CN106848199A - A kind of lithium ion cell nano silicon/porous carbon compound cathode materials and its preparation method and application - Google Patents
A kind of lithium ion cell nano silicon/porous carbon compound cathode materials and its preparation method and application Download PDFInfo
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- CN106848199A CN106848199A CN201710104531.9A CN201710104531A CN106848199A CN 106848199 A CN106848199 A CN 106848199A CN 201710104531 A CN201710104531 A CN 201710104531A CN 106848199 A CN106848199 A CN 106848199A
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- H01M4/00—Electrodes
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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Abstract
The invention discloses a kind of lithium ion cell nano silicon/porous carbon compound cathode materials and its preparation method and application, composite negative pole material is the Core-shell structure material being made up of porous nano silicon grain kernel and porous carbon layer shell, its preparation method is after alusil alloy powder Surface coating organic polymer layers, carry out carbonization treatment, carbonized product passes through acid etch to remove aluminium and to carbon-coating pore-creating, obtain final product nano-silicon/porous carbon compound cathode materials；The preparation method is simple, low cost, meets large-scale production, and the composite negative pole material for preparing can prepare lithium ion battery, show capacity higher, excellent circulation and high rate performance.
Description
Technical field
The present invention relates to a kind of Si-C composite material, more particularly to a kind of nano-silicon/porous carbon with core shell structure is multiple
Close negative material, and its application in the lithium ion battery that capacity is high, high rate performance is excellent is prepared；Belong to battery material technology
Field.
Background technology
Rapid expansion and rapid development of economy with population, the electrochemistry with lithium ion battery as main forms
Energy storage, so that its is environment-friendly, have extended cycle life, self discharge is small, energy density is high and the features such as high voltage it is of great interest,
It is used widely in all kinds of portable type electronic products.But stored up lithium mechanism and low capacity by existing graphite cathode material
Influence, current commercial li-ion battery is difficult to meet the use demand to high-energy-density such as electric automobile.Silicon is known
Theoretical capacity highest negative material (4200mAh/g), far above commercial graphite cathode material (372mAh/g), while have compared with
Abundant earth's crust reserves and suitable operating voltage, it is considered to be one of most potential high-capacity cathode material.
However, silicon is used as semiconductor, the conducting power to lithium ion and electronics is poor, and silicon causes with lithium alloyage reaction
Particle volume expansion up to~300%, easily causes electrode structure to destroy in charge and discharge process, and battery capacity decay is violent.With
Upper problem seriously limits the scale application of silicium cathode material.Silicon grain is reduced to nano-scale, such as below 100nm, and
It is compound with conductive carbon material to have been demonstrated that its chemical property is effectively improved, it is also current high performance silicon negative material research institute
The main way taken.
Current silicon nanoparticle is prepared and mainly prepares silico briquette by high temperature magnesiothermic reduction quartz (silica), and further
Nano-silicon is synthesized by methods such as laser ablation, vapour deposition or magnetron sputterings, the process route synthetic method is cumbersome, cost
It is high and often equipment had higher requirements.And in terms of silicon/carbon composite preparation, often directly using nano silicon particles with
Carbon matrix precursor is combined, and recombination process carbon material coats silicon grain completely, on the one hand can improve silicium cathode electric conductivity, but together
When also hinder the speed of lithium ion and silicon materials electrochemical reaction to a certain extent.
The Chinese patent literature of Publication No. CN105655555A discloses a kind of lithium ion battery silicon-carbon composite negative pole material
The preparation method of material, silicon metal alloy compositions are mixed with graphite, and porous silicon/carbon composite material is obtained by twice pickling, many
Hole silicon/carbon composite mixes with organic carbon source, thermally treated prepared Si-C composite material, and silicon substrate is improved to a certain extent
The chemical property of material, but influenceed by carbon material compact structure in compound, composite discharge capacity and storehouse first first
Human relations are less efficient, high rate performance is poor, and overall chemical property needs further raising.
The content of the invention
There are problems that coulombic efficiency is low first, high rate performance, the purpose of the present invention for existing silicon/carbon composite
Aiming to provide one kind has special core shell structure, can effectively alleviate silicon Volume Changes in charge and discharge process, and improve silicon electric conductivity
And nano-silicon/porous the carbon compound cathode materials of electrochemical reaction activity.
It is to provide the preparation that a kind of operation is simple, energy consumption is low and is easy to large-scale production that second object of the present invention is
The method of lithium ion cell nano silicon/porous carbon compound cathode materials.
It is to provide the nano-silicon/porous carbon compound cathode materials in lithium ion battery that third object of the present invention is
In application, prepared lithium ion battery negative can significantly improve lithium ion battery coulombic efficiency first, improve it is forthright again
The performances such as energy.
To realize above-mentioned technical purpose, the invention provides a kind of lithium ion cell nano silicon/porous carbon compound cathode material
Material, the material is the Core-shell structure material being made up of porous nano silicon grain kernel and porous carbon layer shell.
Nano-silicon of the invention/porous carbon compound cathode materials have special core shell structure, and its kernel is porous nano
Silicon, shell is porous carbon layer, and volumetric expansion of the shell porous carbon layer not only for kernel nano-silicon in charge and discharge process provides slow
Rush space, and improve the electric conductivity of nano-silicon, while kernel nano-silicon has loose structure, its specific surface is big, electrochemistry
It is active high, and shell carbon-coating has porous, can provide lithium ion tunnel, is conducive to improving electrochemical reaction speed, so as to improve
The chemical property of negative material.
Preferred scheme, the external diameter of the Core-shell structure material is 30~120nm.
Preferred scheme, the thickness of the porous carbon layer shell is 1~10nm.
Preferred scheme, the particle diameter of the porous nano silicon grain kernel is 20~100nm.
Preferred scheme, the siliceous amount of the porous nano silicon grain is the 70~95% of Core-shell structure material quality.Silicon
Ratio with carbon is controlled in proper range, can guarantee that porous carbon materials uniformly coat silicon nanoparticle, can effectively improve silicon
Grain electric conductivity and the reaction rate with lithium ion, help further to improve the electricity of obtained nano-silicon/porous carbon composite
Chemical property, especially fast charging and discharging high rate performance.
Present invention also offers a kind of preparation method of the lithium ion cell nano silicon/porous carbon compound cathode materials,
The method is after alusil alloy powder Surface coating organic polymer layers, to carry out carbonization treatment, obtains carbon-coating cladding aluminium silicon and closes
Gold grain；The carbon-coating cladding alusil alloy particle passes through acid etch to remove aluminium and to carbon-coating pore-creating, obtain final product.
It is first organic in its Surface coating with inexpensive business alusil alloy powder as raw material in technical scheme
Polymer, then high temperature cabonization, carbonized product it is critical only that and use acid treatment, removal aluminium can be etched by acid, using the mould of aluminium
Plate effect makes alusil alloy form porous nano silicon, and volume reduces with respect to alusil alloy, is silicon volumetric expansion headspace；And
The hydrogen effusion produced during acid with aluminium vigorous reaction, porous is carried out to coated carbon-coating, that is, obtain with special nucleus
The nano-silicon of shell structure/porous carbon compound cathode materials.
As can be seen from Figure 1 similar silicon carbon material technology of preparing route was different from technical solution of the present invention in the past and institute
Obtain the difference of silicon carbon material architectural feature.The method of similar acid etch treatment metal-silicon alloys was first using acid corrosion gold in the past
Category-silicon alloy, then carry out cladding carbon-coating.And technical scheme it is critical only that the place by changing carbon coating and acid etch
Make sequence in order, first coat carbon-coating, then acid etch, acid etch process realizes that the removal of aluminium component in alusil alloy is more with carbon-coating simultaneously
Kong Hua.Carbon-coating carries out porous and had not only improve the electric conductivity of composite but also be conducive to the quick diffusion of lithium ion, while can enter
One step buffers the volumetric expansion of charge and discharge process silicon grain.
In technical scheme, using inexpensive business alusil alloy powder as raw material, wherein aluminium component both can be with
As the template of porous silicon, can be escaped with acid solution reaction generation hydrogen again and cause that coating carbon-coating has loose structure, and
Without carrying out pore-creating as previous methods need to introduce extra template (such as silica).Compared to existing silicon/carbon composite wood
Preparation method for material, technical scheme can preferably solve the problems, such as the coulombic efficiency first and multiplying power of silicon, so as to one can be entered
Step improves the chemical property of obtained composite.
Preferred scheme, be in the process of alusil alloy powder Surface coating organic polymer layers：By alusil alloy powder
Alcohol dispersion liquid mix with the alcoholic solution of organic polymer, ultrasonic disperse, dry.
Preferred scheme, the quality of the organic polymer is the 5~40% of alusil alloy powder quality.Have by regulation and control
The consumption of machine polymer can realize the regulation and control of nano-silicon/porous carbon compound cathode materials shell carbon layers having thicknesses, to nano-silicon/many
The chemical property of hole carbon compound cathode materials has considerable influence.
Preferred scheme, the silicone content of the alusil alloy powder is 5~40wt%, particle diameter is 50~200nm.Further
Preferred scheme, silicon from aluminum-silicon alloy content is 10~20wt%, and alusil alloy powder diameter is 80~100nm.
Preferred scheme, the organic polymer is polyvinylpyrrolidone.It is preferred that polyvinylpyrrolidone is by carbonization
Nitrogen-doped carbon material can be obtained, carbon-coating electric conductivity is can further improve.
Preferred scheme, the molecular weight of the polyvinylpyrrolidone is 4~60,000.
Preferred scheme, the condition of the carbonization treatment is：Under the conditions of protective atmosphere, 4 are heat-treated in 400~800 DEG C
~8h.
Preferred scheme, the process that the carbon-coating cladding alusil alloy particle passes through acid etch is：Carbon-coating is coated into aluminium silicon
Alloying pellet uses H+Concentration is that the acid solution of 1~4mol/L carries out impregnation process.H in acid solution+Should be not less than and close aluminium silicon
The stoichiometric molar quantities that aluminium fully reacts in gold；H in acid solution+It is 3 with the mol ratio of aluminium in alusil alloy:1~10:1；
Preferably 4:1~6:1.Preferably, the temperature of etch processes is 40~60 DEG C.At the preferred temperature, at etching
The reason time is 2~6h.
In order to further improve the performance of silicon/carbon compound cathode materials, the inventive method also includes to nano-silicon/porous carbon
The purification step of composite negative pole material；It is 5~20% through mass concentration by obtained nano-silicon/porous carbon compound cathode materials
Hydrofluoric acid solution carries out impregnation process, then scrubbed, dry nano-silicon/porous carbon compound cathode materials that must be purified again.
By the hydrofluoric acid treatment of the concentration, remaining product such as silica after etching processing etc. can be further removed miscellaneous
Matter, further improves the performance of nano-silicon/porous carbon compound cathode materials.The treatment temperature of purge process is preferably room temperature；
At the preferred temperature, process time is 8~14h.
The alusil alloy powder used in technical scheme is prepared by existing heat fusing mixed atomizing method,
Or use existing commercial raw material；Its granule-morphology is regular spherical, and what is more important aluminium therein and silicon are with atomic level
It is homogenously mixed together, and forms Al-Si chemical bonds；By the way that gained silicon grain particle diameter is smaller after etching of the invention and is distributed
It is narrow.The performance of the composite prepared compared to existing general silicon and metal dust ball milling lithographic method again, the present invention is more excellent.
Present invention also offers a kind of application of described lithium ion cell nano silicon/porous carbon compound cathode materials, will
It is applied to prepare lithium ion battery negative as negative active core-shell material.
Nano-silicon/porous carbon compound cathode materials are passed through rubbing method in copper by preferred scheme with conductive charcoal and binding agent
Negative electrode material layer is prepared on paper tinsel, lithium ion battery negative is obtained final product.
With nano-silicon/porous carbon compound cathode materials as active material, existing lithium is used with conductive agent and binding agent etc.
Ion battery negative electrode technology of preparing prepares lithium ion battery negative electrode.The conductive agent that uses, binding agent are existing routine
Material.Such as conductive black, sodium carboxymethylcellulose.Such as be dispersed in water by binding agent of sodium carboxymethylcellulose, by the silicon/
Carbon composite is added in the sodium carboxymethyl cellulose solution prepared with carbon black, 8~12h is stirred at room temperature and obtains slurry；Will
The slurry is coated on Copper Foil, and the negative pole of silicon/carbon composite is obtained after drying；Active component silicon contains in described negative pole
It is 50~80wt% to measure.
Compared with the prior art, the beneficial effect that technical scheme is brought is：
1st, nano-silicon of the invention/porous carbon compound cathode materials have special structure, are by porous nano silicon kernel
The Core-shell structure material constituted with porous carbon layer shell.Shell porous carbon layer is not only kernel nano-silicon in charge and discharge process
Volumetric expansion provides cushion space, and improves the electric conductivity of nano-silicon, at the same shell carbon-coating have it is porous, can provide lithium from
Subchannel, is conducive to improving electrochemical reaction speed.And kernel nano-silicon has loose structure, its specific surface is big, and electrochemistry is lived
Property is high.Due to its special structure, nano-silicon/porous carbon compound cathode materials is shown excellent chemical property, be used for
In lithium ion battery, fast with charge-discharge velocity, initial capacity is high, and high rate performance is excellent.
2nd, in technical scheme the preparation of nano-silicon/porous carbon compound cathode materials with cheap alusil alloy powder
It is raw material, preparation method is simple, efficient, low energy consumption, easily large-scale production.
3rd, nano-silicon of the invention/porous carbon compound cathode materials prepare lithium ion battery, table as negative active core-shell material
Reveal excellent chemical property, initial reversible capacity is 2921mAh/g, 500mA/g electric currents such as under 200mA/g current densities
Density initial capacity be 2105mAh/g, and 100 times circulation after capacity maintain 1826mAh/g.In 1000,2000 and 3000mA/
Capacity is respectively 2097,2029 and 1980mAh/g under the big multiplying power current densities of g.Capacity is high, circulate, tool excellent with high rate performance
There is great application prospect.
Brief description of the drawings
【Fig. 1】For the technology of the present invention method is illustrated with previous methods and the difference of resulting materials structure；
【Fig. 2】It is raw materials used alusil alloy powder transmission electron microscope (TEM) figures of embodiment 1-4；
【Fig. 3】Nano-silicon/porous carbon composite thermogravimetric analysis (the calculating silicone content) prepared by embodiment 1-3；
【Fig. 4】Nano-silicon/porous carbon composite transmission electron microscope (TEM) figure prepared by embodiment 1；
【Fig. 5】Nano-silicon/porous carbon composite transmission electron microscope (TEM) figure prepared by embodiment 2；
【Fig. 6】Nano-silicon/porous carbon composite transmission electron microscope (TEM) figure prepared by embodiment 3；
【Fig. 7】Nano-silicon/porous carbon composite circulation, high rate performance figure prepared by embodiment 1；
【Fig. 8】Nano-silicon/porous carbon composite circulation, high rate performance figure prepared by embodiment 2；
【Fig. 9】Nano-silicon/porous carbon composite circulation, high rate performance figure prepared by embodiment 3；
【Figure 10】Nano-silicon/carbon composite circulation, high rate performance figure prepared by embodiment 4.
Specific embodiment
In order that technological means, creation characteristic, reached purpose and effect that the present invention is realized are easy to understand, tie below
Specific embodiment is closed, the present invention is expanded on further.
Embodiment 1
2g alusil alloys powder (particle diameter is the business alusil alloy powder of 50~200nm) and 0.1g PVP are separately added into 30mL
With ultrasonic disperse 5min in 20mL absolute ethyl alcohols, suspension and PVP of the alusil alloy in absolute ethyl alcohol are obtained in absolute ethyl alcohol
In solution, the two is mixed, ultrasound 5min, 80 DEG C of magnetic agitations are evaporated absolute ethyl alcohol and obtain solid powder.Powder is placed in
2 DEG C/min of argon atmosphere is warmed up to 600 DEG C for the treatment of 4h in tube furnace, obtains carbon-coated aluminum silicon alloy powder.Weigh 2g carbon coatings
Alusil alloy powder is added in the aqueous hydrochloric acid solution of 80mL 4mol/L, stirring reaction 4h under the conditions of 40 DEG C, filtering, washing, baking
Dry and grinding obtains solid powder.During powder added into the hydrofluoric acid aqueous solution of 10wt%, room temperature reaction 12h is distilled water, anhydrous
Ethanol centrifuge washing obtains nano-silicon/porous carbon compound cathode materials, and (silicone content 92% can by Fig. 3 to be named as 92%Si/p-NC
).
Take 15mgNa-CMC to be dissolved in 2mL deionized waters, 4h is stirred at room temperature.70mg nano-silicons/porous carbon is taken to be led with 15mg
Electric hydrocarbon black powder ground and mixed is stirred at room temperature 12h and obtains cathode size in uniformly adding Na-CMC solution afterwards, using film applicator by institute
Prepare cathode size to coat on Copper Foil, 110 DEG C of drying 2h, section obtains nano-silicon/porous carbon compound cathode, and silicon contains in negative pole
Measure is 64%.Gained nano-silicon/porous Carbon anode and lithium metal are matched, with 1mol/L LiPF6EC/DEC (volume ratios 1:
1) solution is electrolyte, and 2032 lithium-ion button batteries of assembling are circulated performance test.
Embodiment 2
2g alusil alloys powder (particle diameter is the business alusil alloy powder of 50~200nm) and 0.3g PVP are separately added into 30mL
With ultrasonic disperse 5min in 20mL absolute ethyl alcohols, suspension and PVP of the alusil alloy in absolute ethyl alcohol are obtained in absolute ethyl alcohol
In solution, the two is mixed, ultrasound 5min, 80 DEG C of magnetic agitations are evaporated absolute ethyl alcohol and obtain solid powder.Powder is placed in
2 DEG C/min of argon atmosphere is warmed up to 600 DEG C for the treatment of 4h in tube furnace, obtains carbon-coated aluminum silicon alloy powder.Weigh 2g carbon coatings
Alusil alloy powder is added in the aqueous hydrochloric acid solution of 80mL 4mol/L, stirring reaction 4h under the conditions of 40 DEG C, filtering, washing, baking
Dry and grinding obtains solid powder.During powder added into the hydrofluoric acid aqueous solution of 10wt%, room temperature reaction 12h is distilled water, anhydrous
Ethanol centrifuge washing obtains nano-silicon/porous carbon compound cathode materials, and (silicone content 88% can by Fig. 3 to be named as 88%Si/p-NC
).
Take 15mgNa-CMC to be dissolved in 2mL deionized waters, 4h is stirred at room temperature.70mg nano-silicons/porous carbon is taken to be led with 15mg
Electric hydrocarbon black powder ground and mixed is stirred at room temperature 12h and obtains cathode size in uniformly adding Na-CMC solution afterwards, using film applicator by institute
Prepare cathode size to coat on Copper Foil, 110 DEG C of drying 2h, section obtains nano-silicon/porous carbon compound cathode, and silicon contains in negative pole
Measure is 62%.Gained nano-silicon/porous Carbon anode and lithium metal are matched, with 1mol/L LiPF6EC/DEC (volume ratios 1:
1) solution is electrolyte, and 2032 lithium-ion button batteries of assembling are circulated performance test.
Embodiment 3
2g alusil alloys powder (particle diameter is the business alusil alloy powder of 50~200nm) and 0.5g PVP are separately added into 30mL
With ultrasonic disperse 5min in 20mL absolute ethyl alcohols, suspension and PVP of the alusil alloy in absolute ethyl alcohol are obtained in absolute ethyl alcohol
In solution, the two is mixed, ultrasound 5min, 80 DEG C of magnetic agitations are evaporated absolute ethyl alcohol and obtain solid powder.Powder is placed in
2 DEG C/min of argon atmosphere is warmed up to 600 DEG C for the treatment of 4h in tube furnace, obtains carbon-coated aluminum silicon alloy powder.Weigh 2g carbon coatings
Alusil alloy powder is added in the aqueous hydrochloric acid solution of 80mL 4mol/L, stirring reaction 4h under the conditions of 40 DEG C, filtering, washing, baking
Dry and grinding obtains solid powder.During powder added into the hydrofluoric acid aqueous solution of 10wt%, room temperature reaction 12h is distilled water, anhydrous
Ethanol centrifuge washing obtains nano-silicon/porous carbon compound cathode materials, and (silicone content 79% can by Fig. 3 to be named as 79%Si/p-NC
).
Take 15mgNa-CMC to be dissolved in 2mL deionized waters, 4h is stirred at room temperature.70mg nano-silicons/porous carbon is taken to be led with 15mg
Electric hydrocarbon black powder ground and mixed is stirred at room temperature 12h and obtains cathode size in uniformly adding Na-CMC solution afterwards, using film applicator by institute
Prepare cathode size to coat on Copper Foil, 110 DEG C of drying 2h, section obtains nano-silicon/porous carbon compound cathode, and silicon contains in negative pole
Measure is 55%.Gained nano-silicon/porous Carbon anode and lithium metal are matched, with 1mol/L LiPF6EC/DEC (volume ratios 1:
1) solution is electrolyte, and 2032 lithium-ion button batteries of assembling are circulated performance test.
Embodiment 4
This embodiment is used to illustrate not in strict accordance with the technology of the present invention route or made only with previous methods as a comparison
The pore structure and chemical property of standby composite.
2g alusil alloys powder (particle diameter is the business alusil alloy powder of 50~200nm) is added to the salt of 80mL4mol/L
In aqueous acid, stirring reaction 4h under the conditions of 40 DEG C, filtering, washing, drying and grinding obtain solid powder.Powder is added
In the hydrofluoric acid aqueous solution of 10wt%, room temperature reaction 12h, distilled water, absolute ethyl alcohol centrifuge washing obtain nano-silicon.Weigh 0.2g
Nano silica fume and 0.3g PVP are separately added into ultrasonic disperse 5min in 10mL and 20mL absolute ethyl alcohols, obtain nano-silicon in anhydrous second
The solution of suspension and PVP in alcohol in absolute ethyl alcohol, the two is mixed, ultrasound 5min, and 80 DEG C of magnetic agitations are evaporated anhydrous
Ethanol obtains solid powder.Powder is placed in 2 DEG C/min of argon atmosphere in tube furnace and is warmed up to 600 DEG C for the treatment of 4h, obtain nanometer
Silicon/carbon composite, is named as Si/NC.
Take 15mgNa-CMC to be dissolved in 2mL deionized waters, 4h is stirred at room temperature.70mg nano-silicons/carbon is taken with 15mg conduction charcoals
12h is stirred at room temperature in addition Na-CMC solution after black powder mull is well mixed and obtains cathode size, will be prepared using film applicator
Cathode size is coated on Copper Foil, and 110 DEG C of drying 2h, section obtains nano-silicon/carbon compound cathode, and silicone content is in negative pole
62%.Gained nano-silicon/Carbon anode and lithium metal are matched, with 1mol/L LiPF6EC/DEC (volume ratios 1:1) solution is
Electrolyte, 2032 lithium-ion button batteries of assembling are circulated performance test.
Table 1 be the specific surface area of composite prepared by embodiment 1-4 and pore volume data, as can be seen from the table acid solution etching
Specific surface area is significantly increased after carbon-coated aluminum silicon alloy, and with the increase of carbon content, specific surface area is increasing.Pore volume number
It is demonstrated that after acid etching material mesopore presence, wherein 88%Si/p-NC samples pore volume is maximum.It is real in all composites
Apply the gained Si/NC samples specific surface area of example 4 and pore volume is significantly less than Si/p-NC samples, illustrate not in strict accordance with the technology of the present invention
Route cannot obtain the pore structure of resulting materials of the present invention only with the composite prepared by previous methods.
Fig. 1 illustrates the technology of the present invention method and the structure of prepared nuclear shell structure nano silicon/porous carbon composite is shown
Meaning, with alusil alloy powder as raw material, the knot of prepared material can be significantly affected with the order of acid etch by changing carbon coating
Structure.
Transmission electron microscope Fig. 2 shows alusil alloy raw material for spheric granules, and size is about 100nm.
Fig. 3 is the thermogravimetric curve of nano-silicon/porous carbon composite prepared by embodiment 1-3, can be with by thermogravimetric curve
The content of electro-chemical activity component silicon in prepared composite is calculated, as PVP consumptions increase, clad carbon content gradually increases
Plus, silicone content from the 92% of embodiment 1 88% and the embodiment 3 for being reduced to embodiment 2 respectively 79%.
Nano-silicon/porous carbon composite the particle diameter that can be seen that present invention preparation by transmission electron microscope picture 4-6 is about 50~
100nm, porous carbon is evenly coated on silicon nanoparticle, the phenomenon that there is a small amount of reunion, from embodiment 1-3 with PVP consumptions
Increase, carbon layers having thicknesses are continuously increased.
Fig. 7-9 be respectively embodiment 1-3 electrochemical property test result, it can be seen that the cycle performance of embodiment 2 and
High rate performance is better than embodiment 1 and embodiment 3,88%Si/p-NC composites initial reversible appearance under 200mA/g current densities
It is 2921mAh/g to measure, 500mA/g current densities initial capacity be 2105mAh/g, and 100 times circulation after capacity maintain
1826mAh/g.Capacity is respectively 2097,2029 and 1980mAh/ under the big multiplying power current densities of 1000,2000 and 3000mA/g
g。
Figure 10 is for comparative example 4 using previous methods strictly by the electricity of the technology of the present invention route gained composite
Chemical property test result, it can be seen that the silicon/carbon composite circulation is significantly worse than prepared by the present invention with high rate performance and receives
Rice silicon/porous carbon composite, its 500mA/g current densities initial capacity is 1759mAh/g, and capacity only has after 100 circulations
272mAh/g.Capacity is respectively 1279,1047 and 815mAh/g under the big multiplying power current densities of 1000,2000 and 3000mA/g,
About the 50% of nano-silicon/porous carbon composite.
Table 1：Composite specific surface area, pore volume tables of data prepared by embodiment 1-4；
The master that original position of the present invention prepares lithium ion cell nano silicon/porous carbon compound cathode materials has been shown and described above
Want method characteristic and advantage.It should be understood by those skilled in the art that, the present invention is not limited to the above embodiments, above-mentioned implementation
Merely illustrating the principles of the invention and procedure described in example and specification, before spirit and scope of the invention is not departed from
Put, various changes and modifications of the present invention are possible, these changes and improvements all fall within the protetion scope of the claimed invention.This
The claimed scope of invention is by appending claims and its equivalent thereof.
Claims (10)
1. a kind of lithium ion cell nano silicon/porous carbon compound cathode materials, it is characterised in that：It is by porous nano silicon grain
The Core-shell structure material that core and porous carbon layer shell are constituted.
2. lithium ion cell nano silicon according to claim 1/porous carbon compound cathode materials, it is characterised in that：It is described
The external diameter of Core-shell structure material is 30~120nm；The thickness of the porous carbon layer shell is 1~10nm；The porous nano silicon
The particle diameter of particle kernel is 20~100nm；The siliceous amount of the porous nano silicon grain for Core-shell structure material quality 70~
95%.
3. the preparation method of the lithium ion cell nano silicon described in claim 1 or 2/porous carbon compound cathode materials, its feature
It is：After alusil alloy powder Surface coating organic polymer layers, carbonization treatment is carried out, obtain carbon-coated aluminum silicon alloy
Grain；The carbon-coated aluminum silicon alloy removes aluminium and to carbon-coating pore-creating by acid etch, obtains final product.
4. the preparation method of lithium ion cell nano silicon according to claim 1/porous carbon compound cathode materials, its feature
It is：It is in the process of alusil alloy powder Surface coating organic polymer layers：By the alcohol dispersion liquid of alusil alloy powder with have
The alcoholic solution mixing of machine polymer, ultrasonic disperse is dried.
5. the preparation method of the lithium ion cell nano silicon according to claim 3 or 4/porous carbon compound cathode materials, its
It is characterised by：The quality of the organic polymer is the 5~40% of alusil alloy powder quality.
6. the preparation method of lithium ion cell nano silicon according to claim 5/porous carbon compound cathode materials, its feature
It is：The silicone content of the alusil alloy powder is 5~40wt%, particle diameter is 50~200nm；The organic polymer is poly- second
Alkene pyrrolidone, the molecular weight of the polyvinylpyrrolidone is 4~60,000.
7. the preparation method of lithium ion cell nano silicon according to claim 3/porous carbon compound cathode materials, its feature
It is：Carbonization treatment condition is：Under the conditions of protective atmosphere, 4~8h is heat-treated in 400~800 DEG C.
8. the preparation method of lithium ion cell nano silicon according to claim 3/porous carbon compound cathode materials, its feature
It is：The process that carbon-coating cladding alusil alloy particle passes through acid etch is：Carbon-coating cladding alusil alloy particle is used into H+
Concentration is that the acid solution of 1~4mol/L carries out impregnation process in 20~60 DEG C.
9. the application of the lithium ion cell nano silicon described in claim 1 or 2/porous carbon compound cathode materials, it is characterised in that：
It is applied to prepare lithium ion battery negative as negative active core-shell material.
10. the application of lithium ion cell nano silicon according to claim 9/porous carbon compound cathode materials, its feature exists
In：Nano-silicon/porous carbon compound cathode materials are prepared into negative material by rubbing method with conductive charcoal and binding agent on Copper Foil
Layer, obtains final product lithium ion battery negative.
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