CN102623680A - 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 lithium ion battery with silicon-carbon composite cathode material and preparation method thereof, particularly relate to a kind of silicon-carbon composite cathode material and preparation method thereof with three-dimensional preformed hole structure.
Background technology
At present, the commercial li-ion battery extensively adopts the 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 the key that improves the lithium ion battery performance with application.Silicon materials are considered to one of ideal candidates material that substitutes graphite cathode material owing to have 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 (about 300%); Produce that the silicon grain breaks, phenomenons such as efflorescence and secondary agglomeration; Make and separate between conductive network and the silicon particle, finally cause the electrode interior structural damage, and then influence the cycle performance of battery.This has influenced its extensive industrialization process greatly.
Change in the enormousness that embedding/take off lithium process produces in order to slow down silica-base material, improve the chemical property of silicon-based anode, the researcher has carried out positive exploration both at home and abroad.Study on the modification to silica-base material mainly contains following several kinds of approach at present:
(1) silicon materials carry out nanometerizations, for example patent CN101901897A has reported a kind of nano silicon composite cathode material for lithium ion battery and preparation method thereof.Research shows 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 along with the carrying out of circulation gradually, from and lost the distinctive performance of nano particle, cause destructurized, reversible capacity to be decayed.In addition, also the someone adopts some new technology to prepare the silicium cathode material that has than height ratio capacity, good circulation performance, for example is grown directly upon the silicon nano-array [C.K.Chan on the collector; H.Peng, G.Liu, et al.Nature Nanotechnology; 2008,3:31-35], thin film silicon electrode [M.Uehara, the J.Suzuki of magnetron sputtering method preparation; 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 alloying or partially-alloyed; Utilize the metal material good ductility to alleviate the destruction of the internal stress of the volumetric expansion generation in the removal lithium embedded process 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 because most of metal itself that this type research institute adopts is an inert matter, thereby has limited the raising of specific capacity, and some metalline is crisp partially, after the long-term circulation, possibly crack, and forms irreversible capacity equally.
(3) silicon materials and material with carbon element are compound, itself has good electrical conductivity material with carbon element, 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, the Si-C composite material cycle performance improves significantly.The silicon-carbon complex method generally has mechanical mixing, polymer pyrolysismethod, 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 because just simple physics is compound; Can not fundamentally suppress the bulk effect in the 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; Though the method for copyrolysis can be dispersed in the silicon particle in the carbon base body well; Improve charge-discharge performance to a certain extent, but the structural stability of carbon base body need be furtherd investigate also.Employing benzene such as Liu are unstripped gas, have synthesized surface carbon with the CVD method and have coated silica-base material [W.R.Liu, J.H.Wang; H.C.Wu, et al..J.Electrochem.Soc., 2005; 152 (9): A1719-A1725], but the carbon shell that is coated is being destroyed and CVD method complex process repeatedly easily after the circulation; Process is difficult to control, is difficult to obtain the product of uniformity, is unfavorable for large-scale production.
Think why present Si-C composite material can not solve the expansion issues of silicon in charge and discharge process fully after the present patent application person research, key is that wherein carbon component does not really play the effect of rock-steady structure.After discharging and recharging repeatedly, as the carbon of conducting base since receive silicon swelling stress effect and self recurring structure caves in, the effect of forfeiture protection silicon and its electro-chemical activity is reduced.Therefore research has Si-C composite material of new construction and preparation method thereof, and is very big to the industrialization process meaning that promotes silicon-based anode.
Summary of the invention
First technical problem to be solved by this invention provides a kind ofly to be had the capacity height, has extended cycle life and the silicon-carbon composite cathode material with three-dimensional preformed hole structure that high rate performance is excellent.
Second technical problem to be solved by this invention provides a kind of flow process simple controllable, and be with low cost, 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; Silicon-carbon composite cathode material with three-dimensional preformed hole structure provided by the invention; Silicon particle by carbon base body with high conductivity and rock-steady structure and high power capacity constitutes; 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 an organic carbon source pyrolysis gained.
Described silicon particle is dispersed in the described carbon base body, around each or several described silicon particles, is reserved with the three-dimensional expansion space.
The volume in the described three-dimensional expansion space of reserving 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, may further comprise the steps:
The first step: the silicon particle is carried out surface modification: the equal particle diameter of making even was pressed silicon particle and organic solvent mass ratio 1: 100～1: 10 at the silicon particle of 30nm～1 μ m, and ultrasonic being dispersed in the organic solvent forms uniform silicon particle suspension; The silicon particle suspension is placed the blender mechanical agitation, simultaneously, drip surface modifier, continued stirring reaction 1～2 hour, obtain the high power capacity silicon particle dispersion after the surface modification;
Second step: coated with silica silicon particle: the silicon particle dispersion after the first step of learning from else's experience modification is handled, in ultrasonic process, the pH=8 of regulator solution～10 form finely dispersed alkaline suspension liquid; Slowly drip tetraethoxysilane then in ethanolic solution; The volume ratio of tetraethoxysilane and ethanol is 1: 10～20, and rate of addition 0.1～1mL/min drips back mechanical agitation in 38-42 ℃ water-bath and 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 the drying;
The 3rd step: carbon source precursor coated silica/silicon compound particle: the carbon source precursor is dissolved in the solvent forms carbon source precursor solution, the silicon particle of the second step gained coated with silica is joined in the carbon source precursor solution ultrasonic mixing 0.5～1 hour; Temperature was increased to 55-65 ℃ of mechanical agitation 1～2 hour, changes drying box then over to, earlier 75-85 ℃ predrying 10-14 hour down, the back 140-160 ℃ dry 10-14 hour down, grind the compound particle of the carbon/silica/silicon that obtains particle diameter 1～20 μ m;
The 4th step: high temperature cabonization is handled: with the compound particle of the 3rd step gained carbon/silica/silicon under protective atmosphere; Be warming up to 600～1200 ℃ with 1～10 ℃/minute speed; 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% the hydrofluoric acid that the compound particle of the carbon/silica/silicon of the 4th step gained is joined mass concentration; Mechanical agitation reaction 2～6 hours; Dissolving obtains being used for the silicon-carbon composite cathode material of the three-dimensional preformed hole structure of having of lithium ion battery as the silicon dioxide of preformed hole template.
Organic solvent described in the above-mentioned first step is the various liquid that the silicon particle is disperseed, and is in water, ethanol, propyl alcohol, the acetone one or more; The addition of described surface modifier is 1～20% of a 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 the polyvinylpyrrolidone.
The silicon particle after modification is handled described in above-mentioned second step and the mass ratio of tetraethoxysilane are 1: 2～1: 6, and the mass ratio of silicon particle and silicon dioxide is 1: 1～1: 3 in the silicon particle of described coated with silica.
Carbon source precursor described in above-mentioned the 3rd step be water-soluble or polyvinyl alcohol, polystyrene, phenolic resins, epoxy resin, glucose, sucrose and the starch of organic solvent system in one or more, the mass ratio of described carbon source precursor and silicon particle is 30: 1～1: 6; Described solvent is any solvent that can the dissolving carbon source precursor of selecting for use, is in water, ethanol, methyl alcohol, n-butanol, acetone, espeleton, benzene, toluene and the xylenes one or more.
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 sonicated is 100～200W, and supersonic frequency is 40～80kHz, and ultrasonic time is 0.5～1 hour.
The mixing speed that mechanical agitation is handled is 500～2000r/min.
Adopt silicon-carbon composite cathode material of technique scheme and preparation method thereof with three-dimensional preformed hole structure; Silicon/the carbon compound cathode materials of three-dimensional preformed hole structure with material with carbon element with high conductivity and rock-steady structure as matrix; Hold high power capacity silicon particle dispersedly; Around each or several silicon particles, be reserved with suitable three-dimensional expansion space, the expansion that makes silicon with shrink in the zonule that all occurs in around self, so both guaranteed the independent dispersiveness of silicon grain in carbon base body; The swelling stress that can prevent silicon again destroys carbon base body, thereby obtains constitutionally stable electrode.The three-dimensional expansion spatial volume of reserving among the present invention is 1～3 times of silicon particle volume; If then headspace is too small less than 1 times; Be not enough to play the effect of holding expansion of silicon particle and Stable Carbon basal body structure; If then headspace is excessive greater than 3 times, the material tap density reduces, and can reduce the volume and capacity ratio of material to a great extent.The present invention at first carries out modification at the silicon particle surface; Coat the adjustable silica shell of a layer thickness at the silicon particle surface then; High temperature cabonization prepares the carbon/silica/silicon compound particle of decentralized again, and the silica/silicon particle of several nucleocapsid structures is dispersed in the stable material with carbon element; Utilize hydrofluoric acid that the strong selectivity of silicon and silicon dioxide is reacted the silica shell that removes the silicon particle surface at last, prepared the three-dimensional silicon/carbon compound cathode materials of reserving pore volume that has according to the invention.The present invention compared with prior art has the following advantages:
1. material with carbon element itself has good taking off/embedding lithium performance, has dispersing nanometer silicon, prevents secondary agglomeration and promotes 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 on every side, and the expansion of silicon in charge and discharge process and contraction all occur in the little space around self, have guaranteed the mutual independence of silicon and carbon base body; The swelling stress that prevents silicon destroys carbon base body, keeps stable electrode structure;
3. the preformed hole structure in the material can store electrolyte around nano-silicon; Form the miniature electrolyte storage container of many locals; Guarantee electrically contacting of silicon and high conductive carbon matrix on the one hand; Can shorten the lithium ion migration path greatly on the other hand, lithium ion is taken off/embedding effectively at high speed, reach the purpose that improves high rate performance;
4. flow process is simple, controlled, need not expensive equipment and complicated step, can be mass-produced, and practical application foreground is good.
Description of drawings
Fig. 1 is the stereoscan photograph of embodiment 1 prepared coated with silica silicon particle.
Fig. 2 is embodiment 1 a prepared stereoscan photograph with silicon/carbon composite of three-dimensional preformed hole structure.
Fig. 3 is embodiment 1 a prepared first charge-discharge curve chart with silicon/carbon composite of three-dimensional preformed hole structure.
Fig. 4 is the structural representation with 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 done further explain, 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; Be made up of the silicon particle 3 of the carbon base body with high conductivity and rock-steady structure 1 with 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 an organic carbon source pyrolysis gained; Silicon particle 3 is dispersed in the carbon base body 1, around each or several silicon particles 3, is reserved with three-dimensional expansion space 2, and the volume in the three-dimensional expansion space 2 of reservation is 1～3 times of volume of silicon particle 3.
Embodiment 1:
The first step: the silicon particle is carried out surface modification
Getting the 1g average grain diameter is the nano-silicon particle of 30nm, joins in the 100mL ethanol solution, ultrasonic dispersion 30min, and wherein ultrasonic power is 200W, supersonic frequency is 45kHz, forms uniform silicon particle suspension; Place blender to stir the silicon particle suspension, under the stirring intensity of 1000r/min, add the 0.2g softex kw, continue stirring reaction 2h, obtain the high power capacity silicon particle dispersion after the surface modification;
Second step: coated with silica silicon particle
Silicon particle dispersion 50mL after the first step of learning from else's experience modification is handled in ultrasonic process, is the pH=9 of acidity-basicity regulator regulator solution with ammoniacal liquor, forms finely dispersed alkaline suspension liquid; Slowly drip in the mixed solution of 21mL tetraethoxysilane and ethanol then; Wherein the volume ratio of tetraethoxysilane and ethanol is 1: 20, and rate of addition 0.4mL/min drips back mechanical agitation in 40 ℃ of water-baths and 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 behind 105 ℃ of dry 12h.Fig. 1 is the stereoscan photograph of the prepared coated with silica silicon of present embodiment particle; 10,000 times of multiplication factors; Can find out from figure; The particle size distribution of prepared coated with silica silicon particle is even, and average grain diameter is about 50nm, and the layer of silicon dioxide shell has been described on the 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, and the silicon particle 1g of the second step gained coated with silica is joined in the sucrose solution ultrasonic mixing 0.5 hour; Temperature was increased to 60 ℃ of mechanical agitation 2 hours, changes drying box then over to, earlier 80 ℃ predrying 12 hours down, back 150 ℃ dry 12 hours down, grind the compound particle of the sucrose/silica/silicon that obtains average grain diameter 2 μ m.
The 4th step: high temperature cabonization is handled
The compound particle of the 3rd step gained sucrose/silica/silicon is carried out the high temperature cabonization processing; Under the protective atmosphere of argon gas, be warming up to 1000 ℃ with 5 ℃/minute speed, be incubated 3 hours; Naturally cool to room temperature, obtain the compound particle of carbon/silica/silicon.The argon gas flow is 0.2m
3/ h.
The 5th step: remove silica template
It is in 10% the hydrofluoric acid that the compound particle of carbon/silica/silicon of the 4th step gained is joined mass concentration; Mechanical agitation reaction 4 hours; Dissolving is as the silicon dioxide of preformed hole template; Thereby obtain and the silicon dioxide shape and the consistent three-dimensional reserving hole that distributes, promptly get the silicon-carbon composite cathode material that is used for the three-dimensional preformed hole structure of having of lithium ion battery according to the invention at 105 ℃ of vacuumize 24h.Fig. 2 is the prepared stereoscan photograph with silicon-carbon composite cathode material of three-dimensional preformed hole structure of present embodiment; 10,000 times of multiplication factors; Can find out from figure; The material with carbon element that is formed by the sucrose pyrolysis is coated on the silicon particle wherein basically, forms the spherical particle of the about 1.5 μ m of diameter, the pore space structure after there is a small amount of removal silica template in material surface.
Detect
Gained is had the black and binding agent PVDF of the silicon-carbon composite cathode material, conductive acetylene of three-dimensional preformed hole structure be mixed and made into electrode slice at 80: 10: 10 with mass percent; And form the electrochemistry embedding of half-cell test material/take off the lithium performance with metal lithium sheet, electrolyte is commercially available 1MLiPF
6/ EC+DMC solution.Utilize the Land battery test system that above-mentioned half-cell is at room temperature carried out the constant current charge-discharge performance test, charge-discharge magnification is 100mAh/g, and the charging/discharging voltage scope is 0.01-1.2V.Fig. 3 is the prepared charging and discharging curve with silicon/carbon composite of three-dimensional preformed hole structure of present embodiment; From Fig. 3, can find; Material reversible capacity first is 1025mAh/g, and enclosed pasture efficient is 72.7%, and the reversible capacity that circulates after 100 times is 943mAh/g; Capability retention reaches 92%, shows good cyclical stability.
Embodiment 2:
The first step: the silicon particle is carried out surface modification
Getting the 1g average grain diameter is the nano-silicon particle of 80nm, joins in the 100mL ethanol solution, ultrasonic dispersion 30min, and wherein ultrasonic power is 200W, supersonic frequency is 45kHz, forms uniform silicon particle suspension; Place blender to stir the silicon particle suspension, under the stirring intensity of 1000r/min, add the 0.2g softex kw, continue stirring reaction 2h, obtain the high power capacity silicon particle dispersion after the surface modification.
Second step: coated with silica silicon particle
Silicon particle dispersion 50mL after the first step of learning from else's experience modification is handled in ultrasonic process, is the pH=9 of acidity-basicity regulator regulator solution with ammoniacal liquor, forms finely dispersed alkaline suspension liquid; Slowly drip in the mixed solution of 22mL tetraethoxysilane and ethanol then; Wherein the volume ratio of tetraethoxysilane and ethanol is 1: 10, and rate of addition 0.4mL/min drips back mechanical agitation in 38 ℃ of water-baths and 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 behind 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, and the silicon particle 1g of the second step gained coated with silica is joined in the sucrose solution ultrasonic mixing 0.5 hour; Temperature was increased to 55 ℃ of mechanical agitation 2 hours, changes drying box then over to, earlier 75 ℃ predrying 14 hours down, back 140 ℃ dry 14 hours down, 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 handled, with embodiment 1
The 5th step: remove silica template
It is in 4% the hydrofluoric acid that the compound particle of carbon/silica/silicon of the 4th step gained is joined mass concentration; Mechanical agitation reaction 6 hours; Dissolving is as the silicon dioxide of preformed hole template; Thereby obtain and the silicon dioxide shape and the consistent three-dimensional reserving hole that distributes, promptly get the silicon-carbon composite cathode material that is used for the three-dimensional preformed hole structure of having of lithium ion battery according to the invention at 105 ℃ of vacuumize 24h.
Detect: with embodiment 1.Test result shows that materials reversible capacity first is 816mAh/g, and enclosed pasture efficient is 75.2%, and the reversible capacity that circulates after 100 times is 775mAh/g, and capability retention is 95%, shows good cyclical stability.
Embodiment 3:
The first step: the silicon particle is carried out surface modification
Getting the 1g average grain diameter is the nano-silicon particle of 30nm, joins in the 100mL ethanol solution, ultrasonic dispersion 30min, and wherein ultrasonic power is 200W, supersonic frequency is 45kHz, forms uniform silicon particle suspension; Place blender to stir the silicon particle suspension, 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 the surface modification.
Second step: coated with silica silicon particle
Silicon particle dispersion 50mL after the first step of learning from else's experience modification is handled in ultrasonic process, is the pH=9 of acidity-basicity regulator regulator solution with ammoniacal liquor, forms finely dispersed alkaline suspension liquid; Slowly drip in the mixed solution of 21mL tetraethoxysilane and ethanol then; Wherein the volume ratio of tetraethoxysilane and ethanol is 1: 20, and rate of addition 0.4mL/min drips back mechanical agitation in 40 ℃ of water-baths and 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 behind 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 the second step gained coated with silica is joined in the phenol resin solution ultrasonic mixing 0.5 hour; Temperature was increased to 60 ℃ of mechanical agitation 2 hours, changes drying box then over to, earlier 80 ℃ predrying 12 hours down, back 150 ℃ dry 12 hours down, 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 handled, with embodiment 1
The 5th step: remove silica template
It is in 40% the hydrofluoric acid that the compound particle of carbon/silica/silicon of the 4th step gained is joined mass concentration; Mechanical agitation reaction 2 hours; Dissolving is as the silicon dioxide of preformed hole template; Thereby obtain and the silicon dioxide shape and the consistent three-dimensional reserving hole that distributes, promptly get the silicon-carbon composite cathode material that is used for the three-dimensional preformed hole structure of having of lithium ion battery according to the invention at 105 ℃ of vacuumize 24h.
Detect: with embodiment 1.Test result shows that materials reversible capacity first is 1166mAh/g, and enclosed pasture efficient is 73.5%, and the reversible capacity that circulates after 100 times is 1096mAh/g, and capability retention is 94%, shows good cyclical stability.
Embodiment 4:
The first step: the silicon particle is carried out surface modification
Getting the 1g average grain diameter is the nano-silicon particle of 80nm, joins in the 100mL ethanol solution, ultrasonic dispersion 30min, and wherein ultrasonic power is 200W, supersonic frequency is 45kHz, forms uniform silicon particle suspension; Place blender to stir the silicon particle suspension, 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 the surface modification.
Second step: coated with silica silicon particle
Silicon particle dispersion 50mL after the first step of learning from else's experience modification is handled in ultrasonic process, is the pH=9 of acidity-basicity regulator regulator solution with ammoniacal liquor, forms finely dispersed alkaline suspension liquid; Slowly drip in the mixed solution of 22mL tetraethoxysilane and ethanol then; Wherein the volume ratio of tetraethoxysilane and ethanol is 1: 10, and rate of addition 0.4mL/min drips back mechanical agitation in 40 ℃ of water-baths and 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 behind 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 the second step gained coated with silica is joined in the phenol resin solution ultrasonic mixing 0.5 hour; Temperature was increased to 65 ℃ of mechanical agitation 2 hours, changes drying box then over to, earlier 85 ℃ predrying 10 hours down, back 160 ℃ dry 10 hours down, 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 handled, with embodiment 1
The 5th step: remove silica template, with embodiment 1
Detect: with embodiment 1.Test result shows that material reversible capacity first is 977mAh/g, and enclosed pasture efficient is 78.8%, and the reversible capacity that circulates after 100 times is 947mAh/g, and capability retention is 97%, shows good cyclical stability.
Embodiment 5:
The first step: the silicon particle is carried out surface modification
Getting the 1g average grain diameter is the nano-silicon particle of 1 μ m, joins in the 10mL aqueous propanol solution, ultrasonic dispersion 50min, and wherein ultrasonic power is 200W, supersonic frequency is 40kHz, forms uniform silicon particle suspension; Place blender to stir the silicon particle suspension, under the stirring intensity of 2000r/min, add the 0.2g neopelex, continue stirring reaction 1h, obtain the high power capacity silicon particle dispersion after the surface modification;
Second step: coated with silica silicon particle
Silicon particle dispersion 50mL after the first step of learning from else's experience modification is handled in ultrasonic process, is the pH=8 of acidity-basicity regulator regulator solution with ammoniacal liquor, forms finely dispersed alkaline suspension liquid; Slowly drip in the mixed solution of 21mL tetraethoxysilane and ethanol then; Wherein the volume ratio of tetraethoxysilane and ethanol is 1: 20, and rate of addition 0.1mL/min drips back mechanical agitation in 38 ℃ of water-baths and 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 behind 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 the second step gained coated with silica is joined in polyvinyl alcohol, polystyrene and the epoxy resin solution ultrasonic mixing 1 hour; Temperature was increased to 55 ℃ of mechanical agitation 1 hour, changes drying box then over to, earlier 75 ℃ predrying 14 hours down, back 140 ℃ dry 14 hours down, 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 handled
The compound particle of the 3rd step gained polyvinyl alcohol/silica/silicon is carried out the high temperature cabonization processing; Under protection of nitrogen gas property atmosphere, be warming up to 600 ℃ with 1 ℃/minute speed, be incubated 2 hours; Naturally cool to room temperature, obtain the compound particle of carbon/silica/silicon.The nitrogen gas flow is 0.1m
3/ h.
The 5th step: remove silica template
It is in 10% the hydrofluoric acid that the compound particle of carbon/silica/silicon of the 4th step gained is joined mass concentration; Mechanical agitation reaction 3 hours; Dissolving is as the silicon dioxide of preformed hole template; Thereby obtain and the silicon dioxide shape and the consistent three-dimensional reserving hole that distributes, promptly get the silicon-carbon composite cathode material that is used for the three-dimensional preformed hole structure of having of lithium ion battery according to the invention at 105 ℃ of vacuumize 24h.
Detect: with embodiment 1.Test result shows that materials reversible capacity first is 890mAh/g, and enclosed pasture efficient is 68.5%, and the reversible capacity that circulates after 100 times is 805mAh/g, and capability retention is 90.4%, shows good cyclical stability.
Embodiment 6:
The first step: the silicon particle is carried out surface modification
Getting the 1g average grain diameter is the nano-silicon particle of 60nm, joins in the 100mL acetone soln, ultrasonic dispersion 60min, and wherein ultrasonic power is 100W, supersonic frequency is 80kHz, forms uniform silicon particle suspension; Place blender to stir the silicon particle suspension, under the stirring intensity of 500r/min, add the 0.2g polyvinyl alcohol, continue stirring reaction 1.5h, obtain the high power capacity silicon particle dispersion after the surface modification;
Second step: coated with silica silicon particle
Silicon particle dispersion 50mL after the first step of learning from else's experience modification is handled in ultrasonic process, is the pH=9 of acidity-basicity regulator regulator solution with ammoniacal liquor, forms finely dispersed alkaline suspension liquid; Slowly drip in the mixed solution of 21mL tetraethoxysilane and ethanol then; Wherein the volume ratio of tetraethoxysilane and ethanol is 1: 20, and rate of addition 1mL/min drips back mechanical agitation in 42 ℃ of water-baths and 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 behind 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 xylenes and forms glucose solution, wherein the volume ratio of benzene and xylenes is 1: 5, and the silicon particle 1g of the second step gained coated with silica is joined in the glucose solution ultrasonic mixing 0.5 hour; Temperature was increased to 65 ℃ of mechanical agitation 2 hours, changes drying box then over to, earlier 85 ℃ predrying 10 hours down, back 160 ℃ dry 10 hours down, grind the compound particle of the glucose/silica/silicon that obtains average grain diameter 4 μ m.
The 4th step: high temperature cabonization is handled
The compound particle of the 3rd step gained glucose/silica/silicon is carried out the high temperature cabonization processing; Under the protective atmosphere of argon gas, be warming up to 1200 ℃ with 10 ℃/minute speed, be incubated 5 hours; Naturally cool to room temperature, obtain the compound particle of carbon/silica/silicon.The argon gas flow is 3m
3/ h.
The 5th step: remove silica template
It is in 30% the hydrofluoric acid that the compound particle of carbon/silica/silicon of the 4th step gained is joined mass concentration; Mechanical agitation reaction 5 hours; Dissolving is as the silicon dioxide of preformed hole template; Thereby obtain and the silicon dioxide shape and the consistent three-dimensional reserving hole that distributes, promptly get the silicon-carbon composite cathode material that is used for the three-dimensional preformed hole structure of having of lithium ion battery according to the invention at 105 ℃ of vacuumize 24h.
Detect: with embodiment 1.Test result shows that material reversible capacity first is 1190mAh/g, and enclosed pasture efficient is 78.2%, and the reversible capacity that circulates after 100 times is 1056mAh/g, and capability retention is 88.7%, shows good cyclical stability.
Claims (10)
1. silicon-carbon composite cathode material with three-dimensional preformed hole structure; Constitute by the silicon particle (3) of the carbon base body with high conductivity and rock-steady structure (1) with high power capacity; It is characterized in that: the mass content of described silicon particle (3) is 10～95%, and the mass content of described carbon base body (1) is 5～90%; The average grain diameter of described silicon particle (3) is 30nm～1 μ m; Described carbon base body (1) is an organic carbon source pyrolysis gained.
2. the silicon-carbon composite cathode material with three-dimensional preformed hole structure according to claim 1; It is characterized in that: described silicon particle (3) is dispersed in the described carbon base body (1), around each or several described silicon particles (3), is reserved with three-dimensional expansion space (2).
3. the silicon-carbon composite cathode material with three-dimensional preformed hole structure according to claim 2 is characterized in that: the volume in the described three-dimensional expansion space (2) of reservation is 1～3 times of volume of described silicon particle (3).
4. prepare the described method of claim 1, it is characterized in that: may further comprise the steps with silicon-carbon composite cathode material of three-dimensional preformed hole structure:
The first step: the silicon particle is carried out surface modification: the equal particle diameter of making even was pressed silicon particle and organic solvent mass ratio 1: 100～1: 10 at the silicon particle of 30nm～1 μ m, and ultrasonic being dispersed in the organic solvent forms uniform silicon particle suspension; The silicon particle suspension is placed the blender mechanical agitation, simultaneously, drip surface modifier, continued stirring reaction 1～2 hour, obtain the high power capacity silicon particle dispersion after the surface modification;
Second step: coated with silica silicon particle: the silicon particle dispersion after the first step of learning from else's experience modification is handled, in ultrasonic process, the pH=8 of regulator solution～10 form finely dispersed alkaline suspension liquid; Slowly drip tetraethoxysilane then in ethanolic solution; The volume ratio of tetraethoxysilane and ethanol is 1: 10～20, and rate of addition 0.1～1mL/min drips back mechanical agitation in 38-42 ℃ water-bath and 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 the drying;
The 3rd step: carbon source precursor coated silica/silicon compound particle: the carbon source precursor is dissolved in the solvent forms carbon source precursor solution, the silicon particle of the second step gained coated with silica is joined in the carbon source precursor solution ultrasonic mixing 0.5～1 hour; Temperature was increased to 55-65 ℃ of mechanical agitation 1～2 hour, changes drying box then over to, earlier 75-85 ℃ predrying 10-14 hour down, the back 140-160 ℃ dry 10-14 hour down, grind the compound particle of the carbon/silica/silicon that obtains particle diameter 1～20 μ m;
The 4th step: high temperature cabonization is handled: with the compound particle of the 3rd step gained carbon/silica/silicon under protective atmosphere; Be warming up to 600～1200 ℃ with 1～10 ℃/minute speed; 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% the hydrofluoric acid that the compound particle of the carbon/silica/silicon of the 4th step gained is joined mass concentration; Mechanical agitation reaction 2～6 hours; Dissolving obtains being used for the silicon-carbon composite cathode material of the three-dimensional preformed hole structure of having of lithium ion battery as the silicon dioxide of preformed hole template.
5. preparation according to claim 4 has the method for the silicon-carbon composite cathode material of three-dimensional preformed hole structure; It is characterized in that: organic solvent described in the above-mentioned first step is the various liquid that the silicon particle is disperseed, and is in water, ethanol, propyl alcohol, the acetone one or more; The addition of described surface modifier is 1～20% of a 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 the polyvinylpyrrolidone.
6. has the method for the silicon-carbon composite cathode material of three-dimensional preformed hole structure according to claim 4 or 5 described preparations; It is characterized in that: the silicon particle after modification is handled described in above-mentioned second step and the mass ratio of tetraethoxysilane are 1: 2～1: 6, and the mass ratio of silicon particle and silicon dioxide is 1: 1～1: 3 in the silicon particle of described coated with silica.
7. has the method for the silicon-carbon composite cathode material of three-dimensional preformed hole structure according to claim 4 or 5 described preparations; It is characterized in that: the carbon source precursor described in above-mentioned the 3rd step be water-soluble or polyvinyl alcohol, polystyrene, phenolic resins, epoxy resin, glucose, sucrose and the starch of organic solvent system in one or more, the mass ratio of described carbon source precursor and silicon particle is 30: 1～1: 6; Described solvent is any solvent that can the dissolving carbon source precursor of selecting for use, is in water, ethanol, methyl alcohol, n-butanol, acetone, espeleton, benzene, toluene and the xylenes one or more.
8. have the method for the silicon-carbon composite cathode material of three-dimensional preformed hole structure according to claim 4 or 5 described preparations, it 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.
9. have the method for the silicon-carbon composite cathode material of three-dimensional preformed hole structure according to claim 4 or 5 described preparations, it is characterized in that: the ultrasonic power of sonicated is 100～200W, and supersonic frequency is 40～80kHz, and ultrasonic time is 0.5～1 hour.
10. have the method for the silicon-carbon composite cathode material of three-dimensional preformed hole structure according to claim 4 or 5 described preparations, it is characterized in that: the mixing speed that mechanical agitation is handled is 500～2000r/min.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101527357A (en) * | 2009-04-24 | 2009-09-09 | 清华大学 | Nano-silicon amorphous carbon composition lithium ion battery cathode material and preparation method therefor |
-
2012
- 2012-04-05 CN CN201210097516.3A patent/CN102623680B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101527357A (en) * | 2009-04-24 | 2009-09-09 | 清华大学 | Nano-silicon amorphous carbon composition lithium ion battery cathode material and preparation method therefor |
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| CN113629251A (en) * | 2021-07-09 | 2021-11-09 | 江苏科技大学 | Self-supporting nitrogen-doped porous carbon-coated silicon nanofiber material for lithium ion battery cathode and preparation method and application thereof |
| CN114975976A (en) * | 2022-07-15 | 2022-08-30 | 中国人民解放军国防科技大学 | Nano-silicon-inlaid three-dimensional honeycomb carbon composite negative electrode material and preparation method and application thereof |
| CN114975976B (en) * | 2022-07-15 | 2023-08-22 | 中国人民解放军国防科技大学 | Nano-silicon-inlaid three-dimensional honeycomb carbon composite anode material and preparation method and application thereof |
| CN116936811A (en) * | 2023-09-18 | 2023-10-24 | 赣州立探新能源科技有限公司 | Negative electrode material, preparation method and application thereof |
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