CN103305965A - Silicon-carbon composite material with nano micropores and preparation method as well as application thereof - Google Patents
Silicon-carbon composite material with nano micropores and preparation method as well as application thereof Download PDFInfo
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- 239000002904 solvent Substances 0.000 claims abstract description 8
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a silicon-carbon composite material with nano micropores and a preparation method as well as application thereof. The material comprises nano-silicon (Si) particles and a carbon nanofiber matrix, wherein the nano-silicon particles are dispersed in the carbon nanofiber matrix; and nano pores and micropores communicated with the nano pores are distributed in the carbon nanofiber matrix. The method comprises the steps of dissolving the nano-Si particles and polyacrylonitrile (PAN) in a solvent to prepare a mixed spinning solution, then carrying out electrostatic spinning on the mixed spinning solution, and curing spinning trickles in a coagulating bath to obtain a porous PAN-Si composite nanofiber; and then carrying out oxidation and carbonization treatment in sequence to obtain the silicon-carbon composite material with a nano micropore structure. The silicon-carbon composite material is applied to preparation of lithium ion battery cathode materials. Compared with the prior art, the silicon-carbon composite material ensures the overall electron transport capacity of the material while reserving buffer space for expansion of the nano-Si particles.
Description
Technical field
The present invention relates to nano composite material, especially a kind of Si-C composite material with nanometer micropore gap and preparation method thereof and purposes.
Background technology
Lithium ion battery negative material is generally material with carbon element, and such as graphite, needle coke, carbonaceous mesophase spherules, carbon fiber, carbon nano-fiber etc., the theoretical reversible lithium storage specific capacity of commercial applications graphite cathode material is 372mAh/g at present.Improve the capacity of lithium ion battery, depend primarily on the embedding lithium ability of negative material, the research and development of high power capacity negative material have become the key that improves performance of lithium ion battery.The theoretical lithium storage content of silicon (Si) material is 4200mAh/g, is a kind of ideal material that improves capacity of negative plates.Yet the volumetric expansion of Si material in embedding lithium process can reach 300%, will cause destruction and the mechanical crushing of material structure, so that separate between conductive network and the silicon particle.The poorly conductive of silicon materials, first charge-discharge efficiency is low, energy attenuation is fast, the cycle performance extreme difference, is that such material is applied to the key scientific problems that the high specific energy lithium ion battery needs to be resolved hurrily.In order to alleviate the volumetric expansion of alloy material in charging process, improve its cyclical stability, the silicon grain of preparation nanoscale, or carbon/silicon nano composite material is the comparison effective method.
The employing silane crackings such as Jung get the amorphous silicon film of 50nm, and its first capacity can reach more than the 3000mAh/g, but after 20 circulations, the capacity rapid attenuation is to 400mAh/g[H.Jung, M.Park, Y.Yoon, et al.Journal of Power Sources, 2003,115:346.].Bourderau adopt the CVD legal system standby the Si film of 1.2 μ m, find that capacity can reach 1000mAh/g first, yet circulate after 20 times, capacity namely decays to rapidly [S.Bourderau about 200mAh/g, T.Brousse.Journal of Power Sources, 1999,81:233.].Cui has introduced nucleocapsid structure in preparation Si nano wire, examine to be the good Si line of crystal formation, play constitutionally stable about; Shell is the unformed Si film of one deck, plays the effect [L.Cui, Y.Cui.Nano Letters, 2009,9:491.] of capacity storage.
Silicon and carbon are compound for the preparation of negative material, especially in recent years study hotspot.Researchers have also studied the application of composite aspect lithium ion battery negative material of Si and graphite, carbonaceous mesophase spherules, CNT, Graphene, how empty carbon, amorphous carbon, carbon aerogels etc.Electrostatic spinning technique is the effective ways of preparation nanofiber, the polymer precursor of electrospinning carbon, after the oxidation carbonization, can prepare the carbon nano-fiber with unique microstructures, such as [M.Inagani, Y.Yang, F.Kang.Advanced Materials such as loose structure, hollow structure, embedding nano particle, nucleocapsid structure, surface abnormity, 2012,24:2547.].Polyacrylonitrile (PAN) solution that Li etc. will mix the nano-silicon particle carries out electrostatic spinning, after the oxidation carbonization, obtain the carbon nano-fiber in the silicon grain embedding carbon base body, and with this as the negative material that is lithium ion battery, first capacity can reach 1000mAh/g, and after 50 circulations, capacity attenuation is to 700mAh/g, mainly be because reserve cushion space in the carbon base body expansion of silicon, limited the raising of material cycle performance; And obvious reunion occured in the silicon particle, and a large amount of silicon particles exposes on the surface of carbon nano-fiber [Y.Li, B.Guo, L.Ji, et al.Carbon, 2013,51:185.].Patent CN102623680A discloses a kind of silicon-carbon composite cathode material with three-dimensional preformed hole structure and preparation method thereof, in carbon base body, utilize silica to be template coated Si particle, finally with hydrofluoric acid silica is etched away, thereby obtain the reservation gap structure on silicon grain surface, material first reversible capacity can reach 1190mAh/g, and enclosed pasture efficient is 78.2%, the reversible capacity that circulates after 100 times is 1056mAh/g, and capability retention is 88.7%.But in this patent, because reserving hole forms after by etching silicon dioxide, after silica etches away, can't fully contact (the some contact that only causes because of gravity) with carbon base body thereby silicon particle integral body is arranged in hole, thereby cause its electronic transmission performance relatively poor.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of Si-C composite material with nanometer micropore gap when reserving cushion space for the expansion of silicon nanoparticle, the electron transport ability of assurance material monolithic.
The present invention also provide above-mentioned composite manufacture method with and in ion cathode material lithium preparation purposes.
Think after the inventor herein research: all of Si-C composite material can not solve the expansion issues of silicon in charge and discharge process fully at present, and key is that wherein carbon base body does not really play the effect of rock-steady structure; Most researchs only depend on the coating function of carbon, suppress the swelling stress of silicon; And sufficient cushion space is provided for the expansion of silicon.After discharging and recharging repeatedly, the destruction of self structure finally occurs in carbon base body owing to being subject to the swelling stress of silicon, thereby has reduced the protective effect of silicon and the chemical property of self.Therefore, research has a silicon-carbon nano composite material that cushion space is provided for the volumetric expansion of silicon, and the development of silicon based anode material high-capacity lithium ion cell is had very large impetus.This patent is induced the theory that is separated based on the non-solvent of polymer solution, adopting electrostatic spinning technique to the PAN(polyacrylonitrile of dopen Nano silicon grain) solution carries out the electrostatic spinning moulding, dynamic analysis of spinning carries out double diffusion between solvent-coagulating agent and curing molding in coagulating bath, control curing condition, obtain having the as-spun fibre of multi-pore structure; Nascent nanofiber after oxidation, carbonization, obtain inside contain enrich nanometer micropore, nano-silicon embeds the carbon nano-fiber in the carbon base body, and used as the negative material of lithium ion battery.
Particularly, the present invention solves the problems of the technologies described above by following technological means:
As shown in Figure 1, a kind of Si-C composite material with nanometer micropore gap structure, comprise silicon nanoparticle and carbon nano-fiber matrix, described silicon nanoparticle is dispersed in the described carbon nano-fiber matrix, is distributed with the micropore of nano aperture and the described nano aperture of connection in the described carbon nano-fiber matrix.
Preferably: the average diameter of carbon nano-fiber is 100-600nm in the described carbon nano-fiber matrix, and the average diameter of described silicon nanoparticle is 10-60nm.
Preferably: the mass fraction of described silicon particle is 3-67%, and the mass fraction of described carbon nano-fiber matrix is 33-97%.To improve effect not remarkable if the content of silicon particle is lower than the storage lithium ability of 3% pair of material, if greater than 67% then can cause the formation of aforementioned structure in material to distribute not ideal enough.
Compared with prior art, the present invention induces curing molding by non-solvent, and electrospinning fibre is carried out pore-creating, finally obtains the concrete dynamic modulus nanometer composite Si-C fiber.Si-C composite material of the present invention is encapsulated in silicon in the porous filamentous nanocarbon, the embedding of silicon has improved the integral body storage lithium ability of material, carbon base body can help silicon grain to carry out the electric charge transmission, hole in the carbon nano-fiber matrix and micro hole structure can either effectively be held the volumetric expansion of silicon in charge and discharge process, and described micropore also provides easily passage for the transmission of ion, electric charge.This composite combines the two advantage of silicon-carbon, and has effectively suppressed the shortcoming of the two, thereby has improved the chemical property of material.
The present invention also provides a kind of preparation method with Si-C composite material of nanometer gap structure, may further comprise the steps:
S1, configuration contain the polyacrylonitrile spinning solution of silicon nanoparticle;
S2, the polyacrylonitrile spinning solution that step S1 is obtained are packed in the syringe, carry out after the match electrostatic spinning at high-pressure electrostatic, dynamic analysis of spinning enters through spinning of 2-10cm in air that solidified forming obtains nascent polyacrylonitrile nanofiber in the liquid coagulating bath after the journey, nascent polyacrylonitrile nanofiber is placed 1-3h in the liquid coagulating bath, then carry out vacuumize and obtain the polypropylene nano fiber, wherein, the voltage of described high-voltage electrostatic field is 5-30kV, and the spinning solution flow is 0.1-1.0mL/h;
S3, step S2 is obtained polyacrylonitrile nanofiber carry out oxidation processes and obtain the nanofiber oxide;
S4, described nanofiber oxide is carried out carbonization form described Si-C composite material.
Preferably, described step S1 comprises: the polyacrylonitrile powder is added stirring and dissolving in the organic solvent, then add silicon nanoparticle and continue to stir more than the 24h, and ultrasonic wave disperses to obtain the described polyacrylonitrile spinning solution that contains silicon nanoparticle more than the 1h.
Preferably, described step S2 comprises:
Preferably, described step S3 comprises: described oxidation processes is carried out in air, and the control oxidizing temperature progressively is warming up to 250-300 ℃ with the programming rate of 1-10 ℃/min from room temperature, and taking-up obtains described nanofiber oxide behind the constant temperature 1-3h.
Preferably, described carbonization is carried out in the high temperature carbonization stove, in argon gas atmosphere, progressively is warming up to 600-1500 ℃ with the programming rate of 1-20 ℃/min from room temperature, and constant temperature 1-3h, is cooled to take out after the room temperature to obtain described Si-C composite material.
Preferably, the solvent of described polyacrylonitrile spinning solution is dimethyl formamide.
Preferably, the mass fraction of polyacrylonitrile is 6-15wt% in the dimethyl formamide solution of described polyacrylonitrile, and the mass ratio of silicon nanoparticle and polyacrylonitrile is 1:50-1:1.
Compared with prior art, method of the present invention has the polyacrylonitrile of silicon nanoparticle mixed liquor to carry out the electrostatic spinning moulding to mixing, and dynamic analysis of spinning is middlely induced the curing molding that is separated because non-solvent occurs solidifying, and forms PAN-Si nanometer as-spun fibre.In solidification process, fibrocortex at first solidifies, and solvent progressively to external diffusion, forms a large amount of pore space structure at fibrous inside from fibrous inside.Through subsequent oxidation, carbonisation, PAN progressively forms the network structure of carbon, silicon nanoparticle is covered by in the carbon base body, large pore space structure is retained in the carbon base body, simultaneously owing to the form cracking of non-carbon with gas molecules removes, in carbon base body, form the micro hole structure that is interconnected, finally obtain having the silicon-carbon nano composite material of built-in multi-pore structure.Preparation technology of the present invention is simple, raw material sources are extensive, and physical dimension was stable when prepared silicon-carbon nano composite material was used for lithium ion battery negative material, reversible specific capacity is high, cycle performance is excellent, and.
The described application of Si-C composite material in the preparation lithium ion battery negative material with nanometer micropore gap structure of aforementioned any one can improve reversible capacity and the cyclical stability of negative material in charge and discharge process.
Description of drawings
Fig. 1 is the structural representation of the Si-C composite material of the specific embodiment of the invention 1.
The specific embodiment
Preferred embodiment the invention will be further described for the below's contrast accompanying drawing and combination.
A kind of Si-C composite material with nanometer micropore gap structure, comprise silicon nanoparticle and carbon nano-fiber matrix, described silicon nanoparticle is dispersed in the described carbon nano-fiber matrix, is distributed with the micropore of nano aperture and the described nano aperture of connection in the described carbon nano-fiber matrix.The average diameter of carbon nano-fiber is 100-600nm in the carbon nano-fiber matrix, and the average diameter of described silicon particle is 10-60nm.The mass content of described silicon nanoparticle is 3-67%, and the mass content of described carbon nano-fiber matrix is 33-97%, and the aperture of described nano aperture is preferably 50-100nm, and the aperture of described micropore is preferably less than 10nm.Above-mentioned Si-C composite material can prepare by following method:
Silicon nanoparticle and polyacrylonitrile be dissolved in be prepared into blend spinning liquid in the solvent, then blend spinning liquid is carried out electrostatic spinning, dynamic analysis of spinning curing molding in coagulating bath obtains many spaces PAN-Si nano-composite fiber; Then carry out successively oxidation processes and carbonization treatment, obtain aforementioned Si-C composite material with nanometer micropore gap structure.Wherein, the voltage of electric field of electrostatic spinning is preferably 5-30kV, and the flow velocity of spinning solution is preferably 0.1-1.0Ml/h, preferably adopts molecular weight M
wFor the PAN of 15-20 ten thousand as carbon source, the mass fraction of polyacrylonitrile is preferably 6-15wt% in the polyacrylonitrile solution, the mass ratio of silicon nanoparticle and polyacrylonitrile is preferably 1:50 – 1:1.Oxidation processes is preferably carried out in air, and the control oxidizing temperature progressively is warming up to 250-300 ℃ with the programming rate of 1-10 ℃/min from room temperature, and taking-up obtains described nanofiber oxide behind the constant temperature 1-3h.Carbonization treatment is preferably carried out in the high temperature carbonization stove, in argon gas atmosphere, progressively is warming up to 600-1500 ℃ with the programming rate of 1-20 ℃/min from room temperature, and constant temperature 1-3h, is cooled to take out after the room temperature to obtain described Si-C composite material.
Hereinafter in conjunction with specific embodiment more technical scheme of the present invention is explained:
Comparative example 1
The first step: the preparation of spinning solution.Take by weighing 9g molecular weight M
w=150000 PAN powder is added among the DMF of 96mL, 65 ℃ of lower 24h dissolving, PAN-DMF solution of preparation mass fraction 9% of stirring; The nano-silicon particle that takes by weighing the 2.25g average grain diameter and be 20-40nm is added in the DMF solution of PAN, and 65 ℃ of lower continuation stir 24h, and ultrasonic dispersion 1h, obtain Si homodisperse mixed liquor in the DMF of PAN solution.
Second step: electrostatic spinning prepares the PAN nanofiber of doping Si.The mixed solution that the first step is made is packed in the syringe, flow with 0.3mL/h is extruded spinning solution, electrostatic spinning under the high voltage electric field of 18kV, spinning head is 15cm to the distance of receiver, dynamic analysis of spinning is the desolvation curing molding in air, as-spun fibre is collected at aluminium foil, obtains the PAN-Si composite nano fiber.
The 3rd step: the oxidation processes of nascent nanofiber.Second step is obtained nanofiber in the oxidation furnace of temperature programmed control, carry out oxidation processes, oxidizing atmosphere is air, is warming up to 200 ℃ with the programming rate of 5 ℃/min from room temperature, is warming up to 270 ℃ with 2 ℃/min again, take out behind the constant temperature 1h, prepare to be used for high temperature cabonization and process.
The 4th step: the carbonization of nanofiber oxide and the formation of nano-silicone wire/carbon composite material.In high temperature carbonization furnace, carry out carbonization treatment through snperoxiaized nanofiber; under high-purity argon gas (purity〉99.999%) protection, progressively be warming up to 800 ℃ with the programming rate of 10 ℃/min from room temperature, and constant temperature 1h; take out sample after being cooled to room temperature, obtain the silicon-carbon nano-composite fiber.
The 5th step: the preparation of silicon-carbon nano composite anode material and electrochemical property test.Be that 80:10:10 mixes and makes electrode slice according to silicon-carbon nano composite material, conductive carbon black, binding agent Kynoar (PVDF) three's mass ratio, with metal lithium sheet as to electrode and reference electrode, Clegard2500 makes barrier film, electrolyte is the ethylene carbonate (EC)+diethyl carbonate (DMC) solution (volume ratio of EC and DMC is 1:1) of 1mol/L LiPF6, is assembled into 2032 type button cells in being full of the glove box of high-purity argon gas.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 100mA/g, and the charging/discharging voltage scope is 0.01-3.0V.
By above-mentioned steps operation obtain silicon-carbon composite Nano negative material first reversible capacity be 1074mAh/g, enclosed pasture efficient is 77%, the reversible capacity that circulates after 50 times is 698mAh/g, capability retention is 65%.
Comparative example 2
The first step: the preparation of spinning solution.Take by weighing 9g molecular weight M
w=150000 PAN powder is added among the DMF of 96mL, 65 ℃ of lower 24h dissolving, PAN-DMF solution of preparation mass fraction 9% of stirring; The nano-silicon particle that takes by weighing the 0.47g average grain diameter and be 20-40nm is added in the DMF solution of PAN, and 65 ℃ of lower continuation stir 24h, and ultrasonic dispersion 1h, obtain Si homodisperse mixed liquor in the DMF of PAN solution.
Second step: electrostatic spinning prepares the PAN nanofiber of doping Si.Spinning condition is identical with second step in the comparative example 1.
The 3rd step: the oxidation processes of nascent nanofiber.The oxidation processes condition is identical with the 3rd step in the comparative example 1.
The 4th step: the carbonization of nanofiber oxide and the formation of nano-silicone wire/carbon composite material.Carbonization Conditions is identical with the 4th step of comparative example 1.
The 5th step: the preparation of silicon-carbon nano composite anode material and electrochemical property test.The material preparation is identical with the 5th step in method of testing and the comparative example 1.
By above-mentioned steps operation obtain silicon-carbon composite Nano negative material first reversible capacity be 605mAh/g, enclosed pasture efficient is 83%, the reversible capacity that circulates after 50 times is 466mAh/g, capability retention is 77%.
Comparative example 3
The first step: the preparation of spinning solution.Take by weighing 9g molecular weight M
w=150000 PAN powder is added among the DMF of 96mL, 65 ℃ of lower 24h dissolving, PAN-DMF solution of preparation mass fraction 9% of stirring; The nano-silicon particle that takes by weighing the 6.0g average grain diameter and be 20-40nm is added in the DMF solution of PAN, and 65 ℃ of lower continuation stir 24h, and ultrasonic dispersion 1h, obtain Si homodisperse mixed liquor in the DMF of PAN solution.
Second step: electrostatic spinning prepares the PAN nanofiber of doping Si.Spinning condition is identical with second step in the comparative example 1.
The 3rd step: the oxidation processes of nascent nanofiber.The oxidation processes condition is identical with the 3rd step in the comparative example 1.
The 4th step: the carbonization of nanofiber oxide and the formation of nano-silicone wire/carbon composite material.Carbonization Conditions is identical with the 4th step of comparative example 1.
The 5th step: the preparation of silicon-carbon nano composite anode material and electrochemical property test.The material preparation is identical with the 5th step in method of testing and the comparative example 1.
By above-mentioned steps operation obtain silicon-carbon composite Nano negative material first reversible capacity be 1463mAh/g, enclosed pasture efficient is 67%, the reversible capacity that circulates after 50 times is 717mAh/g, capability retention is 49%.
Embodiment 1
Compare with comparative example 1.
The first step: the preparation of spinning solution.The preparation method of spinning solution is identical with the first step in condition and the comparative example 1, obtains Si homodisperse mixed liquor in the DMF of PAN solution.
Second step: electrostatic spinning prepares the PAN nanofiber of doping Si.The mixed solution that the first step is made is packed in the syringe, with the flow of 0.3mL/h spinning solution is extruded, and electrostatic spinning under the high voltage electric field of 18kV, spinning solution enter curing molding in the coagulating bath behind the air of a segment distance.Air section distance between spinning head and the coagulating bath is 3cm, and coagulating bath is the normal temperature water-bath, and setting time is 2h, and as-spun fibre obtains concrete dynamic modulus PAN-Si composite nano fiber at 60 ℃ of lower vacuumize 12h.
The 3rd step: the oxidation processes of nascent nanofiber.The oxidation processes condition is identical with the 3rd step among the embodiment 1.
The 4th step: the carbonization of nanofiber oxide and the formation of nano-silicone wire/carbon composite material.Carbonization Conditions is identical with the 4th step of comparative example 1.As shown in Figure 1, obtain having and enrich the nano-silicone wire/carbon composite material that micro hole structure, take carbon nano-fiber 100 as matrix, silicon nanoparticle 200 embeds wherein, be distributed with the nano aperture 300 of 50-100nm in this material and the aperture that is interconnected less than the micropore 400 of 10nm.
The 5th step: the preparation of silicon-carbon nano composite anode material and electrochemical property test.The material preparation is identical with the 5th step in method of testing and the comparative example 1.
By above-mentioned steps operation obtain silicon-carbon composite Nano negative material first reversible capacity be 1124mAh/g, enclosed pasture efficient is 81%, the reversible capacity that circulates after 50 times is 934mAh/g, capability retention is 83%.
Embodiment 2
Compare with comparative example 1.
The first step: the preparation of spinning solution.The preparation method of spinning solution is identical with the first step among condition and the embodiment 1, obtains Si homodisperse mixed liquor in the DMF of PAN solution.
Second step: electrostatic spinning prepares the PAN nanofiber of doping Si and PVC.The mixed solution that the first step is made is packed in the syringe, with the flow of 0.3mL/h spinning solution is extruded, and electrostatic spinning under the high voltage electric field of 18kV, spinning solution enter curing molding in the coagulating bath behind the air of a segment distance.Air section distance between spinning head and the coagulating bath is 3cm, and coagulating bath is the normal temperature absolute ethyl alcohol, and setting time is 2h, and as-spun fibre obtains concrete dynamic modulus PAN-Si composite nano fiber at 60 ℃ of lower vacuumize 12h.
The 3rd step: the oxidation processes of nascent nanofiber.The oxidation processes condition is identical with the 3rd step among the embodiment 1.
The 4th step: the carbonization of nanofiber oxide and the formation of nano-silicone wire/carbon composite material.The carbonization treatment condition is identical with the 4th step among the embodiment 1.
The 5th step: the preparation of silicon-carbon nano composite anode material and electrochemical property test.The material preparation is identical with the 5th step among method of testing and the embodiment 1.
By above-mentioned steps operation obtain silicon-carbon composite Nano negative material first reversible capacity be 1166mAh/g, enclosed pasture efficient is 84%, the reversible capacity that circulates after 50 times is 991mAh/g, capability retention is 85%.
Embodiment 3
Compare with comparative example 2.
The first step: the preparation of spinning solution.The preparation method of spinning solution is identical with the first step in condition and the comparative example 2.
Second step: electrostatic spinning prepares the PAN nanofiber of doping Si.Spinning condition is identical with second step among the embodiment 1.
The 3rd step: the oxidation processes of nascent nanofiber.The oxidation processes condition is identical with the 3rd step in the comparative example 2.
The 4th step: the carbonization of nanofiber oxide and the formation of nano-silicone wire/carbon composite material.Carbonization Conditions is identical with the 4th step of comparative example 2.
The 5th step: the preparation of silicon-carbon nano composite anode material and electrochemical property test.The material preparation is identical with the 5th step in method of testing and the comparative example 2.
By above-mentioned steps operation obtain silicon-carbon composite Nano negative material first reversible capacity be 625mAh/g, enclosed pasture efficient is 86%, the reversible capacity that circulates after 50 times is 546mAh/g, capability retention is 87%.
Embodiment 4
Compare with comparative example 3.
The first step: the preparation of spinning solution.The preparation method of spinning solution is identical with the first step in condition and the comparative example 3.
Second step: electrostatic spinning prepares the PAN nanofiber of doping Si.Spinning condition is identical with second step among the embodiment 2.
The 3rd step: the oxidation processes of nascent nanofiber.The oxidation processes condition is identical with the 3rd step in the comparative example 3.
The 4th step: the carbonization of nanofiber oxide and the formation of nano-silicone wire/carbon composite material.Carbonization Conditions is identical with the 4th step of comparative example 3.
The 5th step: the preparation of silicon-carbon nano composite anode material and electrochemical property test.The material preparation is identical with the 5th step in method of testing and the comparative example 3.
By above-mentioned steps operation obtain silicon-carbon composite Nano negative material first reversible capacity be 625mAh/g, enclosed pasture efficient is 86%, the reversible capacity that circulates after 50 times is 546mAh/g, capability retention is 87%.
By above-mentioned steps operation obtain silicon-carbon composite Nano negative material first reversible capacity be 1638mAh/g, enclosed pasture efficient is 75%, the reversible capacity that circulates after 50 times is 1113mAh/g, capability retention is 68%.
Above content is in conjunction with concrete preferred embodiment further description made for the present invention, can not assert that implementation of the present invention is confined to these explanations.For those skilled in the art, without departing from the inventive concept of the premise, can also make some being equal to substitute or obvious modification, and performance or purposes are identical, all should be considered as belonging to protection scope of the present invention.
Claims (10)
1. Si-C composite material with nanometer micropore gap structure, it is characterized in that: comprise silicon nanoparticle and carbon nano-fiber matrix, described silicon nanoparticle is dispersed in the described carbon nano-fiber matrix, is distributed with the nanometer micropore gap of nano aperture and the described nano aperture of connection in the described carbon nano-fiber matrix.
2. Si-C composite material according to claim 1, it is characterized in that: the average diameter of carbon nano-fiber is 100-600nm in the described carbon nano-fiber matrix, the average diameter of described silicon nanoparticle is 10-60nm.
3. Si-C composite material according to claim 1, it is characterized in that: the mass fraction of described silicon particle is 3-67%, the mass fraction of described carbon nano-fiber matrix is 33-97%.
4. the preparation method with Si-C composite material of nanometer gap structure is characterized in that, may further comprise the steps:
S1, configuration contain the polyacrylonitrile spinning solution of silicon nanoparticle;
S2, the polyacrylonitrile spinning solution that step S1 is obtained are packed in the syringe, carry out after the match electrostatic spinning at high-pressure electrostatic, dynamic analysis of spinning enters through spinning of 2-10cm in air that solidified forming obtains nascent polyacrylonitrile nanofiber in the liquid coagulating bath after the journey, nascent polyacrylonitrile nanofiber is placed 1-3h in the liquid coagulating bath, then carry out vacuumize and obtain polyacrylonitrile nanofiber, wherein, the voltage of described high-voltage electrostatic field is 5-30kV, and the spinning solution flow is 0.1-1.0mL/h;
S3, step S2 is obtained polyacrylonitrile nanofiber carry out oxidation processes and obtain the nanofiber oxide;
S4, described nanofiber oxide is carried out carbonization form described Si-C composite material.
5. preparation method according to claim 4, it is characterized in that: described step S1 comprises:
The polyacrylonitrile powder is added stirring and dissolving in the organic solvent, then add silicon nanoparticle and continue to stir more than the 24h, and ultrasonic wave disperses to obtain the described polyacrylonitrile spinning solution that contains silicon nanoparticle more than the 1h.
6. preparation method according to claim 4, it is characterized in that: described step S3 comprises:
Described oxidation processes is carried out in air, and the control oxidizing temperature progressively is warming up to 250-300 ℃ with the programming rate of 1-10 ℃/min from room temperature, and taking-up obtains described nanofiber oxide behind the constant temperature 1-3h.
7. preparation method according to claim 4, it is characterized in that: described step S4 comprises:
Described carbonization is carried out in the high temperature carbonization stove, in argon gas atmosphere, progressively is warming up to 600-1500 ℃ with the programming rate of 1-20 ℃/min from room temperature, and constant temperature 1-3h, is cooled to take out after the room temperature to obtain described Si-C composite material.
8. the described preparation method of any one according to claim 3-5, it is characterized in that: the mass fraction of polyacrylonitrile is 6-15wt% in the described polyacrylonitrile solution, the silicon nanoparticle that adds in the solution again and the mass ratio of polyacrylonitrile are 1:50-1:1.
9. the described preparation method of any one according to claim 4-5, it is characterized in that: the solvent of described polyacrylonitrile spinning solution is dimethyl formamide.
10. such as the described application of Si-C composite material in the preparation lithium ion battery negative material with nanometer micropore gap structure of claim 1-3 any one.
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