CN102623680B - Silicon-carbon composite cathode material with three-dimensional preformed hole structure and preparation method thereof - Google Patents
Silicon-carbon composite cathode material with three-dimensional preformed hole structure and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a silicon-carbon composite cathode material with a three-dimensional preformed hole structure and a preparation method thereof. According to the composite cathode material, a carbon material having high electric conductivity and a stable structure is used as a matrix for dispersedly containing high-volume silicon particles, and proper three-dimensional expansion spaces are reserved around one or several silicon particles. The preparation method comprises the following steps of: carrying out surface modification on the silicon particles; coating the silicon particles by silicon dioxide; coating the silicon dioxide/silicon composite particles by carbon source precursors; carrying out high-temperature carbonization treatment; and removing a silicon dioxide template, and the like. When the composite material prepared by the preparation method is used for a lithium ion battery, the reversible specific capacity is high, and the cycle performance is excellent. The silicon-carbon composite cathode material has the advantages of simple preparation process and wide raw material resource and is suitable for industrial production.
Description
Technical field
The present invention relates to a kind of silicon-carbon composite anode material for lithium ion battery and preparation method thereof, particularly relate to a kind of silicon-carbon composite cathode material with three-dimensional preformed hole structure and preparation method thereof.
Background technology
At present, commercial li-ion battery extensively adopts graphite-like material with carbon element as negative material, its theoretical capacity lower (372mAh/g), and the research of high power capacity negative material has become with application the key that improves performance of lithium ion battery.Silicon materials are considered to one of ideal candidates material substituting graphite cathode material owing to having high theoretical lithium storage content (4200mAh/g), good security performance and rich in natural resources.Yet the greatest problem of silicon during as negative pole is, lithium ion causes that when inserting enormousness changes (approximately 300%), produce that silicon grain breaks, the phenomenon such as efflorescence and secondary agglomeration, make to occur between conductive network and silicon particle separated, finally cause electrode interior structural damage, and then affect the cycle performance of battery.This has affected its extensive industrialization process greatly.
In order to slow down silica-base material, in the enormousness that embedding/de-lithium process produces, change, improve the chemical property of silicon-based anode, researcher has carried out positive exploration both at home and abroad.At present the study on the modification of silica-base material is mainly contained to following several approach:
(1) silicon materials are carried out to nanometer, for example patent CN101901897A has reported a kind of nano silicon composite cathode material for lithium ion battery and preparation method thereof.Studies show that, grain refine can alleviate the absolute volume intensity of variation of silicon, can also reduce the diffusion length of lithium ion simultaneously, improves electrochemical reaction speed.But nano-silicon is reunited gradually along with the carrying out of circulation, from and lost the distinctive performance of nano particle, cause destructurized, reversible capacity to be decayed.In addition; also someone adopts some new technology to prepare the silicium cathode material having compared with height ratio capacity, good circulation performance; for example be grown directly upon the silicon nano-array [C.K.Chan on collector; H.Peng; G.Liu; et al.Nature Nanotechnology; 2008,3:31-35], magnetron sputtering method the thin film silicon electrode [M.Uehara, the J.Suzuki that prepare; K.Tamura; et al.J.Power Sources, 2005,146:441-444]; but these method preparation costs are high, complex technical process, are difficult to large-scale production.
(2) silicon materials and the metallic element that can form stable compound are carried out to alloying or partially-alloyed, utilize the good ductility of metal material to alleviate internal stress that the volumetric expansion in removal lithium embedded process the produces destruction to material structure, for example patent CN1786221 discloses a kind of preparation method of high capacity tin antimony nickel alloy complex lithium ion battery cathode material.But the most of metal itself adopting due to Zhe Lei research institute is inert matter, thereby has limited the raising of specific capacity, and some metalline is partially crisp, after long-term circulation, may crack, form equally irreversible capacity.
(3) silicon materials and material with carbon element are compound, material with carbon element itself has good conductivity, can effectively improve the electric conductivity of material after mixing, and Stability Analysis of Structures, in silicon generation deformation, produce supporting role, thereby compare with pure silicon, Si-C composite material cycle performance improves significantly.Silicon-carbon complex method generally has mechanical mixing, Polymer-pyrolysis method, vapour deposition process etc.Patent CN102340001A discloses a kind of mixing and ball milling preparation method of silicon/carbon negative pole material, mechanical mixing is owing to being that simple physics is compound, can not fundamentally suppress the bulk effect in charge and discharge process, capacity still can be decayed along with the increase of circulation.Patent CN1913200 has reported the composite negative pole material of a kind of silicon and organic matter pyrolysis carbon, although the method for copyrolysis can be dispersed in carbon base body by silicon particle well, improve to a certain extent charge-discharge performance, but the structural stability of carbon base body also needs further investigation.The employing benzene such as Liu are unstripped gas; with CVD method, material with carbon-coated surface silica-base material [W.R.Liu, J.H.Wang, H.C.Wu have been synthesized; et al..J.Electrochem.Soc.; 2005,152 (9): A1719-A1725], but coated carbon shell after iterative cycles, easily destroyed; and CVD method complex process; process is difficult to control, and is difficult to obtain the product of uniformity, is unfavorable for large-scale production.
After present patent application person research, think why current Si-C composite material can not solve the expansion issues of silicon in charge and discharge process completely, key is that carbon component wherein does not really play the effect of rock-steady structure.After discharging and recharging repeatedly, as the carbon of conducting base due to be subject to silicon swelling stress effect and self recurring structure caves in, lose the effect of protection silicon and its electro-chemical activity reduced.Therefore research has Si-C composite material of new construction and preparation method thereof, very large to the industrialization process meaning of promotion silicon-based anode.
Summary of the invention
First technical problem to be solved by this invention be to provide a kind of have capacity high, have extended cycle life and the silicon-carbon composite cathode material with three-dimensional preformed hole structure of high rate performance excellence.
It is simply controlled, with low cost that second technical problem to be solved by this invention is to provide a kind of flow process, can be mass-produced, and the preparation that practical application foreground is good has the method for the silicon-carbon composite cathode material of three-dimensional preformed hole structure.
In order to solve above-mentioned first technical problem, the silicon-carbon composite cathode material with three-dimensional preformed hole structure provided by the invention, by thering is the carbon base body of high conductivity and rock-steady structure and the silicon particle of high power capacity forms, the mass content of described silicon particle is 10～95%, and the mass content of described carbon base body is 5～90%; The average grain diameter of described silicon particle is 30nm～1 μ m; Described carbon base body is organic carbon source pyrolysis gained.
Described silicon particle is dispersed in described carbon base body, in the surrounding of each or the silicon particle described in several, is reserved with three-dimensional expansion space.
The volume in reserved described three-dimensional expansion space is 1～3 times of volume of described silicon particle.
In order to solve above-mentioned second technical problem, preparation provided by the invention has the method for the silicon-carbon composite cathode material of three-dimensional preformed hole structure, comprises the following steps:
The first step: silicon particle is carried out to surface modification: be averaged particle diameter at the silicon particle of 30nm～1 μ m, by silicon particle and organic solvent mass ratio 1: 100～1: 10, ultrasonic being dispersed in organic solvent, formed uniform silicon particle suspension; Silicon particle suspension is placed in to blender mechanical agitation, meanwhile, drips surface modifier, continue stirring reaction 1～2 hour, obtain the high power capacity silicon particle dispersion after surface modification;
Second step: coated with silica silicon particle: the silicon particle dispersion after the first step of learning from else's experience modification, in ultrasonic process, pH=8～10 of regulator solution, form finely dispersed alkaline suspension liquid; Then slowly drip tetraethoxysilane in ethanolic solution, the volume ratio of tetraethoxysilane and ethanol is 1: 10～20, rate of addition 0.1～1mL/min, after dripping, in the water-bath of 38-42 ℃, mechanical agitation is reacted 1～2 hour, after reaction finishes, the centrifugal supernatant of removing, with absolute ethyl alcohol and water washing, obtains the silicon particle of coated with silica after being dried;
The 3rd step: carbon source precursor coated silica/silicon compound particle: carbon source precursor is dissolved in solvent and forms carbon source precursor solution, the silicon particle of second step gained coated with silica is joined in carbon source precursor solution to ultrasonic mixing 0.5～1 hour; Temperature is increased to 55-65 ℃ of mechanical agitation 1～2 hour, then proceeds to drying box, first predrying 10-14 hour at 75-85 ℃, after at 140-160 ℃ dry 10-14 hour, grind the compound particle of the carbon/silica/silicon that obtains particle diameter 1～20 μ m;
The 4th step: high temperature cabonization is processed: by the compound particle of the 3rd step gained carbon/silica/silicon under protective atmosphere, with the speed of 1～10 ℃/min, be warming up to 600～1200 ℃, be incubated 2～5 hours, naturally cool to room temperature, obtain the compound particle of carbon/silica/silicon;
The 5th step: remove silica template: it is in 4～40% hydrofluoric acid that the compound particle of the carbon/silica/silicon of the 4th step gained is joined to mass concentration, mechanical agitation reaction 2～6 hours, dissolving, as the silicon dioxide of preformed hole template, obtains the silicon-carbon composite cathode material for the three-dimensional preformed hole structure of having of lithium ion battery.
Organic solvent described in the above-mentioned first step is the various liquid that can make silicon particle disperse, and is one or more in water, ethanol, propyl alcohol, acetone; The addition of described surface modifier is 1～20% of high power capacity silicon mass particle, and described surface modifier is selected from one or more in alkyl silane coupling agent, amino silicane coupling agent, softex kw, dodecyl sodium sulfate, neopelex, polyvinyl alcohol and polyvinylpyrrolidone.
The mass ratio of the silicon particle after modification described in above-mentioned second step and tetraethoxysilane is 1: 2～1: 6, and in the silicon particle of described coated with silica, the mass ratio of silicon particle and silicon dioxide is 1: 1～1: 3.
Carbon source precursor described in above-mentioned the 3rd step is water-soluble or the polyvinyl alcohol of organic solvent system, polystyrene, phenolic resins, epoxy resin, glucose, sugarcane sugar and starch in one or more, described carbon source precursor and the mass ratio of silicon particle are 30: 1～1: 6; Described solvent is any solvent that can dissolve selected carbon source precursor, is one or more in water, ethanol, methyl alcohol, n-butanol, acetone, espeleton, benzene, toluene and dimethylbenzene.
Protective atmosphere described in above-mentioned the 4th step is nitrogen or argon gas, and gas flow is 0.1～3m
3/ h.
The ultrasonic power of ultrasonic processing is 100～200W, and supersonic frequency is 40～80kHz, and ultrasonic time is 0.5～1 hour.
The mixing speed that mechanical agitation is processed is 500～2000r/min.
Adopt silicon-carbon composite cathode material with three-dimensional preformed hole structure of technique scheme and preparation method thereof, silicon/the carbon compound cathode materials of three-dimensional preformed hole structure using there is high conductivity and rock-steady structure material with carbon element as matrix, hold dispersedly high power capacity silicon particle, in each or several silicon particles, be reserved with suitable three-dimensional expansion space around, the Swelling and contraction of silicon is all occurred in self zonule around, so both guaranteed the independent dispersiveness of silicon grain in carbon base body, the swelling stress that can prevent again silicon destroys carbon base body, thereby obtain constitutionally stable electrode.In the present invention, reserved three-dimensional expansion spatial volume is 1～3 times of silicon particle volume, if headspace is too small to be less than 1 times, be not enough to play the effect of holding the expansion of silicon particle and Stable Carbon basal body structure, if headspace is excessive to be greater than 3 times, material tap density reduces, and can reduce to a great extent the volume and capacity ratio of material.First the present invention carries out modification at silicon particle surface; Then at the coated adjustable silica shell of a layer thickness of silicon particle surface; High temperature cabonization is prepared carbon/silica/silicon compound particle of decentralized again, and the silica/silicon particle of several nucleocapsid structures is dispersed in stable material with carbon element; Finally utilize hydrofluoric acid the strong selectivity of silicon and silicon dioxide to be reacted to remove the silica shell of silicon particle surface, prepared the silicon/carbon compound cathode materials with three-dimensional reserved pore volume of the present invention.The present invention compared with prior art, has the following advantages:
1. material with carbon element itself have good de-/embedding lithium performance, there is dispersing nanometer silicon, prevent secondary agglomeration and promote the double action of electrode capacity;
2. material with carbon element Stability Analysis of Structures, particularly in the present invention, each or several nano-silicons have all been reserved enough expansion spaces around, the Swelling and contraction of silicon in charge and discharge process all occurs in the little space around self, guaranteed the mutual independence of silicon and carbon base body, the swelling stress that prevents silicon destroys carbon base body, maintains stable electrode structure;
3. the preformed hole structure in material can be at surrounding's storage electrolyte of nano-silicon, form the miniature electrolyte storage container of many locals, guarantee on the one hand electrically contacting of silicon and high conductive carbon matrix, can greatly shorten lithium ion migration path on the other hand, make take off effectively at high speed/embedding of lithium ion, reach the object that improves high rate performance;
4. flow process is simple, controlled, without expensive equipment and complicated operation, can be mass-produced, and practical application foreground is good.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph of the prepared coated with silica silicon of embodiment 1 particle.
Fig. 2 is the prepared stereoscan photograph with the silicon/carbon composite of three-dimensional preformed hole structure of embodiment 1.
Fig. 3 is the prepared first charge-discharge curve chart with the silicon/carbon composite of three-dimensional preformed hole structure of embodiment 1.
Fig. 4 is the structural representation with the silicon-carbon composite cathode material of three-dimensional preformed hole structure of the present invention.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail, but the present invention is not limited to following examples.
Referring to Fig. 4, a kind of silicon-carbon composite cathode material with three-dimensional preformed hole structure, the carbon base body 1 with high conductivity and rock-steady structure, consist of with the silicon particle 3 of high power capacity, the mass content of silicon particle 3 is 10～95%, and the mass content of carbon base body 1 is 5～90%; The average grain diameter of silicon particle 3 is 30nm～1 μ m; Carbon base body 1 is organic carbon source pyrolysis gained; Silicon particle 3 is dispersed in carbon base body 1, in the surrounding of each or several silicon particles 3, is reserved with three-dimensional expansion space 2, and the volume in reserved three-dimensional expansion space 2 is 1～3 times of volume of silicon particle 3.
Embodiment 1:
The first step: silicon particle is carried out to surface modification
Getting 1g average grain diameter is the nano-silicon particle of 30nm, joins in 100mL ethanol solution, ultrasonic dispersion 30min, and wherein ultrasonic power is 200W, supersonic frequency is 45kHz, forms uniform silicon particle suspension; Silicon particle suspension is placed in to blender and stirs, under the stirring intensity of 1000r/min, add 0.2g softex kw, continue stirring reaction 2h, obtain the high power capacity silicon particle dispersion after surface modification;
Second step: coated with silica silicon particle
Silicon particle dispersion 50mL after the first step of learning from else's experience modification, in ultrasonic process, the pH=9 that the ammoniacal liquor of take is acidity-basicity regulator regulator solution, forms finely dispersed alkaline suspension liquid; Then slowly drip in the mixed solution of 21mL tetraethoxysilane and ethanol, wherein the volume ratio of tetraethoxysilane and ethanol is 1: 20, rate of addition 0.4mL/min, after dripping, in 40 ℃ of water-baths, mechanical agitation is reacted 2 hours, after reaction finishes, the centrifugal supernatant of removing, with absolute ethyl alcohol and water washing, obtains the silicon particle of coated with silica after 105 ℃ of dry 12h.Fig. 1 is the stereoscan photograph of the prepared coated with silica silicon of the present embodiment particle, 10,000 times of multiplication factors, as can be seen from Fig., the particle diameter of prepared coated with silica silicon particle is evenly distributed, average grain diameter is about 50nm, and layer of silicon dioxide shell has been described in nano-silicon coated with uniform.
The 3rd step: carbon source precursor coated silica/silicon compound particle
Sucrose 5g is dissolved in the mixed solution of 60mL water and ethanol and forms sucrose solution, wherein the volume ratio of water and ethanol is 1: 5, the silicon particle 1g of second step gained coated with silica is joined in sucrose solution to ultrasonic mixing 0.5 hour; Temperature is increased to 60 ℃ of mechanical agitation 2 hours, then proceeds to drying box, first at 80 ℃ predrying 12 hours, at latter 150 ℃ dry 12 hours, grind the compound particle of the sucrose/silica/silicon that obtains average grain diameter 2 μ m.
The 4th step: high temperature cabonization is processed
The compound particle of the 3rd step gained sucrose/silica/silicon is carried out to high temperature cabonization processing; under the protective atmosphere of argon gas, with the speed of 5 ℃/min, be warming up to 1000 ℃, be incubated 3 hours; naturally cool to room temperature, obtain the compound particle of carbon/silica/silicon.Argon gas flow is 0.2m
3/ h.
The 5th step: remove silica template
It is in 10% hydrofluoric acid that the compound particle of the carbon/silica/silicon of the 4th step gained is joined to mass concentration, mechanical agitation reaction 4 hours, dissolving is as the silicon dioxide of preformed hole template, thereby obtain and silicon dioxide shape and the consistent three-dimensional reserving hole that distributes, at 105 ℃ of vacuumize 24h, obtain the silicon-carbon composite cathode material for the three-dimensional preformed hole structure of having of lithium ion battery of the present invention.Fig. 2 is the prepared stereoscan photograph with the silicon-carbon composite cathode material of three-dimensional preformed hole structure of the present embodiment, 10,000 times of multiplication factors, as can be seen from Fig., the material with carbon element being formed by sucrose pyrolysis is coated on silicon particle wherein substantially, form the spherical particle of diameter 1.5 μ m, at material surface, have a small amount of pore space structure of removing after silica template.
Detect
Gained is had to the black and binding agent PVDF of silicon-carbon composite cathode material, the conductive acetylene of three-dimensional preformed hole structure and with mass percent, be mixed and made into electrode slice at 80: 10: 10, and forming the electrochemistry embedding/de-lithium performance of half-cell test material with metal lithium sheet, electrolyte is commercially available 1MLiPF
6/ EC+DMC solution.Utilize Land battery test system at room temperature to carry out constant current charge-discharge performance test to above-mentioned half-cell, charge-discharge magnification is 100mAh/g, and charging/discharging voltage scope is 0.01-1.2V.Fig. 3 is the prepared charging and discharging curve with the silicon/carbon composite of three-dimensional preformed hole structure of the present embodiment, from Fig. 3, can find, material first reversible capacity is 1025mAh/g, coulomb efficiency is 72.7%, the reversible capacity circulating after 100 times is 943mAh/g, capability retention reaches 92%, shows good cyclical stability.
Embodiment 2:
The first step: silicon particle is carried out to surface modification
Getting 1g average grain diameter is the nano-silicon particle of 80nm, joins in 100mL ethanol solution, ultrasonic dispersion 30min, and wherein ultrasonic power is 200W, supersonic frequency is 45kHz, forms uniform silicon particle suspension; Silicon particle suspension is placed in to blender and stirs, under the stirring intensity of 1000r/min, add 0.2g softex kw, continue stirring reaction 2h, obtain the high power capacity silicon particle dispersion after surface modification.
Second step: coated with silica silicon particle
Silicon particle dispersion 50mL after the first step of learning from else's experience modification, in ultrasonic process, the pH=9 that the ammoniacal liquor of take is acidity-basicity regulator regulator solution, forms finely dispersed alkaline suspension liquid; Then slowly drip in the mixed solution of 22mL tetraethoxysilane and ethanol, wherein the volume ratio of tetraethoxysilane and ethanol is 1: 10, rate of addition 0.4mL/min, after dripping, in 38 ℃ of water-baths, mechanical agitation is reacted 2 hours, after reaction finishes, the centrifugal supernatant of removing, with absolute ethyl alcohol and water washing, obtains the silicon particle of coated with silica after 105 ℃ of dry 12h.
The 3rd step: carbon source precursor coated silica/silicon compound particle
Sucrose 10g is dissolved in the mixed solution of 60mL water and ethanol and forms sucrose solution, wherein the volume ratio of water and ethanol is 1: 5, the silicon particle 1g of second step gained coated with silica is joined in sucrose solution to ultrasonic mixing 0.5 hour; Temperature is increased to 55 ℃ of mechanical agitation 2 hours, then proceeds to drying box, first at 75 ℃ predrying 14 hours, at latter 140 ℃ dry 14 hours, grind the compound particle of the sucrose/silica/silicon that obtains average grain diameter 3.5 μ m.
The 4th step: high temperature cabonization is processed, with embodiment 1
The 5th step: remove silica template
It is in 4% hydrofluoric acid that the compound particle of the carbon/silica/silicon of the 4th step gained is joined to mass concentration, mechanical agitation reaction 6 hours, dissolving is as the silicon dioxide of preformed hole template, thereby obtain and silicon dioxide shape and the consistent three-dimensional reserving hole that distributes, at 105 ℃ of vacuumize 24h, obtain the silicon-carbon composite cathode material for the three-dimensional preformed hole structure of having of lithium ion battery of the present invention.
Detect: with embodiment 1.Test result demonstration, material material first reversible capacity is 816mAh/g, and coulomb efficiency is 75.2%, and the reversible capacity circulating after 100 times is 775mAh/g, and capability retention is 95%, shows good cyclical stability.
Embodiment 3:
The first step: silicon particle is carried out to surface modification
Getting 1g average grain diameter is the nano-silicon particle of 30nm, joins in 100mL ethanol solution, ultrasonic dispersion 30min, and wherein ultrasonic power is 200W, supersonic frequency is 45kHz, forms uniform silicon particle suspension; Silicon particle suspension is placed in to blender and stirs, under the stirring intensity of 1000r/min, add 2mL KH550 model silane coupler, continue stirring reaction 2h, obtain the high power capacity silicon particle dispersion after surface modification.
Second step: coated with silica silicon particle
Silicon particle dispersion 50mL after the first step of learning from else's experience modification, in ultrasonic process, the pH=9 that the ammoniacal liquor of take is acidity-basicity regulator regulator solution, forms finely dispersed alkaline suspension liquid; Then slowly drip in the mixed solution of 21mL tetraethoxysilane and ethanol, wherein the volume ratio of tetraethoxysilane and ethanol is 1: 20, rate of addition 0.4mL/min, after dripping, in 40 ℃ of water-baths, mechanical agitation is reacted 2 hours, after reaction finishes, the centrifugal supernatant of removing, with absolute ethyl alcohol and water washing, obtains the silicon particle of coated with silica after 105 ℃ of dry 12h.
The 3rd step: carbon source precursor coated silica/silicon compound particle
Phenolic resins 6g is dissolved in the acetone of 50mL and forms phenol resin solution, the silicon particle 1g of second step gained coated with silica is joined in phenol resin solution to ultrasonic mixing 0.5 hour; Temperature is increased to 60 ℃ of mechanical agitation 2 hours, then proceeds to drying box, first at 80 ℃ predrying 12 hours, at latter 150 ℃ dry 12 hours, grind the compound particle of the phenolic resins/silica/silicon that obtains average grain diameter 3 μ m.
The 4th step: high temperature cabonization is processed, with embodiment 1
The 5th step: remove silica template
It is in 40% hydrofluoric acid that the compound particle of the carbon/silica/silicon of the 4th step gained is joined to mass concentration, mechanical agitation reaction 2 hours, dissolving is as the silicon dioxide of preformed hole template, thereby obtain and silicon dioxide shape and the consistent three-dimensional reserving hole that distributes, at 105 ℃ of vacuumize 24h, obtain the silicon-carbon composite cathode material for the three-dimensional preformed hole structure of having of lithium ion battery of the present invention.
Detect: with embodiment 1.Test result demonstration, material material first reversible capacity is 1166mAh/g, and coulomb efficiency is 73.5%, and the reversible capacity circulating after 100 times is 1096mAh/g, and capability retention is 94%, shows good cyclical stability.
Embodiment 4:
The first step: silicon particle is carried out to surface modification
Getting 1g average grain diameter is the nano-silicon particle of 80nm, joins in 100mL ethanol solution, ultrasonic dispersion 30min, and wherein ultrasonic power is 200W, supersonic frequency is 45kHz, forms uniform silicon particle suspension; Silicon particle suspension is placed in to blender and stirs, under the stirring intensity of 1000r/min, add 2mL KH550 model silane coupler, continue stirring reaction 2h, obtain the high power capacity silicon particle dispersion after surface modification.
Second step: coated with silica silicon particle
Silicon particle dispersion 50mL after the first step of learning from else's experience modification, in ultrasonic process, the pH=9 that the ammoniacal liquor of take is acidity-basicity regulator regulator solution, forms finely dispersed alkaline suspension liquid; Then slowly drip in the mixed solution of 22mL tetraethoxysilane and ethanol, wherein the volume ratio of tetraethoxysilane and ethanol is 1: 10, rate of addition 0.4mL/min, after dripping, in 40 ℃ of water-baths, mechanical agitation is reacted 2 hours, after reaction finishes, the centrifugal supernatant of removing, with absolute ethyl alcohol and water washing, obtains the silicon particle of coated with silica after 105 ℃ of dry 12h.
The 3rd step: carbon source precursor coated silica/silicon compound particle
Phenolic resins 12g is dissolved in the acetone of 50mL and forms phenol resin solution, the silicon particle 1g of second step gained coated with silica is joined in phenol resin solution to ultrasonic mixing 0.5 hour; Temperature is increased to 65 ℃ of mechanical agitation 2 hours, then proceeds to drying box, first at 85 ℃ predrying 10 hours, at latter 160 ℃ dry 10 hours, grind the compound particle of the phenolic resins/silica/silicon that obtains average grain diameter 5 μ m.
The 4th step: high temperature cabonization is processed, with embodiment 1
The 5th step: remove silica template, with embodiment 1
Detect: with embodiment 1.Test result demonstration, material first reversible capacity is 977mAh/g, and coulomb efficiency is 78.8%, and the reversible capacity circulating after 100 times is 947mAh/g, and capability retention is 97%, shows good cyclical stability.
Embodiment 5:
The first step: silicon particle is carried out to surface modification
Getting 1g average grain diameter is the nano-silicon particle of 1 μ m, joins in 10mL aqueous propanol solution, ultrasonic dispersion 50min, and wherein ultrasonic power is 200W, supersonic frequency is 40kHz, forms uniform silicon particle suspension; Silicon particle suspension is placed in to blender and stirs, under the stirring intensity of 2000r/min, add 0.2g neopelex, continue stirring reaction 1h, obtain the high power capacity silicon particle dispersion after surface modification;
Second step: coated with silica silicon particle
Silicon particle dispersion 50mL after the first step of learning from else's experience modification, in ultrasonic process, the pH=8 that the ammoniacal liquor of take is acidity-basicity regulator regulator solution, forms finely dispersed alkaline suspension liquid; Then slowly drip in the mixed solution of 21mL tetraethoxysilane and ethanol, wherein the volume ratio of tetraethoxysilane and ethanol is 1: 20, rate of addition 0.1mL/min, after dripping, in 38 ℃ of water-baths, mechanical agitation is reacted 1 hour, after reaction finishes, the centrifugal supernatant of removing, with absolute ethyl alcohol and water washing, obtains the silicon particle of coated with silica after 105 ℃ of dry 12h.
The 3rd step: carbon source precursor coated silica/silicon compound particle
Polyvinyl alcohol 5g is dissolved in the mixed solution of 60mL methyl alcohol and n-butanol and forms poly-vinyl alcohol solution, wherein the volume ratio of methyl alcohol and n-butanol is 1: 5, the silicon particle 1g of second step gained coated with silica is joined in polyvinyl alcohol, polystyrene and epoxy resin solution to ultrasonic mixing 1 hour; Temperature is increased to 55 ℃ of mechanical agitation 1 hour, then proceeds to drying box, first at 75 ℃ predrying 14 hours, at latter 140 ℃ dry 14 hours, grind the compound particle of the polyvinyl alcohol/silica/silicon that obtains average grain diameter 10 μ m.
The 4th step: high temperature cabonization is processed
The compound particle of the 3rd step gained polyvinyl alcohol/silica/silicon is carried out to high temperature cabonization processing; under the protective atmosphere of nitrogen, with the speed of 1 ℃/min, be warming up to 600 ℃, be incubated 2 hours; naturally cool to room temperature, obtain the compound particle of carbon/silica/silicon.Nitrogen gas flow is 0.1m
3/ h.
The 5th step: remove silica template
It is in 10% hydrofluoric acid that the compound particle of the carbon/silica/silicon of the 4th step gained is joined to mass concentration, mechanical agitation reaction 3 hours, dissolving is as the silicon dioxide of preformed hole template, thereby obtain and silicon dioxide shape and the consistent three-dimensional reserving hole that distributes, at 105 ℃ of vacuumize 24h, obtain the silicon-carbon composite cathode material for the three-dimensional preformed hole structure of having of lithium ion battery of the present invention.
Detect: with embodiment 1.Test result demonstration, material material first reversible capacity is 890mAh/g, and coulomb efficiency is 68.5%, and the reversible capacity circulating after 100 times is 805mAh/g, and capability retention is 90.4%, shows good cyclical stability.
Embodiment 6:
The first step: silicon particle is carried out to surface modification
Getting 1g average grain diameter is the nano-silicon particle of 60nm, joins in 100mL acetone soln, ultrasonic dispersion 60min, and wherein ultrasonic power is 100W, supersonic frequency is 80kHz, forms uniform silicon particle suspension; Silicon particle suspension is placed in to blender and stirs, under the stirring intensity of 500r/min, add 0.2g polyvinyl alcohol, continue stirring reaction 1.5h, obtain the high power capacity silicon particle dispersion after surface modification;
Second step: coated with silica silicon particle
Silicon particle dispersion 50mL after the first step of learning from else's experience modification, in ultrasonic process, the pH=9 that the ammoniacal liquor of take is acidity-basicity regulator regulator solution, forms finely dispersed alkaline suspension liquid; Then slowly drip in the mixed solution of 21mL tetraethoxysilane and ethanol, wherein the volume ratio of tetraethoxysilane and ethanol is 1: 20, rate of addition 1mL/min, after dripping, in 42 ℃ of water-baths, mechanical agitation is reacted 1.5 hours, after reaction finishes, the centrifugal supernatant of removing, with absolute ethyl alcohol and water washing, obtains the silicon particle of coated with silica after 105 ℃ of dry 12h.
The 3rd step: carbon source precursor coated silica/silicon compound particle
Glucose 5g is dissolved in the mixed solution of 60mL benzene and dimethylbenzene and forms glucose solution, wherein the volume ratio of benzene and dimethylbenzene is 1: 5, the silicon particle 1g of second step gained coated with silica is joined in glucose solution to ultrasonic mixing 0.5 hour; Temperature is increased to 65 ℃ of mechanical agitation 2 hours, then proceeds to drying box, first at 85 ℃ predrying 10 hours, at latter 160 ℃ dry 10 hours, grind the compound particle of the glucose/silica/silicon that obtains average grain diameter 4 μ m.
The 4th step: high temperature cabonization is processed
The compound particle of the 3rd step gained glucose/silica/silicon is carried out to high temperature cabonization processing; under the protective atmosphere of argon gas, with the speed of 10 ℃/min, be warming up to 1200 ℃, be incubated 5 hours; naturally cool to room temperature, obtain the compound particle of carbon/silica/silicon.Argon gas flow is 3m
3/ h.
The 5th step: remove silica template
It is in 30% hydrofluoric acid that the compound particle of the carbon/silica/silicon of the 4th step gained is joined to mass concentration, mechanical agitation reaction 5 hours, dissolving is as the silicon dioxide of preformed hole template, thereby obtain and silicon dioxide shape and the consistent three-dimensional reserving hole that distributes, at 105 ℃ of vacuumize 24h, obtain the silicon-carbon composite cathode material for the three-dimensional preformed hole structure of having of lithium ion battery of the present invention.
Detect: with embodiment 1.Test result demonstration, material first reversible capacity is 1190mAh/g, and coulomb efficiency is 78.2%, and the reversible capacity circulating after 100 times is 1056mAh/g, and capability retention is 88.7%, shows good cyclical stability.
Claims (7)
1. a preparation method with the silicon-carbon composite cathode material of three-dimensional preformed hole structure, is characterized in that: comprise the following steps:
The first step: silicon particle is carried out to surface modification: be averaged particle diameter at the silicon particle of 30nm～1 μ m, by silicon particle and organic solvent mass ratio 1:100～1:10, ultrasonic being dispersed in organic solvent, forms uniform silicon particle suspension; Silicon particle suspension is placed in to blender mechanical agitation, meanwhile, drips surface modifier, continue stirring reaction 1～2 hour, obtain the high power capacity silicon particle dispersion after surface modification;
Second step: coated with silica silicon particle: the silicon particle dispersion after the first step of learning from else's experience modification, in ultrasonic process, pH=8～10 of regulator solution, form finely dispersed alkaline suspension liquid; Then slowly drip the ethanolic solution of tetraethoxysilane in finely dispersed alkaline suspension liquid, the volume ratio of tetraethoxysilane and ethanol is 1:10～20, rate of addition 0.1～1mL/min, after dripping, in the water-bath of 38-42 ℃, mechanical agitation is reacted 1～2 hour, after reaction finishes, the centrifugal supernatant of removing, with absolute ethyl alcohol and water washing, obtains the silicon particle of coated with silica after being dried;
The 3rd step: carbon source precursor coated silica/silicon compound particle: carbon source precursor is dissolved in solvent and forms carbon source precursor solution, the silicon particle of second step gained coated with silica is joined in carbon source precursor solution to ultrasonic mixing 0.5～1 hour; Temperature is increased to 55-65 ℃ of mechanical agitation 1～2 hour, then proceeds to drying box, first predrying 10-14 hour at 75-85 ℃, after at 140-160 ℃ dry 10-14 hour, grind the compound particle of the carbon/silica/silicon that obtains particle diameter 1～20 μ m;
The 4th step: high temperature cabonization is processed: by the compound particle of the 3rd step gained carbon/silica/silicon under protective atmosphere, with the speed of 1～10 ℃/min, be warming up to 600～1200 ℃, be incubated 2～5 hours, naturally cool to room temperature, obtain the compound particle of carbon/silica/silicon;
The 5th step: remove silica template: it is in 4～40% hydrofluoric acid that the compound particle of the carbon/silica/silicon of the 4th step gained is joined to mass concentration, mechanical agitation reaction 2～6 hours, dissolving, as the silicon dioxide of preformed hole template, obtains the silicon-carbon composite cathode material for the three-dimensional preformed hole structure of having of lithium ion battery.
2. the preparation method with the silicon-carbon composite cathode material of three-dimensional preformed hole structure according to claim 1, it is characterized in that: organic solvent described in the above-mentioned first step is the various liquid that can make silicon particle disperse, is one or more in water, ethanol, propyl alcohol, acetone; The addition of described surface modifier is 1～20% of high power capacity silicon mass particle, and described surface modifier is selected from one or more in alkyl silane coupling agent, amino silicane coupling agent, softex kw, dodecyl sodium sulfate, neopelex, polyvinyl alcohol and polyvinylpyrrolidone.
3. the preparation method with the silicon-carbon composite cathode material of three-dimensional preformed hole structure according to claim 1 and 2, it is characterized in that: the mass ratio of the silicon particle after modification described in above-mentioned second step and tetraethoxysilane is 1:2～1:6, and in the silicon particle of described coated with silica, the mass ratio of silicon particle and silicon dioxide is 1:1～1:3.
4. the preparation method with the silicon-carbon composite cathode material of three-dimensional preformed hole structure according to claim 1 and 2, it is characterized in that: the carbon source precursor described in above-mentioned the 3rd step is water-soluble or the polyvinyl alcohol of organic solvent system, polystyrene, phenolic resins, epoxy resin, glucose, sugarcane sugar and starch in one or more, described carbon source precursor and the mass ratio of silicon particle are 30:1～1:6; Described solvent is any solvent that can dissolve selected carbon source precursor, is one or more in water, ethanol, methyl alcohol, n-butanol, acetone, espeleton, benzene, toluene and dimethylbenzene.
5. the preparation method with the silicon-carbon composite cathode material of three-dimensional preformed hole structure according to claim 1 and 2, is characterized in that: the protective atmosphere described in above-mentioned the 4th step is nitrogen or argon gas, and gas flow is 0.1～3m
3/ h.
6. the preparation method with the silicon-carbon composite cathode material of three-dimensional preformed hole structure according to claim 1 and 2, is characterized in that: the ultrasonic power of ultrasonic processing is 100～200W, and supersonic frequency is 40～80kHz, and ultrasonic time is 0.5～1 hour.
7. the preparation method with the silicon-carbon composite cathode material of three-dimensional preformed hole structure according to claim 1 and 2, is characterized in that: the mixing speed that mechanical agitation is processed is 500～2000r/min.
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