：
Step 1, weighs 150g melamines first, and 200g citric acids are as organic acid, 5g modified graphene powder, Silicon suspension (ethanol as solvent) 100g of 10% solid content is put into agitator tank, and the grain size of silicon is 30~100nm, is stirred small-sized Mixing on device is mixed, 1000g D50=15 μm artificial graphites is then weighed again, pours into agitator tank, after stirring evenly, transfer is put into It is dry in 80 DEG C of baking ovens.Wherein, modified graphene is to be grafted with-OOH, the graphene of-OH functional groups
Step 2 is ground after drying, crosses 325 mesh sieve, and powder turns to be put into revolution furnace cavity, and the rotating speed of rotary furnace is 800rpm is passed through N2 protections, is heated to 300 DEG C, keeps the temperature 3h, the amino of melamine respectively in organic acid, modified graphene Carboxyl reaction, generate key containing C-N, the functional structure group of the hydroxyl generation esters in the carboxyl and modified graphene of organic acid Point, after silicon nanoparticle insertion melamine and organic acid, modified graphite alkene reaction in generated in-situ functional structure component.So After be continuously heating to 800 DEG C carbonization 4h.After sample cooling, sample is taken out, 325 mesh screens are crossed in grinding, are obtained fine and close nitrogen and are mixed The Si-C composite material of miscellaneous carbon coating silicon composite graphite.
It is to be embedded with nano-silicon that the nitrogen-doped carbon coated Si composite graphite material that step 2 obtains, which has nucleocapsid, shell, N doping carbon-coating, stratum nucleare is graphite, and N doping carbon-coating is by being given birth in situ after melamine and organic acid, modified graphite alkene reaction At functional structure component be carbonized.The quality of shell is the 15% of stratum nucleare quality, and shell thickness is in 500nm~5 μm.
Embodiment 2
A kind of preparation method of nitrogen-doped carbon coated Si composite graphite material is present embodiments provided, following step is included at least Suddenly：
Step 1, weighs 250g melamines first, and 250g citric acids are as organic acid, 8g modified graphene powder, Silicon suspension (acetone as solvent) 80g of 12% solid content is put into agitator tank, and the grain size of silicon is 30~100nm, is stirred small-sized Mixing on device is mixed, 1000g D50=10 μm natural graphites is then weighed again, pours into agitator tank, after stirring evenly, transfer is put into It is dry in 100 DEG C of baking ovens.Wherein, modified graphene is to be grafted with-OOH, the graphene of-OH functional groups
Step 2 is ground after drying, crosses 325 mesh sieve, and powder turns to be put into revolution furnace cavity, and the rotating speed of rotary furnace is 600rpm is passed through argon gas protection, is heated to 400 DEG C, keeps the temperature 4h, the amino of melamine respectively with organic acid, modified graphene In carboxyl reaction, generate key containing C-N, the functional structure group of the hydroxyl generation esters in the carboxyl and modified graphene of organic acid Point, after silicon nanoparticle insertion melamine and organic acid, modified graphite alkene reaction in generated in-situ functional structure component.So After be continuously heating to 900 DEG C carbonization 5h.After sample cooling, sample is taken out, 325 mesh screens are crossed in grinding, are obtained fine and close nitrogen and are mixed The Si-C composite material of miscellaneous carbon coating silicon composite graphite.
It is to be embedded with nano-silicon that the nitrogen-doped carbon coated Si composite graphite material that step 2 obtains, which has nucleocapsid, shell, N doping carbon-coating, stratum nucleare is graphite, and N doping carbon-coating is by being given birth in situ after melamine and organic acid, modified graphite alkene reaction At functional structure component be carbonized.The quality of shell is the 17% of stratum nucleare quality, and shell thickness is in 500nm~5 μm.
Embodiment 3
A kind of preparation method of nitrogen-doped carbon coated Si composite graphite material is present embodiments provided, following step is included at least Suddenly：
Step 1, weighs 200g melamines first, and 180g stearic acid is as organic acid, 4g modified graphene powder, Silicon suspension (isopropanol makees solvent) 50g of 20% solid content is put into agitator tank, and the grain size of silicon is 30~100nm, small-sized Then mixing on blender weighs 1000g D50=18 μm natural graphites, pours into agitator tank again, after stirring evenly, transfer is put Enter dry in 150 DEG C of baking ovens.Wherein, modified graphene is to be grafted with-OOH, the graphene of-OH functional groups.
Step 2 is ground after drying, crosses 325 mesh sieve, and powder turns to be put into revolution furnace cavity, and the rotating speed of rotary furnace is 500rpm is passed through argon gas protection, is heated to 200 DEG C, keeps the temperature 2h, the amino of melamine respectively with organic acid, modified graphene In carboxyl reaction, generate key containing C-N, the functional structure group of the hydroxyl generation esters in the carboxyl and modified graphene of organic acid Point, after silicon nanoparticle insertion melamine and organic acid, modified graphite alkene reaction in generated in-situ functional structure component.So After be continuously heating to 700 DEG C carbonization 6h.After sample cooling, sample is taken out, 325 mesh screens are crossed in grinding, are obtained fine and close nitrogen and are mixed The Si-C composite material of miscellaneous carbon coating silicon composite graphite.
It is to be embedded with nano-silicon that the nitrogen-doped carbon coated Si composite graphite material that step 2 obtains, which has nucleocapsid, shell, N doping carbon-coating, stratum nucleare is graphite, and N doping carbon-coating is by being given birth in situ after melamine and organic acid, modified graphite alkene reaction At functional structure component be carbonized.The quality of shell is the 18% of stratum nucleare quality, and shell thickness is in 500nm~5 μm.
Embodiment 4
A kind of preparation method of nitrogen-doped carbon coated Si composite graphite material is present embodiments provided, following step is included at least Suddenly：
Step 1, weighs 120g melamines first, and 220g ethanedioic acids are as organic acid, 7g modified graphene powder, Silicon suspension (isopropanol makees solvent) 100g of 25% solid content is put into agitator tank, and the grain size of silicon is 30~100nm, small-sized Then mixing on blender weighs 1000g D50=20 μm carbonaceous mesophase spherules, pours into agitator tank again, after stirring evenly, turn Shifting is put into 120 DEG C of baking ovens dry.Wherein, modified graphene is to be grafted with-OOH, the graphene of-OH functional groups.
Step 2 is ground after drying, crosses 325 mesh sieve, and powder turns to be put into revolution furnace cavity, and the rotating speed of rotary furnace is 300rpm is passed through argon gas protection, is heated to 250 DEG C, keeps the temperature 2.5h, the amino of melamine respectively with organic acid, modified graphite Carboxyl reaction in alkene, generates key containing C-N, and the hydroxyl in the carboxyl and modified graphene of organic acid generates the functional structure of esters Component, silicon nanoparticle are embedded in after melamine and organic acid, modified graphite alkene reaction in generated in-situ functional structure component. It then proceedes to be warming up to 750 DEG C of carbonization 10h.After sample cooling, sample is taken out, 325 mesh screens are crossed in grinding, obtain densification The Si-C composite material of nitrogen-doped carbon coated Si composite graphite.
It is to be embedded with nano-silicon that the nitrogen-doped carbon coated Si composite graphite material that step 2 obtains, which has nucleocapsid, shell, N doping carbon-coating, stratum nucleare is graphite, and N doping carbon-coating is by being given birth in situ after melamine and organic acid, modified graphite alkene reaction At functional structure component be carbonized.The quality of shell is the 20% of stratum nucleare quality, and shell thickness is in 500nm~5 μm.
Embodiment 5
A kind of preparation method of nitrogen-doped carbon coated Si composite graphite material is present embodiments provided, following step is included at least Suddenly：
Step 1, weighs 280g melamines first, and 110g citric acids are as organic acid, 8g modified graphene powder, Silicon suspension (ethanol as solvent) 90g of 16% solid content is put into agitator tank, and the grain size of silicon is 30~100nm, is stirred small-sized Mixing on device is mixed, 1000g D50=15 μm artificial graphites is then weighed again, pours into agitator tank, after stirring evenly, transfer is put into It is dry in 130 DEG C of baking ovens.Wherein, modified graphene is to be grafted with-OOH, the graphene of-OH functional groups
Step 2 is ground after drying, crosses 325 mesh sieve, and powder turns to be put into revolution furnace cavity, and the rotating speed of rotary furnace is 750rpm is passed through N2 protections, is heated to 350 DEG C, keeps the temperature 3.5h, the amino of melamine respectively with organic acid, modified graphene In carboxyl reaction, generate key containing C-N, the functional structure group of the hydroxyl generation esters in the carboxyl and modified graphene of organic acid Point, after silicon nanoparticle insertion melamine and organic acid, modified graphite alkene reaction in generated in-situ functional structure component.So After be continuously heating to 850 DEG C carbonization 12h.After sample cooling, sample is taken out, 325 mesh screens are crossed in grinding, obtain fine and close nitrogen The Si-C composite material of doped carbon coated Si composite graphite.
It is to be embedded with nano-silicon that the nitrogen-doped carbon coated Si composite graphite material that step 2 obtains, which has nucleocapsid, shell, N doping carbon-coating, stratum nucleare is graphite, and N doping carbon-coating is by being given birth in situ after melamine and organic acid, modified graphite alkene reaction At functional structure component be carbonized.The quality of shell is the 12% of stratum nucleare quality, and shell thickness is in 500nm~5 μm.
Embodiment 6
A kind of preparation method of nitrogen-doped carbon coated Si composite graphite material is present embodiments provided, following step is included at least Suddenly：
Step 1, weighs 260g melamines first, and 130g citric acids are as organic acid, 5.5g modified graphene powder, Silicon suspension (water as solvent) 70g of 26% solid content is put into agitator tank, and the grain size of silicon is 30~100nm, in small-sized stirring Then mixing on device weighs 1000g D50=35 μm artificial graphites, pours into agitator tank again, after stirring evenly, transfer is put into It is dry in 140 DEG C of baking ovens.Wherein, modified graphene is to be grafted with-OOH, the graphene of-OH functional groups
Step 2 is ground after drying, crosses 325 mesh sieve, and powder turns to be put into revolution furnace cavity, and the rotating speed of rotary furnace is 550rpm is passed through argon gas protection, is heated to 150 DEG C, keeps the temperature 1.5h, the amino of melamine respectively with organic acid, modified graphite Carboxyl reaction in alkene, generates key containing C-N, and the hydroxyl in the carboxyl and modified graphene of organic acid generates the functional structure of esters Component, silicon nanoparticle are embedded in after melamine and organic acid, modified graphite alkene reaction in generated in-situ functional structure component. It then proceedes to be warming up to 650 DEG C of carbonization 20h.After sample cooling, sample is taken out, 325 mesh screens are crossed in grinding, obtain densification The Si-C composite material of nitrogen-doped carbon coated Si composite graphite.
It is to be embedded with nano-silicon that the nitrogen-doped carbon coated Si composite graphite material that step 2 obtains, which has nucleocapsid, shell, N doping carbon-coating, stratum nucleare is graphite, and N doping carbon-coating is by being given birth in situ after melamine and organic acid, modified graphite alkene reaction At functional structure component be carbonized.The quality of shell is the 10% of stratum nucleare quality, and shell thickness is in 500nm~5 μm.
Embodiment 7
A kind of preparation method of nitrogen-doped carbon coated Si composite graphite material is present embodiments provided, following step is included at least Suddenly：
Step 1, weighs 160g melamines first, and 230g citric acids are as organic acid, 4.5g modified graphene powder, Silicon suspension (water as solvent) 75g of 21% solid content is put into agitator tank, and the grain size of silicon is 30~100nm, in small-sized stirring Then mixing on device weighs 1000g D50=35 μm artificial graphites, pours into agitator tank again, after stirring evenly, transfer is put into It is dry in 180 DEG C of baking ovens.Wherein, modified graphene is to be grafted with-OOH, the graphene of-OH functional groups
Step 2 is ground after drying, crosses 325 mesh sieve, and powder turns to be put into revolution furnace cavity, and the rotating speed of rotary furnace is 650rpm is passed through argon gas protection, is heated to 210 DEG C, keeps the temperature 1.8h, the amino of melamine respectively with organic acid, modified graphite Carboxyl reaction in alkene, generates key containing C-N, and the hydroxyl in the carboxyl and modified graphene of organic acid generates the functional structure of esters Component, silicon nanoparticle are embedded in after melamine and organic acid, modified graphite alkene reaction in generated in-situ functional structure component. It then proceedes to be warming up to 720 DEG C of carbonization 18h.After sample cooling, sample is taken out, 325 mesh screens are crossed in grinding, obtain densification The Si-C composite material of nitrogen-doped carbon coated Si composite graphite.
It is to be embedded with nano-silicon that the nitrogen-doped carbon coated Si composite graphite material that step 2 obtains, which has nucleocapsid, shell, N doping carbon-coating, stratum nucleare is graphite, and N doping carbon-coating is by being given birth in situ after melamine and organic acid, modified graphite alkene reaction At functional structure component be carbonized.The quality of shell is the 15% of stratum nucleare quality, and shell thickness is in 500nm~5 μm.
Embodiment 8
A kind of preparation method of nitrogen-doped carbon coated Si composite graphite material is present embodiments provided, following step is included at least Suddenly：
Step 1, weighs 155g melamines first, and 205g citric acids are as organic acid, 2.5g modified graphene powder, Silicon suspension (ethanol as solvent) 80g of 12% solid content is put into agitator tank, and the grain size of silicon is 30~100nm, is stirred small-sized Mixing on device is mixed, 1000g D50=15 μm artificial graphites is then weighed again, pours into agitator tank, after stirring evenly, transfer is put into It is dry in 160 DEG C of baking ovens.Wherein, modified graphene is to be grafted with-OOH, the graphene of-OH functional groups
Step 2 is ground after drying, crosses 325 mesh sieve, and powder turns to be put into revolution furnace cavity, and the rotating speed of rotary furnace is 750rpm is passed through argon gas protection, is heated to 230 DEG C, keeps the temperature 1.6h, the amino of melamine respectively with organic acid, modified graphite Carboxyl reaction in alkene, generates key containing C-N, and the hydroxyl in the carboxyl and modified graphene of organic acid generates the functional structure of esters Component, silicon nanoparticle are embedded in after melamine and organic acid, modified graphite alkene reaction in generated in-situ functional structure component. It then proceedes to be warming up to 780 DEG C of carbonization 14h.After sample cooling, sample is taken out, 325 mesh screens are crossed in grinding, obtain densification The Si-C composite material of nitrogen-doped carbon coated Si composite graphite.
It is to be embedded with nano-silicon that the nitrogen-doped carbon coated Si composite graphite material that step 2 obtains, which has nucleocapsid, shell, N doping carbon-coating, stratum nucleare is graphite, and N doping carbon-coating is by being given birth in situ after melamine and organic acid, modified graphite alkene reaction At functional structure component be carbonized.The quality of shell is the 15% of stratum nucleare quality, and shell thickness is in 500nm~5 μm.
Comparative example 1
Using commercially available silicon-carbon cathode, shell is carbon, and stratum nucleare is silicon, and the quality of shell is the 10% of stratum nucleare quality, and shell is thick Degree is in 500nm~5 μm.
Electrochemistry cycle performance is tested using following methods：The material that material and comparative example 1 prepared by Example 1-8 provides Material, by following proportioning：Si-C composite material：SP:CMC：SBR=94：2：1.5:2.5 mass ratio mixing, is added suitable pure Water purification is tuned into slurry as dispersant, is coated on copper foil, and vacuum dried, roll-in, is prepared into negative plate；Anode is using gold Belong to lithium piece, uses the LiPF of 1mol/L6Three component mixed solvents press the electrolyte of EC: DMC: EMC=1: 1: 1 (v/v) mixing, adopt It is diaphragm with microporous polypropylene membrane, in the inert atmosphere glove box system assembles full of argon gas at CR2016 type button cells.Button The charge-discharge test of formula battery is on Shenzhen Xin Wei Co., Ltds Neware battery test systems, in normal temperature condition, 0.1C constant currents Charge and discharge, charging/discharging voltage are limited in 0.005~1.5V.
Sample prepared by each embodiment and comparative example is assembled into button cell respectively, then carries out electric performance test, for the first time Charge and discharge gram volume and coulombic efficiency is as described in Table 1 for the first time.
Table 1：Including the button cell for the material that the material and comparative example 1 that are prepared using the method for embodiment 1 to 8 are provided Electricity
The performance test results.
Table 2：Using the high rate performance test result of embodiment 1 and the button cell of the material of the offer of comparative example 1.
Known to table 1,2：Material circulation performance and high rate performance prepared by method using the present invention is excellent, can be more preferable Meet the needs of power lithium-ion battery.In addition, present invention process is simple, and it is easy to operate, it is suitable for large-scale production and makes It is standby.
According to the disclosure and teachings of the above specification, those skilled in the art in the invention can also be to above-mentioned embodiment party Formula carries out change and modification appropriate.Therefore, the invention is not limited in specific implementation modes disclosed and described above, to this Some modifications and changes of invention should also be as falling into the scope of the claims of the present invention.In addition, although this specification In used some specific terms, these terms are merely for convenience of description, does not limit the present invention in any way.

Claims (10)

1. a kind of preparation method of nitrogen-doped carbon coated Si composite graphite material, which is characterized in that include at least following steps：
Step 1, using melamine as nitrogen source, organic acid is carbon source, and modified graphene is conductive bridge, by melamine, organic Acid, modified graphene are uniformly mixed with nano-silicon suspension, then add graphite, are uniformly mixed, dry；
The dried material mixed in step 1 is ground up, sieved, then transfers the material into rotary furnace by step 2, is passed through lazy Property atmosphere, be heated to 100 ~ 500 DEG C, keep the temperature 0.1 ~ 5h, silicon nanoparticle is embedded in melamine and organic acid, modified graphene are anti- After answering in generated in-situ functional structure component；Then proceed to be warming up to 500 ~ 1000 DEG C, carbonization 0.5 ~ for 24 hours, broken up after cooling, Sieving obtains fine and close nitrogen-doped carbon coated Si composite graphite material.
2. the preparation method of nitrogen-doped carbon coated Si composite graphite material according to claim 1, which is characterized in that step Two obtained nitrogen-doped carbon coated Si composite graphite materials have nucleocapsid, and shell is the nitrogen-doped carbon for being embedded with nano-silicon Layer, stratum nucleare is graphite, and the N doping carbon-coating is by generated in-situ work(after melamine and organic acid, modified graphite alkene reaction Energy structural constituent is carbonized.
3. the preparation method of nitrogen-doped carbon coated Si composite graphite material according to claim 2, which is characterized in that shell Quality be stratum nucleare quality 5 ~ 30%.
4. the preparation method of nitrogen-doped carbon coated Si composite graphite material according to claim 1, which is characterized in that step Modified graphene described in one is to be grafted with-COOH, the graphene of-OH functional groups.
5. the preparation method of nitrogen-doped carbon coated Si composite graphite material according to claim 1, which is characterized in that step Organic acid described in one is the organic matter containing-COOH, and the number of-COOH functional groups is 1 ~ 5, and carbon atom number is 2 ~ 20.
6. the preparation method of nitrogen-doped carbon coated Si composite graphite material according to claim 1, which is characterized in that step The silicone content in nano-silicon suspension described in one is 5 ~ 50%, and the grain size of silicon is 30 ~ 100nm, the liquid in nano-silicon suspension For at least one of water, ethyl alcohol, acetone, isopropanol, n-butanol, tetrahydrofuran and espeleton.
7. the preparation method of nitrogen-doped carbon coated Si composite graphite material according to claim 1, which is characterized in that step One graphite is at least one of artificial graphite, natural graphite and carbonaceous mesophase spherules.
8. the preparation method of nitrogen-doped carbon coated Si composite graphite material according to claim 1, which is characterized in that step 60 ~ 200 DEG C of the temperature of drying described in one.
9. the preparation method of nitrogen-doped carbon coated Si composite graphite material according to claim 1, which is characterized in that step In one, organic acid, modified graphene, melamine, silicon nanoparticle, graphite mass ratio be（10~30）：（0.1~1）：（10~ 30）：（0.1~5）：100.
10. the preparation method of nitrogen-doped carbon coated Si composite graphite material according to claim 1, which is characterized in that step The rotating speed of rapid two rotary furnace is 0.1rpm ~ 1000rpm；The inert atmosphere includes helium, nitrogen, argon gas, carbon dioxide At least one of.
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