CN101527357A - Nano-silicon amorphous carbon composition lithium ion battery cathode material and preparation method therefor - Google Patents
Nano-silicon amorphous carbon composition lithium ion battery cathode material and preparation method therefor Download PDFInfo
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Abstract
The invention relates to a nano-silicon amorphous carbon composition lithium ion battery cathode material and a preparation method therefore, belonging to the field of electrochemistry power supply. The cathode material consists of a substrate and granules distributed evenly thereon, wherein, cores of the nano-granules are nano-silicon while shells thereof are amorphous carbon obtained by pyrogenation of organic substance; and the substrate thereof is obtained by pyrogenation and carbonization of organic electrospun fibre; wherein, content range of monomer silicon is 10%-50% and content range of amorphous carbon is 90%-50%. The preparation method comprises that nano-silicon granules and electrospun-available organic substances are uniformly stirred and mixed in solvent; high-voltage static electrospun is carried out to obtain fibrous composition; temperature is maintained at 80-200 DEG C, so as to volatilize the solvent completely; and carbonization is then carried out at 400-1000 DEG C. The silicon/carbon composition cathode material prepared by the method can effectively control volume change of silicon electrode material in charging and discharging process. Therefore, the electrode structure is maintained integral; the volume is released gradually. And the silicon/carbon composition cathode material has large circular volume, long circular service life and excellent electrochemical performance.
Description
Technical field
The present invention relates to a kind of structure and embed lithium ion battery silicon/carbon compound cathode materials of carbon base body and preparation method thereof for the nano core-shell particle, belong to field of electrochemical power source.
Background technology
Because it is the fast development and the extensive use of various portable electric appts and electric automobile, very urgent for the demand of energy height, the lithium ion battery that has extended cycle life.The main negative material graphite of present commercial Li-ion batteries, because theoretical capacity low (372mAh/g), high-rate charge-discharge capability is poor, has limited the further raising of lithium ion battery energy.
Up to now, the theoretical capacity of silicon is the highest in the negative material, and Li and Si form alloy Li
xSi (0＜x≤4.4) is when forming Li
4.4Theoretical capacity during the Si compound is up to 4200mAh/g, much larger than the theoretical capacity of graphite; But the alloying of Li-Si alloy and removal alloying are accompanied by huge change in volume, and its volumetric expansion is up to 300%, and the efflorescence of silicon causes the electrode structure unstability and lost efficacy.Particularly common pure silicon, stable circulation is very poor, and the capacity that circulates after 5 times is just almost nil from reducing to more than the 3000mAh/g.
For fear of the shortcoming of above-mentioned silicon, utilize " buffering skeleton " to come the method that compensative material expands to come into one's own in numerous schemes.In theory, as long as the electrode potential of two kinds of materials is incomplete same, the phase of electro-chemical activity just can be embedded in the skeleton of relative non-electrochemical activity, and non-active material plays the effect that disperses and cushion medium.Utilize the cooperative effect between each component of composite material, can reach the purpose of mutual supplement with each other's advantages, the method has been widely used in the study on the modification of lithium ion battery negative material.
Carbonaceous negative material change in volume in charge and discharge process is less relatively, has stable circulation performance preferably, and itself is the good conductor of electronics, therefore is selected as the basis material (being dispersible carrier) of dispersed silicon particle naturally.The chemical property of silicon and carbon is close in addition, and the two can be combined closely.Silicon grain is if can be nano-dispersed in material with carbon element, the space between structure that material with carbon element itself is had and the silicon grain that is nano-dispersed all can be lithium ion provides a large amount of passages, increases the embedded location of lithium ion.Silicon and carbon are compound, and carbon can reach and improve the silicon bulk effect, improves the purpose of its electrochemical stability.Therefore multiple material with carbon element is used to and the compound negative material of preparing high power capacity and excellent cycle performance of silicon.
Agraphitic carbon is wherein generally produced in cracking carbonization below 1000 ℃ by resin or organic polymer, and such material with carbon element mostly has very high embedding lithium capacity.Amorphous carbon is easy to coat silicon grain by methods such as high-temperature decomposition, chemical vapour deposition technique and ball-milling methods, forms nucleocapsid structure, plays the volume cushioning effect, so be the first-selection of preparation silico-carbo composite material.The preparation method of all silicon-agraphitic carbon composite material, all be to wish that amorphous carbon is when combining closely with silicon, can imporously be coated on the silicon grain surface again, when reducing surperficial SEI deposition, make silicon electrode in charge and discharge process, keep structural intergrity, the expansion of volume is effectively suppressed, thereby makes the increase of enclosed pasture efficient and the irreversible capacity of electrode reduce.But existing method is difficult to allow silicon closely be coated equably or be distributed among the carbon, and silicon slow destruction of structure in reversible charge and discharge process still can not be avoided fully.
Summary of the invention
The present invention has just provided a kind of new preparation method, in conjunction with stirring, high-pressure electrostatic electrospinning and high temperature cabonization, has prepared a kind of structure embeds carbon base body for the nano core-shell particle lithium ion battery silicon/carbon negative pole material.In charge and discharge process, the change in volume of silicon electrode material is effectively controlled, and electrode structure is kept perfectly, and the progressive release of capacity has extended cycle life, the chemical property excellence.
A kind of lithium ion battery silicon amorphous carbon composite negative pole material that the present invention proposes is characterized in that: this negative material by carrier and the particle that evenly distributes on it form, and wherein particle is a kind of core-shell structure particles with nano-scale.The nuclear of described nano particle is nano-silicon, and the agraphitic carbon that shell obtains for the organic substance pyrolysis, described matrix are to obtain after organic electrospinning fibre pyrolysis carbonization, are the agraphitic carbon network configuration of irregular multiple hole.The content range of elemental silicon is 10%～50% in described silicon/carbon composite, and the content range of agraphitic carbon is 90%～50%.
Above-mentioned lithium ion battery silicon amorphous carbon composite negative pole material is characterized in that, the preparation method of silicon/amorphous carbon composite lithium ion battery cathode material that the silicon nanoparticle that is coated by the reticulated carbon matrix of irregular loose structure and carbon is formed is:
(1) in the water-bath of room temperature～90 ℃, utilizes mechanical agitation or magnetic agitation, the organic precursor of agraphitic carbon evenly is dissolved in the solvent, form transparent solution;
(2) after silicon nanoparticle is dispersed in the solvent, mixes with solution in the step 1 and to stir more than 12 hours, make silicon nanoparticle be distributed in the organic precursor uniformly; The mass ratio of solvent and organic precursors is 70/30～95/5; The mass ratio of organic precursor and nano silica fume is controlled to be 15/4～90/1;
(3) suspension-turbid liquid with gained in the step 2 carries out the high-pressure electrostatic electrospinning, and the product that obtains carbonization under inert gas shielding is with 1 ℃ of min
-1Speed is warming up to the solvent boiling point temperature, is incubated 0.5～3 hour, makes solvent volatilize fully; Continuation is with 5～10 ℃ of min
-1Speed is warming up to 400～1000 ℃, is incubated 0.5～5 hour, with the stove cooling, makes nano silica fume be coated by amorphous carbon, and is dispersed in the carbon base body.
But the above-mentioned electrospinning and the organic precursors of carbonization comprise polyvinyl alcohol, polyacrylonitrile, polyurethane, polyvinyl chloride, polyethylene glycol oxide, polyacrylate, polymethyl methacrylate.
Above-mentioned nano silica fume particle diameter is 10～100nm, and its processing method is:
(1) be to add in the certain amount of solvent in 1: 1～1: 5 surfactant benzyl sodium sulfonate and nano silica fume by mass ratio;
(2) ultrasonic and magnetic agitation was alternately carried out 3～8 hours altogether, made that nano particle is soft-agglomerated to open, and was uniformly distributed in the solvent formation suspension-turbid liquid.
Above-mentioned solvent is deionized water, dimethyl formamide, oxolane or other organic precursors are soluble and volatile solution between 80～200 ℃.
A kind of structure that the present invention proposes is lithium ion battery silicon/carbon negative pole material that the nano core-shell particle embeds carbon base body, has the progressive release of capacity, capacity is big and the advantage that has extended cycle life.
Description of drawings
Fig. 1 is the electrical property figure of a kind of structure of the present invention for the lithium ion battery silicon/carbon negative pole material of nano core-shell particle embedding carbon base body, chemical property excellence.
Fig. 2 is the stereoscan photograph of a kind of structure of the present invention for the lithium ion battery silicon/carbon compound cathode materials of nano core-shell particle embedding carbon base body, and nano particle is not reunited as can be seen, is distributed in equably in the matrix of random hole network configuration.
Embodiment
Below in conjunction with specific embodiment technical scheme of the present invention is described further:
1) in the water-bath of room temperature～90 ℃, utilizes mechanical agitation or magnetic agitation, but the organic precursors and the solvent of electrospinning stirred more than 12 hours, form transparent solution; Described organic precursors comprises polyvinyl alcohol, polyacrylonitrile, polyurethane, polyvinyl chloride, polyethylene glycol oxide, polyacrylate, polymethyl methacrylate; Described solvent is deionized water, dimethyl formamide, oxolane or other organic precursors are soluble and volatile solution between 80～200 ℃.
2) with nano silica fume (particle diameter be 10～100nm) with surfactant benzyl sodium sulfonate be after 1: 1～5: 1 ratio is added in the described solvent of a certain amount of step 1 in mass ratio, hocket ultrasonic and magnetic agitation to it, totally 3～8 hours, making that nano particle is soft-agglomerated opens, and be uniformly distributed in the solvent, form suspension-turbid liquid.
3) solution in the above-mentioned steps 1 is mixed with suspension-turbid liquid in the step 2 stir more than 12 hours, be distributed in the organic precursor uniformly to silicon nanoparticle; The mass ratio of solvent and organic precursors is controlled to be 70/30～95/5, and the mass ratio of organic precursor and nano silica fume is controlled to be 15/4～90/1.
4) suspension-turbid liquid with gained in the step 3 injects syringe, carries out electrostatic spinning by the high-voltage electrostatic field, obtains nano-silicon-organic nanofibers composite material.
5) with the nano-silicon-organic nanofibers composite material carbonization under inert gas shielding that obtains in the step 4, with 1-2 ℃ of min
-1Speed is warming up near solvent boiling point temperature (80～200 ℃), is incubated 0.5～3 hour, makes solvent volatilize fully; Continuation is with 5～10 ℃ of min
-1Speed is warming up to 400～1000 ℃, is incubated 0.5～5 hour, with the stove cooling, makes nano silica fume be coated by amorphous carbon, and is dispersed in the carbon base body.
Embodiment 1
A) in 90 ℃ of water-baths, the pure polyvinyl alcohol of 15g (molecular weight is 80000) utilizes powerful mechanical agitation to mix 12 hours to even white transparence with the 135g deionized water solvent;
B) be that the deionized water of the surfactant benzyl sodium sulfonate of nano silica fume, 0.5g of 40nm and 10g mixes and magnetic agitation 1 hour with the particle diameter of 1g, ultrasonic 1 hour, stirred again at last 2 hours;
C) solution of step a and b is mixed after, utilize powerful mechanical agitation 12h after, deionized water solvent, nano silica fume and polyvinyl alcohol mix evenly;
D) suspension-turbid liquid with gained among the step c injects syringe, utilizes the pulsed electrostatic generator to produce the 25KV high pressure and carries out electrospinning; Needle tip polishes, and internal diameter is 1mm, and flow is controlled by syringe pump, and flow is 1ml/h, and fiber collecting is to the ground connection aluminium foil that places syringe needle the place ahead, and the distance between syringe needle and the aluminium foil is 12cm;
E) with the carbonization under the high-purity argon gas protection of the fibrous paper shape composite material in the steps d, with 1 ℃ of min
-1Speed is warming up to 100 ℃, is incubated 1 hour, makes deionized water evaporate fully; Continuation is with 5 ℃ of min
-1Speed is warming up to 500 ℃, is incubated 2 hours, with the stove cooling, makes nano silica fume be coated by amorphous carbon, and is dispersed in the carbon base body.
Lithium ion battery silicon/carbon compound cathode materials capacity that the nano core-shell particle that the method obtains embeds carbon base body increases and increases along with cycle-index, circulate 30 times discharge capacity up to 900.5mAh/g, more primary capacity has increased by 44.2%, specifically sees figure one.
Embodiment 2
A) in 50 ℃ of water-baths, 5g polyacrylonitrile (molecular weight is 90000) carries out 12 hours extremely even yellow transparent shapes of powerful magnetic agitation with 45g solvent dimethyl formamide;
B) be that the nano silica fume of 40nm, the surfactant benzyl sodium sulfonate of 0.2g and the dimethyl formamide of 10g mixed magnetic agitation 1 hour with the particle diameter of 0.4g, ultrasonic 1 hour, magnetic agitation 2h more at last;
C) after the solution mixing with step a and b, utilize powerful magnetic agitation 12h, solvent dimethylformamide, nano silica fume and polyacrylonitrile mix;
D) suspension-turbid liquid with gained among the step c injects syringe, utilizes the pulsed electrostatic generator to produce the 20KV high pressure and carries out electrospinning; Needle tip polishes, and internal diameter is 1mm, and flow is controlled by syringe pump, and flow is 1ml/h, and fiber collecting is to the ground connection aluminium foil that places syringe needle the place ahead, and the distance between syringe needle and the aluminium foil is 14cm;
E) with the carbonization under the high-purity argon gas protection of the composite material in the steps d, be warming up to 160 ℃, be incubated 2 hours, make solvent volatilize fully with 1 ℃ of min-1 speed; Continuation is warming up to 900 ℃ with 5 ℃ of min-1 speed, is incubated 1 hour, with the stove cooling, makes nano silica fume be coated by amorphous carbon, and is dispersed in the carbon base body.
Nano core-shell particle that the method obtains embeds the lithium ion battery silicon/carbon compound cathode materials capacity height of carbon base body, good cycling stability, and circulating, discharge capacity is 410mAh/g after 20 times.
Embodiment 3
A) in 40 ℃ of water-baths, 4g polymethyl methacrylate (molecular weight is 30000) and 40g solvent dimethyl formamide carry out powerful magnetic agitation 3 hours to the homogeneous transparent shape;
B) be that the nano silica fume of 40nm, the surfactant benzyl sodium sulfonate of 0.5g and the dimethyl formamide of 8g mixed magnetic agitation 1 hour with the particle diameter of 1g, ultrasonic 1 hour, magnetic agitation 2h more at last;
D) after the solution mixing with step a and b, utilize powerful magnetic agitation 12h, solvent dimethylformamide, nano silica fume and polymethyl methacrylate mix;
D) suspension-turbid liquid with gained among the step c injects syringe, utilizes the pulsed electrostatic generator to produce the 18KV high pressure and carries out electrospinning; Needle tip polishes, and internal diameter is 1mm, and flow is controlled by syringe pump, and flow is 1ml/h, and fiber collecting is to the ground connection aluminium foil that places syringe needle the place ahead, and the distance between syringe needle and the aluminium foil is 12cm;
E) with the carbonization under the high-purity argon gas protection of the composite material in the steps d, be warming up to 160 ℃, be incubated 2 hours, make solvent volatilize fully with 1 ℃ of min-1 speed; Continuation is warming up to 400 ℃ with 5 ℃ of min-1 speed, is incubated 1 hour, with the stove cooling, makes nano silica fume be coated by amorphous carbon, and is dispersed in the carbon base body.
Embodiment 4
A) in 40 ℃ of water-baths, 13g PAUR (molecular weight is 200000) and 90g solvent dimethyl formamide carry out powerful magnetic agitation 4 hours to the homogeneous transparent shape;
B) be that the nano silica fume of 40nm, the surfactant benzyl sodium sulfonate of 0.5g and the dimethyl formamide of 10g mixed magnetic agitation 1 hour with the particle diameter of 1g, ultrasonic 1 hour, magnetic agitation 2h more at last;
E) after the solution mixing with step a and b, utilize powerful magnetic agitation 12h, solvent dimethylformamide, nano silica fume and polyurethane mix;
D) suspension-turbid liquid with gained among the step c injects syringe, utilizes the pulsed electrostatic generator to produce the 20KV high pressure and carries out electrospinning; Needle tip polishes, and internal diameter is 1mm, and flow is controlled by syringe pump, and flow is 1ml/h, and fiber collecting is to the ground connection aluminium foil that places syringe needle the place ahead, and the distance between syringe needle and the aluminium foil is 12cm;
E) with the carbonization under the high-purity argon gas protection of the composite material in the steps d, be warming up to 160 ℃, be incubated 1 hour, make solvent volatilize fully with 1 ℃ of min-1 speed; Continuation is warming up to 450 ℃ with 5 ℃ of min-1 speed, is incubated 1 hour, with the stove cooling, makes nano silica fume be coated by amorphous carbon, and is dispersed in the carbon base body.
Claims (5)
1. lithium ion battery silicon amorphous carbon composite negative pole material is characterized in that: this negative material is made up of matrix and the particle that evenly distributes wherein, and wherein particle is a kind of core-shell structure particles with nano-scale; The nuclear of described nano particle is nano-silicon, and the agraphitic carbon that shell obtains for the organic substance pyrolysis, described matrix are to obtain after organic electrospinning fibre pyrolysis carbonization, are the agraphitic carbon network configuration of irregular multiple hole; The content range of elemental silicon is at 10%～50% in described silicon/carbon composite, and the content range of agraphitic carbon is 90%～50%.
2. composite negative pole material according to claim 1 is characterized in that, the preparation method of silicon/amorphous carbon lithium ion battery negative material that the silicon nanoparticle that is coated by the reticulated carbon matrix of irregular loose structure and carbon is formed is:
(1) in the water-bath of room temperature～90 ℃, utilizes mechanical agitation or magnetic agitation, the organic precursor of agraphitic carbon evenly is dissolved in the solvent, form transparent solution;
(2) after being dispersed in silicon nanoparticle in the solvent, mix stirring, make silicon nanoparticle be distributed in the organic precursor equably with solution in the step 1; The mass ratio of solvent and organic precursors is 70/30～95/5; The mass ratio of organic precursor and nano silica fume is controlled at 15/4～90/1;
(3) suspension-turbid liquid with gained in the step 2 carries out the high-pressure electrostatic electrospinning, and the product that obtains carbonization under inert gas shielding is with 1 ℃ of min
-1Speed is warming up to the solvent boiling point temperature, is incubated 0.5～3 hour, makes solvent volatilize fully; Continuation is with 5～10 ℃ of min
-1Speed is warming up to 400～1000 ℃, is incubated 0.5～5 hour, with the stove cooling, makes nano silica fume be coated by amorphous carbon, and is dispersed in the carbon base body.
3. composite negative pole material according to claim 1 and 2, it is characterized in that, but the organic precursors of described electrospinning and carbonization comprises polyvinyl alcohol, polyacrylonitrile, polyurethane, polyvinyl chloride, polyethylene glycol oxide, polyacrylate or polymethyl methacrylate.
4. negative material according to claim 2 is characterized in that, the method for the suspension-turbid liquid of the even dispersing nanometer silica flour of described step 2 preparation is:
(1) the silicon grain particle diameter is 10～100nm;
(2) be in 1/1～1/5 adding certain amount of solvent with surfactant benzyl sodium sulfonate and nano silica fume by mass ratio;
(3) powerful ultrasonic and magnetic agitation hocketed 3～8 hours totally, made that nano particle is soft-agglomerated to open, and was uniformly distributed in the solvent, formed suspension-turbid liquid.
5. according to right 2 or 4 described composite negative pole materials, it is characterized in that described solvent is deionized water, dimethyl formamide, oxolane or other organic precursors are soluble and volatile solution between 80～200 ℃.
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