CN108448103A - A kind of high performance silicon carbon composite with nucleocapsid and preparation method thereof and the application in lithium ion battery - Google Patents
A kind of high performance silicon carbon composite with nucleocapsid and preparation method thereof and the application in lithium ion battery Download PDFInfo
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- CN108448103A CN108448103A CN201810379754.0A CN201810379754A CN108448103A CN 108448103 A CN108448103 A CN 108448103A CN 201810379754 A CN201810379754 A CN 201810379754A CN 108448103 A CN108448103 A CN 108448103A
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- 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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- 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
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—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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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- H—ELECTRICITY
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- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of high performance silicon carbon composites with nucleocapsid and preparation method thereof and the application in lithium ion battery, belong to lithium ion battery material technical field.The preparation method is：By bulky grain silica flour ball-milling treatment, then the compound of processed silica flour, lithiated compound and titanium oxygen compound, conductive black, expanded graphite and carbon nanotube are mixed and carry out ball milling, zirconium ball is finally separating, obtains Si-C composite material.Wherein micron silicon particle is as core part；Expanded graphite coats silicon particle as shell parts, main to play volume expansion that is conductive and inhibiting silicon；Conductive black and carbon nanotube increase the electric conductivity of material as conductive agent；The compound of lithiated compound and titanium oxygen compound has the characteristic of zero stress, plays a supportive role to entire nucleocapsid.Material of the present invention can be used as the high-power field lithium ion battery negative material such as New-energy electric vehicle, have higher specific capacity, long period good cycle and excellent high rate performance.
Description
Technical field
The invention belongs to technical field of lithium ion battery negative, and in particular to a kind of high-performance with nucleocapsid
Si-C composite material and preparation method thereof and the application in lithium ion battery.
Background technology
In the 21st century, is become increasingly conspicuous due to energy problem and environmental problem, and there is an urgent need to find a kind of new energy by people
Source substitutes gradually exhausted fossil energy.Lithium ion battery has been increasingly becoming since last century the nineties commercial applications
The leader of the energy solution in information technoloy equipment field.Since lithium ion battery has high-energy density, ripe business application
Pattern is considered as " the No.1 seed " for substituting fossil energy by people.The especially rise in New-energy electric vehicle field in recent years,
The requirement with higher energy density and greater security even more is proposed to lithium ion battery, obtains people's extensive concern.Lithium
Whether ion battery has high energy density, largely both depends on the selection of negative material, major R＆D institution pair
Negative material with high-energy density and long circulation life has carried out extensive research.In these materials, silica-base material due to
Safe, rich reserves, relatively low discharge voltage (<0.5V) and high theoretical capacity (4200mAh g-1) etc. it is excellent
Point becomes and most possibly replaces commercialized graphite cathode material at present.
However, silicon based anode material similarly encounters some challenges during industrialized.Alloy is carried out in silicon and lithium
When changing reaction electric discharge, due to the insertion of lithium ion, the volume of silicon can acutely expand (>300%), the process of lithium is taken off in charging
In, the volume of silicon can be shunk.Stress variation so moves in circles, it will the broken and dusting for leading to silicon particle also results in silicon
Particle surface can not form stable SEI films, eventually lead to the sharp-decay in the reduction and capacity of coulombic efficiency.Therefore, lead to
The method that scientific and effective method finds the volume expansion for inhibiting silicon particle is crossed, is had for the commercial applications of silicon based anode material
There is vital effect.
The present inventor is started with by ingenious design from space structure design, is combined using conductive agent point, line, surface to increase
Strong material conductivity improves high rate performance.Introduce simultaneously a kind of zero stress substance come to entire conductive agent three-D space structure into
Row support, it is ensured that material structure stability.Design has synthesized a kind of high performance silicon carbon composite with nucleocapsid, effectively
The volume expansion problem for alleviating silicon particle, preferably improve the chemical property of silicon based anode material.
Silicon is coated using a variety of materials effectively the volume expansion problem of silicon to be inhibited to have been obtained for Depth Study,
And extensive approval is obtained.Guo et al. has synthesized the nanometer material of hard carbon coated Si using the method that graphite oxide and pitch are sintered
Material.During removal lithium embedded, the stable structure of silicon.In 200mA g-1500 circle of cycle, reversible capacity are still protected under current density
It holds as 800mAh g-1.The method of Wu et al. graphenes and potassium ferrate ball milling coated Si has synthesized a kind of Si-C composite material.
In 2A g-1Current density under carry out long period cycle, reversible capacity still reaches 600mAh g-1, tested in high rate performance
In also have preferable performance.
Invention content
In order to make up the not high defect of Current commercial graphite negative material of lithium ion battery energy density, head of the invention
Syllabus is to provide a kind of high-performance silicon carbon lithium ion battery cathode with nucleocapsid.
It is a further object of the present invention to provide a kind of simple process and low cost is honest and clean, safe, environmental-friendly above-mentioned silicon
The preparation method of carbon composite.
Another object of the present invention is to provide a kind of high performance silicon carbon composite with nucleocapsid in lithium-ion electric
Application on the cathode of pond.
The object of the invention is achieved through the following technical solutions.
A kind of preparation method of the high performance silicon carbon composite with nucleocapsid, this method is ball-milling method, specific to wrap
Include following steps：
(1) the bulky grain silica flour bought is weighed, zirconium ball (mill is situated between) is added, ball mill ball milling obtains micron order silica flour.
(2) micron silica flour in step (1) is weighed successively, zero stress substance buffers conductive materials, and zirconium ball (mill is situated between) is added,
Ball mill ball milling.
(3) and then by product and the washing of zirconium ball, filtering, separation, drying it can be obtained a kind of high property with nucleocapsid
It can Si-C composite material.
Preferably, the bulky grain silica flour described in step (1) is one or more of millimeter silica flour or micron silica flour.
Preferably, step (1), ball milling described in (2) rotating speed be 40~800rpm, Ball-milling Time is 4~140h.
Preferably, the mass ratio of step (1), zirconium ball described in (2) and raw material is 5:1~50:1.
Preferably, the zero stress substance described in step (2) is in silicon oxide compound, titanium oxygen compound and lithiated compound
More than one, the buffering conductive materials are super P, hard carbon, soft carbon, activated carbon, carbon nanotube, carbon nanocoils, carbon nanometer
One or more of band and carbon nano-fiber.
Preferably, it is 1 that zero stress substance, which is mass ratio, in step (2):9~9:1 lithiated compound and titanium oxygen compound
Compound.
In above-mentioned preparation process, ball milling mainly has following effect：(1) it by the Strong shear power of zirconium ball, effectively reduces swollen
The number of plies of swollen graphite obtains few number of plies graphite.(2) by the Strong shear power of zirconium ball, by bulky grain silica flour ball milling at little particle silicon
Powder.(3) a kind of high performance silicon carbon composite with nucleocapsid is obtained.
A kind of high performance silicon carbon composite with nucleocapsid can be made by above-described preparation method.
Preferably, in the high performance silicon carbon composite with nucleocapsid silicon mass fraction be 10%~
70%, the mass fraction of expanded graphite is 10%~70%, the mass fraction of the compound of lithiated compound and titanium oxygen compound
It is 1%~20%, the mass fraction of conductive black is 0.1%~10%, and the mass fraction of carbon nanotube is 1%~20%, lithium
The ratio of oxygen compound and titanium oxygen compound is 1:9~9:1.
It is further preferred that in the high performance silicon carbon composite of the nucleocapsid silicon mass fraction be 30%~
60%, the mass fraction of expanded graphite is 20%~40%, the mass fraction of the compound of lithiated compound and titanium oxygen compound
It is 5%~20%, the mass fraction of conductive black is 1%~5%, and the mass fraction of carbon nanotube is 5%~15%, lithium
The ratio for closing object and titanium oxygen compound is 3:7~7:3.
Most preferably, the mass fraction of silicon is 42.8% in the high performance silicon carbon composite of the nucleocapsid, expansion
The mass fraction of graphite is 28.6%, and the mass fraction of the compound of lithiated compound and titanium oxygen compound is 14.3%, conductive
The mass fraction of carbon black is 2.8%, and the mass fraction of carbon nanotube is 11.5%, and lithiated compound and titanium oxygen compound are chemical combination
Object lithium titanate.
A kind of above-described high performance silicon carbon composite with nucleocapsid is as lithium ion battery negative material
Application.
Preferably, the above concrete application process is：By with nucleocapsid high performance silicon carbon composite, carbon black and
PVDF mixed pulps, are coated on copper foil, obtain negative electrode of lithium ion battery.
It is further preferred that the application process is：Weighing 0.16g has the high-performance silicon-carbon composite wood of nucleocapsid
Material, 0.02g PVDF, 0.02g carbon blacks are transferred in vial after mixed grinding, 2ml NMP, magnetic agitation 1h are added, by material
Material, which is coated on copper foil, is made electrode, is used as using metal lithium sheet and is assembled into CR2016 types button electricity in glove box to electrode
Pond.
Compared with prior art, the present invention has the following advantages and beneficial outcomes：
(1) present invention uses ball-milling method easy to operate, high-performance silicon-carbon of the one-step synthesis with nucleocapsid compound
Material is simultaneously successfully applied to lithium ion battery negative material.Expanded graphite effectively alleviates in lithiumation and goes lithiumation process
The variation of middle micron silicon particle volume, increases the electric conductivity of material, improves material electrochemical stability.
(2) present invention is combined using expanded graphite, conductive black and carbon nanotube, constitutes flexible carbon-based conductive network,
It is effectively increased the electric conductivity of material, improves the performance of material.
(3) low in raw material price used in the present invention, the synthetic method of use is easy to operate, and yield is high.In addition to this, originally
Invention also has safe, advantages of environment protection.Thus, the present invention has the potentiality of large-scale commercial application.
(4) the high performance silicon carbon composite with nucleocapsid that the present invention synthesizes is applied to negative electrode of lithium ion battery
When, show excellent cyclical stability and high rate performance.When silicone content is 20%~50%, can be surveyed by various performances
Examination.It is 200mA g in current density-1100 circle of lower cycle, can keep about 1000mAh g-1~1500mAh g-1Reversible appearance
Amount.And in 2A g-1Current density under cycle 200 circle, still can keep 650mAh g-1~800mAh g-1Reversible capacity.
It can be seen that the lithium ion battery negative material that the present invention synthesizes not only has preferable cycle performance, and in larger current density
Under, still there is good performance, the application for lithium ion battery in large-power occasions such as New-energy electric vehicles provides guarantor
Barrier.
Description of the drawings
Fig. 1 is the high performance silicon carbon composite 2000mA g that 5 gained of the embodiment of the present invention has nucleocapsid-1Electric current
Charging and discharging capacity curve and coulombic efficiency curve graph under density.
Fig. 2 is that the TG of 5 ball milling resulting materials of the embodiment of the present invention schemes.
Fig. 3 is the XRD diagram of 5 ball milling resulting materials of the embodiment of the present invention.
Fig. 4 is that the SEM of 5 ball milling resulting materials of the embodiment of the present invention schemes.
Specific implementation mode
The present invention is described in further detail with reference to embodiment and attached drawing, but embodiments of the present invention are not limited to
This.
Embodiment 1
The processing of one, silica flours：20g500 mesh business silica flours are weighed, ball grinder is added, in addition sealing in 200g zirconiums ball (mill is situated between)
Obtained micron silicon and zirconium ball warp sieve are filtered out zirconium ball and carry out separating treatment to get micron silicon by circle, the ball milling 4h at 400rpm
Powder.
Two, have the preparation of the high performance silicon carbon composite of nucleocapsid：7g microns of silica flours are weighed successively, and 1g expands stone
Ink, 0.5g lithium titanates, 0.2g conductive blacks, 1.3g carbon nanotubes and 50g zirconiums ball (mill is situated between) are added in ball grinder, in addition sealing
Circle, ball milling 48h, filters out zirconium ball through sieve by obtained sample, obtains the high-performance silicon-carbon with nucleocapsid at 500 rpm
Composite material.
Take the high performance silicon carbon composite with nucleocapsid obtained by 0.16g the present embodiment, 0.025g PVDF,
0.025 carbon black is transferred in vial after mixed grinding, and 2ml NMP are added, and material is coated on copper foil by magnetic agitation 1h
Electrode is made, using lithium metal as CR2016 type button cells are assembled into glove box to electrode, carries out chemical property
Test.
Embodiment 2
The processing of one, silica flours：20g500 mesh business silica flours are weighed, ball grinder is added, in addition sealing in 200g zirconiums ball (mill is situated between)
Obtained micron silicon and zirconium ball warp sieve are filtered out zirconium ball and carry out separating treatment to get micron by circle, the ball milling 15h at 400rpm
Silica flour.
Two, have the preparation of the high performance silicon carbon composite of nucleocapsid：6.31g microns of silica flours, 1.75g are weighed successively
Expanded graphite, 0.3g lithium titanates, 0.1g conductive blacks, 1.54g carbon nanotubes and 100g zirconiums ball (mill is situated between) are added in ball grinder,
In addition obtained sample is filtered out zirconium ball through sieve, obtains the height with nucleocapsid by sealing ring, the ball milling 20h at 400rpm
Performance Si-C composite material.
Take the high performance silicon carbon composite with nucleocapsid obtained by 0.16g the present embodiment, 0.025g PVDF,
0.025 carbon black is transferred in vial after mixed grinding, and 2ml NMP are added, and material is coated on copper foil by magnetic agitation 1h
Electrode is made, using lithium metal as CR2016 type button cells are assembled into glove box to electrode, carries out chemical property
Test.
Embodiment 3
The processing of one, silica flours：20g500 mesh business silica flours are weighed, ball grinder is added, in addition sealing in 200g zirconiums ball (mill is situated between)
Obtained micron silicon and zirconium ball warp sieve are filtered out zirconium ball and carry out separating treatment to get micron by circle, the ball milling 28h at 400rpm
Silica flour.
Two, have the preparation of the high performance silicon carbon composite of nucleocapsid：5.54g microns of silica flours are weighed successively, and 3g is swollen
Swollen graphite, 0.1g lithium titanates, 0.06g conductive blacks, 1.3g carbon nanotubes and 150g zirconiums ball (mill is situated between) are added in ball grinder, are added
Upper sealing ring, ball milling 40h, zirconium ball is filtered out by obtained sample through sieve at 800 rpm, obtains the high property with nucleocapsid
It can Si-C composite material.
Take the high performance silicon carbon composite with nucleocapsid obtained by 0.16g the present embodiment, 0.025g PVDF,
0.025 carbon black is transferred in vial after mixed grinding, and 2ml NMP are added, and material is coated on copper foil by magnetic agitation 1h
Electrode is made, using lithium metal as CR2016 type button cells are assembled into glove box to electrode, carries out chemical property
Test.
Embodiment 4
The processing of one, silica flours：20g500 mesh business silica flours are weighed, ball grinder is added, in addition sealing in 200g zirconiums ball (mill is situated between)
Obtained micron silicon and zirconium ball warp sieve are filtered out zirconium ball and carry out separating treatment to get micron by circle, the ball milling 42h at 400rpm
Silica flour.
Two, have the preparation of the high performance silicon carbon composite of nucleocapsid：4.82g microns of silica flours, 3.57g are weighed successively
Expanded graphite, 1g lithium titanates, 0.3g conductive blacks, 0.31g carbon nanotubes and 200g zirconiums ball (mill is situated between) are added in ball grinder, are added
Upper sealing ring, ball milling 72h, zirconium ball is filtered out by obtained sample through sieve at 200 rpm, obtains the high property with nucleocapsid
It can Si-C composite material.
Take the high performance silicon carbon composite with nucleocapsid obtained by 0.16g the present embodiment, 0.025g PVDF,
0.025 carbon black is transferred in vial after mixed grinding, and 2ml NMP are added, and material is coated on copper foil by magnetic agitation 1h
Electrode is made, using lithium metal as CR2016 type button cells are assembled into glove box to electrode, carries out chemical property
Test.
Embodiment 5
The processing of one, silica flours：20g500 mesh business silica flours are weighed, ball grinder is added, in addition sealing in 200g zirconiums ball (mill is situated between)
Obtained micron silicon and zirconium ball warp sieve are filtered out zirconium ball and carry out separating treatment to get micron by circle, the ball milling 72h at 400rpm
Silica flour.
Two, have the preparation of the high performance silicon carbon composite of nucleocapsid：4g microns of silica flours are weighed successively, and 3.14g is swollen
Swollen graphite, 1.43g lithium titanates, 0.28g conductive blacks, 1.15g carbon nanotubes and 250g zirconiums ball (mill is situated between) are added in ball grinder,
In addition obtained sample is filtered out zirconium ball through sieve, obtains the height with nucleocapsid by sealing ring, the ball milling 12h at 700rpm
Performance Si-C composite material.
Take the high performance silicon carbon composite with nucleocapsid obtained by 0.16g the present embodiment, 0.025g PVDF,
0.025 carbon black is transferred in vial after mixed grinding, and 2ml NMP are added, and material is coated on copper foil by magnetic agitation 1h
Electrode is made, using lithium metal as CR2016 type button cells are assembled into glove box to electrode, carries out chemical property
Test.
There is TG figures, XRD diagram and the SEM of the high performance silicon carbon composite of nucleocapsid to scheme respectively such as obtained by the present embodiment
Shown in Fig. 2, Fig. 3, Fig. 4.From TG figure it can be seen that carbon content be about 37%, from XRD diagram it can be seen that in material only have lithium titanate,
Three kinds of substances of silicon and carbon.
There is the high performance silicon carbon composite 2000mA g of nucleocapsid obtained by the present embodiment-1Current density under charge and discharge
Electric specific capacity curve and coulombic efficiency curve graph are as shown in Figure 1.It will be seen from figure 1 that being by preceding 5 loop current density
After 200mA/g activation, after being recycled to 100 circles, still there is the reversible capacity of 739mAh/g, and ascendant trend, coulombic efficiency is presented
Often circle is held at 99% or more.Carbon content is 37% in milling material obtained by this ratio.
Embodiment 6
The processing of one, silica flours：20g500 mesh business silica flours are weighed, ball grinder is added, in addition sealing in 200g zirconiums ball (mill is situated between)
Obtained micron silicon and zirconium ball warp sieve are filtered out zirconium ball and carry out separating treatment to get micron by circle, the ball milling 84h at 400rpm
Silica flour.
Two, have the preparation of the high performance silicon carbon composite of nucleocapsid：3.83g microns of silica flours, 3.58g are weighed successively
Expanded graphite, 1.03g lithium titanates, 0.51g conductive blacks, 1.05g carbon nanotubes and 300g zirconiums ball (mill is situated between) are added to ball grinder
In, in addition sealing ring, ball milling 30h, filters out zirconium ball through sieve by obtained sample, obtains having nucleocapsid at 600 rpm
High performance silicon carbon composite.
Take the high performance silicon carbon composite with nucleocapsid obtained by 0.16g the present embodiment, 0.025g PVDF,
0.025 carbon black is transferred in vial after mixed grinding, and 2ml NMP are added, and material is coated on copper foil by magnetic agitation 1h
Electrode is made, using lithium metal as CR2016 type button cells are assembled into glove box to electrode, carries out chemical property
Test.
Embodiment 7
The processing of one, silica flours：20g500 mesh business silica flours are weighed, ball grinder is added, in addition sealing in 200g zirconiums ball (mill is situated between)
Obtained micron silicon and zirconium ball warp sieve are filtered out zirconium ball and carry out separating treatment to get micron by circle, the ball milling 90h at 400rpm
Silica flour.
Two, have the preparation of the high performance silicon carbon composite of nucleocapsid：3.04g microns of silica flours, 4.56g are weighed successively
Expanded graphite, 0.94g lithium titanates, 0.62g conductive blacks, 0.84g carbon nanotubes and 350g zirconiums ball (mill is situated between) are added to ball grinder
In, in addition obtained sample is filtered out zirconium ball through sieve, obtains having nucleocapsid by sealing ring, the ball milling 38h at 400rpm
High performance silicon carbon composite.
Take the high performance silicon carbon composite with nucleocapsid obtained by 0.16g the present embodiment, 0.025g PVDF,
0.025 carbon black is transferred in vial after mixed grinding, and 2ml NMP are added, and material is coated on copper foil by magnetic agitation 1h
Electrode is made, using lithium metal as CR2016 type button cells are assembled into glove box to electrode, carries out chemical property
Test.
Embodiment 8
The processing of one, silica flours：20g500 mesh business silica flours are weighed, ball grinder is added, in addition sealing in 200g zirconiums ball (mill is situated between)
Obtained micron silicon and zirconium ball warp sieve are filtered out zirconium ball and carry out separating treatment to get micron by circle, the ball milling 96h at 400rpm
Silica flour.
Two, have the preparation of the high performance silicon carbon composite of nucleocapsid：2.55g microns of silica flours, 4.87g are weighed successively
Expanded graphite, 1.13g lithium titanates, 0.2g conductive blacks, 1.25g carbon nanotubes and 400g zirconiums ball (mill is situated between) are added to ball grinder
In, in addition obtained sample is filtered out zirconium ball through sieve, obtains having nucleocapsid by sealing ring, the ball milling 28h at 550rpm
High performance silicon carbon composite.
Take the high performance silicon carbon composite with nucleocapsid obtained by 0.16g the present embodiment, 0.025g PVDF,
0.025 carbon black is transferred in vial after mixed grinding, and 2ml NMP are added, and material is coated on copper foil by magnetic agitation 1h
Electrode is made, using lithium metal as CR2016 type button cells are assembled into glove box to electrode, carries out chemical property
Test.
Embodiment 9
The processing of one, silica flours：20g500 mesh business silica flours are weighed, ball grinder is added, in addition sealing in 200g zirconiums ball (mill is situated between)
Obtained micron silicon and zirconium ball warp sieve are filtered out zirconium ball and carry out separating treatment to get micron by circle, the ball milling 120h at 400rpm
Silica flour.
Two, have the preparation of the high performance silicon carbon composite of nucleocapsid：1.83g microns of silica flours, 5.75g are weighed successively
Expanded graphite, 0.89g lithium titanates, 0.47g conductive blacks, 1.06g carbon nanotubes and 450g zirconiums ball (mill is situated between) are added to ball grinder
In, in addition obtained sample is filtered out zirconium ball through sieve, obtains having nucleocapsid by sealing ring, the ball milling 58h at 650rpm
High performance silicon carbon composite.
Take the high performance silicon carbon composite with nucleocapsid obtained by 0.16g the present embodiment, 0.025g PVDF,
0.025 carbon black is transferred in vial after mixed grinding, and 2ml NMP are added, and material is coated on copper foil by magnetic agitation 1h
Electrode is made, using lithium metal as CR2016 type button cells are assembled into glove box to electrode, carries out chemical property
Test.
Embodiment 10
The processing of one, silica flours：20g500 mesh business silica flours are weighed, ball grinder is added, in addition sealing in 200g zirconiums ball (mill is situated between)
Obtained micron silicon and zirconium ball warp sieve are filtered out zirconium ball and carry out separating treatment to get micron by circle, the ball milling 140h at 400rpm
Silica flour.
Two, have the preparation of the high performance silicon carbon composite of nucleocapsid：1g microns of silica flours, 6.4g expansions are weighed successively
Graphite, 1.38g lithium titanates, 0.05g conductive blacks, 1.17g carbon nanotubes and 50g zirconiums ball (mill is situated between) are added in ball grinder, are added
Upper sealing ring, ball milling 48h, zirconium ball is filtered out by obtained sample through sieve at 500 rpm, obtains the high property with nucleocapsid
It can Si-C composite material.
Take the high performance silicon carbon composite with nucleocapsid obtained by 0.16g the present embodiment, 0.025g PVDF,
0.025 carbon black is transferred in vial after mixed grinding, and 2ml NMP are added, and material is coated on copper foil by magnetic agitation 1h
Electrode is made, using lithium metal as CR2016 type button cells are assembled into glove box to electrode, carries out chemical property
Test.
Performance test：
Above-described embodiment prepare material be using X-ray diffraction technology (XRD), Raman spectrum (Raman Spectra),
Table is made in Fourier Transform Infrared Spectroscopy (FT-IR), scanning electron microscope (SEM), transmission electron microscope (TEM), thermogravimetric analysis (TGA)
Sign means fully analyze its grain size, pattern, composition and carbon content.
After battery prepared by above-described embodiment shelves 12h, using cell tester (the new prestige in Shenzhen) and BTS7.5.5 softwares,
Test temperature is room temperature, and current density is 200mA g-1~2000mA g-1In the case of, constant current charge-discharge is carried out to it, and (electric discharge is cut
Only voltage is 0.01V, charging voltage 3V), test the cycle performance and high rate performance of battery.The electrical property of sample refers to table 1.
Cyclic voltammetry (CV) and ac impedance measurement are carried out to it using electrochemical workstation (CHI600E, Shanghai Chen Hua).
Table 1
The high performance silicon carbon composite that the present invention is prepared for having nucleocapsid using ball-milling method, passes through feed change
Ratio and ratio of grinding media to material find the material of best performance, also studied the chemical property of respective material：Cycle performance and forthright again
Energy is equal.By comparing 10 embodiments, it is found that ratio of grinding media to material is 20:When 1, the sample that silicon mass fraction is 30.4%~48.2%,
It, can be in 200mA g with good circulation performance-1Under current density 1000mAh g are kept after 200 circle of cycle-1Above may be used
Inverse capacity；The sample that silicon mass fraction is 25.5% is in 2000mAg-1After 100 circle of cycle, reversible capacity reaches 987mAg-1；Silicon
The sample that mass fraction is 63.1% is in 200mAg-1After 100 circle of cycle, reversible capacity reaches 1219mAh g-1。
Embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not limited by the above embodiments
System, it is other it is any without departing from the spirit and principles of the present invention made by changes, modifications, substitutions, combinations, simplifications,
Equivalent substitute mode is should be, is included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of the high performance silicon carbon composite with nucleocapsid, which is characterized in that include the following steps：
（1）Bulky grain silica flour is weighed, zirconium ball is added and is situated between as mill, ball milling detaches zirconium ball up to processed silica flour；
（2）To step（1）Zero stress substance, buffering conductive materials and zirconium ball, ball milling are added in processed silica flour；
（3）By step（2）Products therefrom detaches, and obtains the high performance silicon carbon composite with nucleocapsid.
2. preparation method according to claim 1, which is characterized in that step（2）The zero stress substance is silica chemical combination
It is one or more in object, titanium oxygen compound and lithiated compound；The buffering conductive materials be super P, hard carbon, soft carbon,
It is one or more in activated carbon, carbon nanotube, carbon nanocoils, carbon nanobelts and carbon nano-fiber.
3. preparation method according to claim 1, which is characterized in that step（1）, step（2）Described in ball milling when turn
Speed is 40 ~ 800 rpm, and Ball-milling Time is 4 ~ 140h.
4. preparation method according to claim 1, which is characterized in that step（2）Middle zero stress substance is lithium titanate；It is described
It includes expanded graphite, conductive black and carbon nanotube to buffer conductive materials.
5. preparation method according to claim 1, which is characterized in that step（1）, step（2）Described in zirconium ball and raw material
Mass ratio is 5:1~50:1.
6. a kind of high-performance silicon-carbon with nucleocapsid made from claim 1-5 any one of them preparation methods is compound
Material.
7. a kind of high performance silicon carbon composite with nucleocapsid according to claim 6, which is characterized in that described
The mass fraction of silicon is 10% ~ 70% in Si-C composite material, and the mass fraction of expanded graphite is 10% ~ 70%, lithiated compound and
The mass fraction of the compound of titanium oxygen compound is 1% ~ 20%, and the mass fraction of conductive black is 0.1% ~ 10%, carbon nanotube
Mass fraction is 1% ~ 20%.
8. a kind of high performance silicon carbon composite with nucleocapsid according to claim 7, which is characterized in that described
The mass fraction of silicon is 30% ~ 60% in Si-C composite material, and the mass fraction of expanded graphite is 20% ~ 40%, lithiated compound and
The mass fraction of the compound of titanium oxygen compound is 5% ~ 20%, and the mass fraction of conductive black is 1% ~ 5%, the quality of carbon nanotube
Score is 5% ~ 15%.
9. a kind of high performance silicon carbon composite with nucleocapsid according to claim 8, which is characterized in that described
The mass fraction of silicon is 42.8% in Si-C composite material, and the mass fraction of expanded graphite is 28.6%, lithiated compound and titanyl
The mass fraction of the compound of compound is 14.3%, and the mass fraction of conductive black is 2.8%, and the mass fraction of carbon nanotube is
11.5%。
10. a kind of high performance silicon carbon composite with nucleocapsid of claim 6-9 any one of them is as lithium ion
The application of cell negative electrode material.
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Application publication date: 20180824 |