CN103915609A - Silicon-silicon oxide-carbon composite material, lithium ion secondary battery anode material, preparation methods of two and application of composite material - Google Patents

Silicon-silicon oxide-carbon composite material, lithium ion secondary battery anode material, preparation methods of two and application of composite material Download PDF

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CN103915609A
CN103915609A CN201210594097.4A CN201210594097A CN103915609A CN 103915609 A CN103915609 A CN 103915609A CN 201210594097 A CN201210594097 A CN 201210594097A CN 103915609 A CN103915609 A CN 103915609A
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silicon
particle
carbon
silica
carbon composite
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CN103915609B (en
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沈龙
董爱想
娄文君
乔永民
黄亮
刘广豹
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Ningbo Shanshan Silicon Based Materials Co ltd
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NINGBO SHANSHAN NEW MATERILA TECHNOLOGY Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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

Abstract

The invention provides a silicon-silicon oxide-carbon composite material, a lithium ion secondary battery anode material, preparation methods of the two materials and application of the composite material. The provided silicon-silicon oxide-carbon composite material successively comprises hard carbon particles and a second amorphous carbon layer along the ball diameter direction; the hard carbon particle inside comprises first particles each coated with a first amorphous carbon layer in a dispersion manner; and the first particle is silicon oxide particle and inside comprises simple-substance silicon particles in a dispersion manner. The silicon-silicon oxide-carbon composite material is applied to prepare the lithium ion secondary battery anode material. The lithium ion secondary battery anode material disclosed by the invention is large in charge/discharge capacity, high in first efficiency and long in capacity conservation rate after being recycled for a long time, and has wide market application prospect.

Description

Silicon-silica-carbon composite, ion secondary battery cathode material lithium, its preparation method and application
Technical field
The present invention relates to silicon-silica-carbon composite, ion secondary battery cathode material lithium, its preparation method and application.
Background technology
Business-like ion secondary battery cathode material lithium mostly is native graphite, Delanium, middle equal various graphite type material, and the lithium secondary battery chemical power source of preparing with these materials is widely used in portable electric appts, energy storage device and electric automobile.The theoretical capacity of graphite is 372mAh/g, and the reality of graphite negative electrodes material in half-cell takes off lithium capacity up to 365mAh/g at present, but is difficult to further promote.Take 18650 batteries as example, graphite cathode cannot meet the energy density requirement of battery more than 3.0Ah, and this turn of the market requires the negative material of a kind of novel high-energy metric density of essential exploitation to replace graphite type material.
As Novel anode material, elemental silicon, silica or both composite materials have demonstrated higher gram volume.The theoretical gram volume of elemental silicon is 4200mAh/g, silica theoretical capacity 2043mAh/g, and de-lithium current potential platform 0.45V left and right is all better than graphite in capacity and security performance.But, the electrical property defect of this class silica-base material of silicon or silica also clearly, mainly that silica-base material can produce 100%～300% volumetric expansion in removal lithium embedded process, huge change in volume can cause active material structure breaking, the efflorescence on collector, active material comes off from collector, and the cycle performance of battery sharply declines.Silica is compared with elementary silicon, and its theoretical specific capacity is low, but its structural stability in removal lithium embedded process is better than elementary silicon, and therefore, silica has more advantage in practical application compared with elemental silicon.
For example, the patent of invention of publication number CN1674325A, by by the primary fine particles of silicon, silicon alloy or silica and organo-silicon compound or its mixture sintering, prepares the composite particles of silicon.Silicon or silicon alloy microparticulate are in silica-based inorganic compound binding agent.Although this inventive embodiment has provided the initiation of charge capacity of 900mAh/g～2200mAh/g, has very high capacity, when capacity is in the time that 2000mAh/g is above, the capability retention of circulation in its 50 weeks is lower; When capacity is in the time that 900mAh/g is above, efficiency is lower first for it.For another example, the patent of invention of publication number CN101047234A, by the silica after ball milling is mixed with lithium powder, ball milling again under inert gas shielding, obtains silicon-silicon oxide-lithium composite negative pole material.Although the example that this invention provides shows that efficiency is greater than 80% first, its weak point is only having capability retention data and the capability retention of 50 weeks also lower, from the practical application request of lithium rechargeable battery also away from.
Application number is 201110275091.6 Chinese invention patent, by being oxidized sub-silicon high temperature sintering, generate the Si oxide complex that contains nano particle silicon, then ball milling makes the silicon composite cathode material of required particle diameter.This technique has solved the problem that the difficulty of nano-silicon in material disperseed to a certain extent, and preparation method is simple, but the half-cell that prepared composite material is made still has the decay of 50% left and right capacity after circulating 100 weeks, this mainly possible reason be, although nano-silicon has been dispersed in the matrix of Si oxide more uniformly, but be oxidized sub-silicon and in circulating battery, exist equally larger change in volume, just its bulking effect is less than the silicon of same volume, and exposed silicon directly contacts with electrolyte with Si oxide, the compatibility of itself and electrolyte is poor, electrolyte is consumed rapidly, silicon structure changes, and then cause capacity to decay fast.
Although above-mentioned patent has been introduced silica based materials, successfully promote the charge/discharge capacity of negative material, still defectiveness of material structure itself, capability retention is lower, and cycle performance is poor, cannot reach the level of direct use.And also there are a lot of defects in preparation technology.This present situation is urgently to be resolved hurrily.
Summary of the invention
Technical problem to be solved by this invention is to have overcome the Si-C composite material that existing silica is silicon source, charge/discharge capacity is less, it is low that the lower or long-time use of efficiency first recycles capability retention, cannot reach the defects such as application, be at present silicon-silica-carbon composite, ion secondary battery cathode material lithium, its preparation method and the application of the Si-C composite material electrical property in silicon source based on silica and a kind of being better than is provided.Ion secondary battery cathode material lithium charge/discharge capacity of the present invention is large, and efficiency is high first, recycles for a long time capability retention high, has wide market application foreground.
The invention provides silicon-silica-carbon composite, described silicon-silica-carbon composite comprises hard carbon particle and the second amorphous carbon layer successively along sphere diameter direction; The inner dispersion of described hard carbon particle has the coated primary particle of the first amorphous carbon layer, and described primary particle is that silicon oxide particle and inner dispersion have elemental silicon particle.
In the present invention, the particle diameter of described hard carbon particle is preferably 2 μ m～19.8 μ m.
In the present invention, the particle diameter D50 of described elemental silicon particle is preferably 5nm～30nm.
In the present invention, the particle diameter D50 of described silicon oxide particle is preferably 100nm～1 μ m.
In the present invention, the thickness of the first described amorphous carbon layer is preferably 10nm～100nm.
In the present invention, the thickness of the second described amorphous carbon layer is preferably 10nm～100nm.
In the present invention, the particle diameter of described silicon-silica-carbon composite is preferably 3 μ m～20 μ m.
In the present invention, described thickness is sphere diameter thickness.
In the present invention, the total carbon mass content of described silicon-silica-carbon composite is preferably 5%～20%.
In the present invention, the mass percent of described elemental silicon particle in silicon-silica-carbon composite preferably 2%～15%.
The present invention also provides the preparation method of above-mentioned silicon-silica-carbon composite, and it comprises the following steps:
Step 1: under the protection of non-oxidizing gas, by the SiO of the submicron order in fluidized state xpowder and organic carbon source carry out chemical vapour deposition reaction, disproportionated reaction occur simultaneously, obtain the coated primary particle of the first amorphous carbon layer; Described organic carbon source is the organic carbon source that cracking obtains amorphous carbon;
Step 2: in solvent, coated the first amorphous carbon layer making in step 1 primary particle and thermoplastic resin are cured to polymerization reaction, then low temperature preroast, pyrolysis, disproportionated reaction occur simultaneously, then classification, obtains hard carbon particle;
Step 3: the hard carbon particle making in step 2 is carried out to chemical vapour deposition reaction with organic carbon source under fluidized state, obtain the coated hard carbon particle of the second amorphous carbon layer; Described organic carbon source is with described in step 1.
In step 1, described SiO xpowder is the conventional SiO in this area xpowder, the SiO that in the present invention, preferably China fir China fir new material graduate model in Shanghai is SS-SiOx-3 xpowder; Commercially available obtaining.
Wherein, described SiO xpreferred 100nm～1 of the particle diameter μ m of powder; Described SiO xpowder, preferably 0.5 < X≤1, further preferred 0.7 < X < 0.9.
In step 1, described chemical vapour deposition reaction and disproportionated reaction can obtain elemental silicon particle, and described elemental silicon particle General Decentralized is in silicon oxide particle inside.Wherein, the preferred 5nm～30nm of particle diameter D50 of described elemental silicon particle.
In step 1, described non-oxidizing gas is the conventional non-oxidizing gas that carries out chemical vapour deposition reaction in this area, preferably inert gas and/or hydrogen.Described inert gas is the conventional inert gas in this area, as one or more in nitrogen, helium, argon gas, Krypton, xenon and radon gas, and preferred nitrogen and/or argon gas.
In step 1, the preferred 0.01NL/M～0.3NL/M of the flow of described non-oxidizing gas; Described NL/M, represents under standard state, 20 ℃, and under 1 atmospheric pressure, liter/min.
In step 1, one or more in organic carbon source optimization methane, ethane, ethene, acetylene, benzene and the toluene of described cracking acquisition amorphous carbon.
In step 1, preferably (1:1) of described organic carbon source and the flow-rate ratio of non-oxidizing gas～(1:6).
In step 1, described chemical vapour deposition reaction and disproportionated reaction are generally carried out in reactor, preferably have the reactor of heater; The described reactor with heater is the popular response device that such reaction occurs in this area, preferred streams fluidized bed reactor or have the rotary furnace of stock guide.
In step 1, described chemical vapour deposition reaction and the temperature of disproportionated reaction are the conventional temperature of carrying out chemical vapour deposition reaction, preferably 700 ℃～1100 ℃, are further preferably warming up to 700 ℃～1100 ℃ with the speed of 2 ℃/min～10 ℃/min.After finishing, chemical vapour deposition reaction is naturally cooled to room temperature by this area popular response device.
In step 1, described chemical vapour deposition reaction and the time of disproportionated reaction, preferably 2 hours～6 hours, can determine according to the conventionally test method in this area, described chemical vapour deposition reaction and the reaction end of disproportionated reaction are better to be determined with resistivity value, described resistivity value is preferably 0.2 Ω mm～10 Ω mm, more preferably 0.2 Ω mm～6 Ω mm, and described resistivity value is preferably tested by four probe method.
In step 2, described solvent is the conventional solvent that is cured polymerization reaction in this area, preferably organic solvent, one or more in further preferred cyclohexane, ethanol, washing oil, quinoline, toluene and dimethylbenzene.
In step 2, described thermoplastic resin is carbochain polymer and/or the heterochain polymer resin that such curing polymerization reaction occurs in this area, preferably one or more in polyvinyl chloride, acrylic resin, Merlon, epoxy resin, phenolic resins, furfuryl alcohol and polyformaldehyde.
In step 2, preferably (19:1) of the mass ratio of the primary particle that the first amorphous carbon layer of making in described step 1 is coated and described thermoplastic resin～(4:1).
In step 2, described curing polymerization reaction is preferably also added curing agent.
Described curing agent is the conventional curing agent that such curing polymerization reaction occurs in this area, preferably one or more in hexamethylenetetramine, hexamethylene diamine, m-phenylene diamine (MPD), aniline-formaldehyde resin, phthalic anhydride, benzene sulfonic acid and p-methyl benzenesulfonic acid.The mass percent of described curing agent preferably 1%～30%; Described mass percent is the mass percent that curing agent accounts for thermoplastic resin total amount.
In step 2, described elemental silicon particle shared mass percent in hard carbon particle is preferably 2%～15%, and the mass percent of described elemental silicon particle can be determined according to the conventionally test method in this area, preferably measure by ISO DIS9286.
In step 2, described classification processing, is the conventional hierarchical processing method in this area, preferably adopts gas flow sizing machine to carry out classification processing.
In step 2,, for there is the conventional temperature of such curing polymerization reaction, preferably 20 ℃～60 ℃ in the temperature of described curing polymerization reaction in this area.
In step 2, the time of described curing polymerization reaction, can determine according to the conventionally test method in this area, as DSC method is measured polymer reaction degree, preferably 3h～24h.
In step 2, the temperature of described low temperature preroast is the conventional temperature that such low temperature preroast occurs in this area, preferably 150 ℃～300 ℃, is further preferably warming up to 150 ℃～300 ℃ with the speed of 1 ℃/min～10 ℃/min.
In step 2, the preferred 2h～10h of time of described low temperature preroast.
In step 2, the temperature of described pyrolysis is the conventional temperature that such pyrolysis occurs in this area, preferably 800 ℃～1200 ℃, is further preferably warming up to 800 ℃～1200 ℃ with the speed of 1 ℃/min～10 ℃/min.
In step 2, preferred 1h～6h of the time of described pyrolysis.
In step 2, the degree of described disproportionated reaction can be determined by conventionally test method in this area, preferably determines by the measured XRD spectra of X-ray diffraction method, and calculates the size of silicon particle diameter by Scherrer formula.
Each reaction condition described in step 3 is all identical with each reaction condition of step 1.
In step 3, after obtaining the coated hard carbon particle of the second amorphous carbon layer, preferably also comprise the step of classification processing.Described classification processing, for the conventional hierarchical processing method in this area, in the present invention, preferably employing equipment carries out classification processing, described equipment is the conventional equipment that carries out diameter of particle classification in this area, preferred shunting Ultramicro-powder gas flow sizing machine, Multi-stage airflow grader or reverse-flow gas flow sizing machine in the present invention.
The present invention also provides aforesaid silicon-silica-carbon composite in the application of preparing in ion secondary battery cathode material lithium.
The present invention also provides ion secondary battery cathode material lithium to comprise graphite and aforesaid silicon-silica-carbon composite.
In the present invention, described graphite is the conventional graphite in this area, preferably one or more in Delanium, middle phase graphite and native graphite.
In the present invention, the particle diameter D50 of described graphite is 6 μ m～20 μ m preferably.
In the present invention, preferably (1:9) of the mass ratio of described silicon-silica-carbon composite and described graphite～(3:7).
The present invention also provides the preparation method of ion secondary battery cathode material lithium, comprises the following steps: graphite sample is mixed with described silicon-silica-carbon composite.
Each composition and the ratio of described composition are all same as above.
In the present invention, preferably adopt following method mixed: in mixed process, randomly draw three groups of the materials of zones of different, its three groups of specific area values approach, not on the same group between error be no more than 0.1, three groups of tap density data approach, not on the same group between error be no more than 0.1, reach mixed requirement.
In the present invention, the equipment of described mixing is batch mixer, described batch mixer is in this area, to carry out sample mix conventional batch mixer used, preferred double helix cantilever conical mixer, agravic twin shaft paddle mixer, ribbon flat mixer, horizontal colter mixing, drum mixer, single screw scraper type mixer, single-screw band mixer or Homotaxial paddle mixer in the present invention.
In the present invention, the described mixed time can be determined according to the physicochemical property according to material conventional in this area, be preferably 2h～10h.
Without prejudice to the field on the basis of common sense, above-mentioned each optimum condition, can combination in any, obtains the preferred embodiments of the invention.
Agents useful for same of the present invention and raw material be commercially available obtaining all.
Positive progressive effect of the present invention is:
1, silicon-silica-carbon composite of the present invention has critical effect for the energy density that improves lithium secondary battery;
2, silicon-silica-carbon composite provided by the invention, by compound with graphite, has higher efficiency first, good cycle performance, and 0.1C circulates 300 weeks capability retentions more than 80%.
Accompanying drawing explanation
The TEM figure of the primary particle that Fig. 1 embodiment 1 makes.
Fig. 2 is silicon-silica-carbon composite SEM photo prepared by embodiment 1.
Fig. 3 is the charging and discharging curve figure of the half-cell that makes of silicon-silica-carbon composite of embodiment 1.
Fig. 4 is silicon-silica of the present invention-carbon composite structures schematic diagram.
Embodiment
Mode below by embodiment further illustrates the present invention, but does not therefore limit the present invention among described scope of embodiments.The experimental technique of unreceipted actual conditions in the following example, according to conventional method and condition, or selects according to catalogue.
Embodiment 1
Step 1: the SiO powder of particle diameter D50=100nm (the SiO powder that the model that Shanghai Shan Shan new material research institute produces is SS-SiO-3d, commercially available obtaining) 200g is placed in to rotary furnace, rotary furnace internal diameter 8cm, long 0.5m.Take argon gas as protective gas, argon flow amount 0.01NL/M, prevents the oxidation of SiO powder.Rise to 700 ℃ with the heating rate of 2 ℃/min.When temperature rises to after 700 ℃, pass into acetylene, now, the flow-rate ratio of acetylene and argon gas is 1:3, insulation 2h post-reactor is cooled to room temperature naturally.With four probe method test resistance rate value be 3.132m Ω .mm.
The characterizing method of this structure, first cuts primary particle with FIB, observes its cross section by TEM, and as shown in Figure 1,1 represents elemental silicon particle to result; 2 represent 1 the electron diffraction diagram of choosing; 3 represent amorphous carbon layer.Carry out selected area electron diffraction sign, Si(111 to 1) crystal face d=0.31353nm, approach theoretical value 0.31355nm.With the cross section of Electronic Speculum observing samples, recording the first amorphous carbon layer thickness is 15nm.
Step 2: collect the primary particle making in step 1, take furfuryl alcohol as thermoplastic resin, both mass ratioes are 9.5:0.5, and cyclohexane is solvent, adds curing agent p-methyl benzenesulfonic acid simultaneously, the quality of curing agent is furfuryl alcohol 1%.Under 20 ℃ of conditions, stir 24h, tentatively obtain solidifying the product of polymerization reaction.Then the product that solidifies polymerization reaction is carried out to roasting, take argon gas as protective atmosphere, roasting temperature increasing schedule is as follows: 1 ℃/min is warming up to 150 ℃, and insulation 2h, is warming up to 800 ℃ of pyrolysis with 1 ℃/min, and insulation 1h, is cooled to room temperature.Collect the sample after roasting, adopt jet mill grinding machine to pulverize same time stage to sample, obtaining particle diameter is the hard carbon particle of D50=4.1 μ m.
Step 3: take argon gas as protective gas, argon flow amount 0.01NL/M, rises to 700 ℃ with the heating rate of 2 ℃/min.When temperature rises to after 700 ℃, pass into acetylene, now, the flow-rate ratio of acetylene and argon gas is 1:3, insulation 2h post-reactor is cooled to room temperature naturally.Adopt gas flow sizing machine, sample is carried out to classification, obtain silicon-silica-carbon composite of D50=4.3 μ m, its pattern is shown in Fig. 2.With the cross section of Electronic Speculum observing samples, recording the second amorphous carbon layer thickness is 100nm.
The structural representation of the silicon-silica-carbon composite of the present embodiment as shown in Figure 4, comprise successively hard carbon particle 4 and the second amorphous carbon layer 5 along sphere diameter direction, the inner dispersion of described hard carbon particle 4 has the coated primary particle of the first amorphous carbon layer 3, described primary particle is that silicon oxide particle 1 and inner dispersion have elemental silicon particle 2, and silicon oxide particle 1 and elemental silicon particle 2 are combined the primary particle into the present embodiment.
By the thing phase of XRD analysis " silicon-silica-carbon composite ", calculate the particle diameter of silicon crystallite (111 crystal face) with Scherrer formula, 1 is of a size of 10nm; 2 are of a size of raw material particle size; EDS analyzing total carbon mass content is 5%, elemental silicon mass content 8%.
Silicon-silica-carbon composite is as the application of negative material: for obtain can commercial applications silicon based anode material, on the basis of silicon-silica-carbon composite of preparing at the present embodiment, by itself and native graphite (graphite that the model that Shanghai Shanshan Science and Technology Co., Ltd produces is MGS-2, commercially available obtaining) in mass ratio 1:9 fully mix 2h.Batch mixer is double helix cantilever conical mixer.Biased sample is crossed 150 mesh standard sieves, and power supply performance test is used.
Electrochemical property test:
Adopt button cell CR2430 type, take lithium sheet as to electrode, adopting barrier film is that Celgard2300PP/PE/PP(PP represents polypropylene, PE represents polyethylene) three layers of microporous compound film, represent ethylene carbonate with 1M LiPF6/EC+DMC+EMC(EC, DMC represents dimethyl carbonate, and EMC represents ethyl-methyl carbonic ester) solution is supporting electrolyte.Product by making in embodiment 1: SP:CMC:SBR(SP represents conductive carbon black, CMC represents sodium carboxymethylcellulose, SBR represents butadiene-styrene rubber) fit in slurry in 95:2:1.5:1.5 ratio, then be coated on copper-foil conducting electricity, 120 ℃ of dry 2h, use roller press, roll-forming under the pressure of 10MPa.By after positive, negative electrode plate, barrier film and electrolyte assembling, punching press sealing.All assembling processes are all carried out in the dry glove box that is full of argon gas.
The lithium ion battery of above-mentioned structure allows at room temperature incubated overnight.Utilize Arbin punching/discharge tester test battery charge-discharge performance.Test charging and discharging currents density is 0.6mA/cm 2, cut-off charging/discharging voltage is 0.005-2.000V.Measure initial capacity and the coulombic efficiency of described lithium-ions battery, by repeating aforesaid operations, carry out 300 circulations of charge/discharge test on described lithium rechargeable battery, its test result is in table 1.First charge-discharge curve is shown in Fig. 3, and in Fig. 3, abscissa represents discharge capacity (mAh/g), and ordinate represents voltage (V).
Embodiment 2
Step 1:
The SiO powder of particle diameter D50=1 μ m (the SiO powder that the Shanghai graduate model of China fir China fir new material is SS-SiO-3e, commercially available obtaining) 200g is placed in to rotary furnace, rotary furnace internal diameter 8cm, long 0.5m.Take argon gas as protective gas, argon flow amount 0.01NL/M, prevents the oxidation of SiO powder.Rise to 700 ℃ with the heating rate of 2 ℃/min.When temperature rises to after 700 ℃, pass into acetylene, now, the flow-rate ratio of acetylene and argon gas is 1:3, insulation 2h post-reactor is cooled to room temperature naturally.With four probe method test resistance rate value be 10.856m Ω .mm.With the cross section of Electronic Speculum observing samples, recording the first amorphous carbon layer thickness is 10nm.
The operating procedure of step 2 and step 3 is identical with the operating procedure of step 2 in embodiment 1 and step 3.The D50=10.5 μ m of hard carbon particle, obtains silicon-silica-carbon composite of D50=10.7 μ m.With the cross section of Electronic Speculum observing samples, recording the second amorphous carbon layer thickness is 100nm.
By the thing phase of XRD analysis " silicon-silica-carbon composite ", calculate the particle diameter of silicon crystallite (111 crystal face) with Scherrer formula, 1 is of a size of 5.8nm; 2 are of a size of raw material particle size; EDS analyzing total carbon mass content is 5%, elemental silicon mass content 7%.
Electrochemical property test method is identical with the method for testing of embodiment 1, and its test result is in table 1.
Embodiment 3
Preparation method is identical with the preparation method of embodiment 1.Silicon-silica-carbon composite physical index is referring to embodiment 1.
Silicon-silica-carbon composite is as the application of negative material:
For obtain can commercial applications silicon based anode material, on the basis of silicon-silica-carbon composite of preparing at the present embodiment 3, by itself and mesocarbon micro mist (the mesocarbon micro mist that the model of Shanghai Shanshan Science and Technology Co., Ltd is MCP, commercially available obtaining) in mass ratio 1:9 fully mix 2h.Batch mixer is double helix cantilever conical mixer.Biased sample is crossed 150 mesh standard sieves, and power supply performance test is used.
Electrochemical property test method is identical with the method for testing of embodiment 1, and its test result is in table 1.
Embodiment 4
Step 1:
By the SiO of particle diameter D50=0.5 μ m 0.9powder (the SiO that the Shanghai graduate model of China fir China fir new material is SS-SiO-3c 0.9powder, commercially available obtaining) 200g is placed in rotary furnace, rotary furnace internal diameter 8cm, long 0.5m.Take argon gas as protective gas, argon flow amount 0.06NL/M, prevents SiO 0.9powder oxidation.Rise to 1000 ℃ with the heating rate of 10 ℃/min.When temperature rises to after 1000 ℃, pass into acetylene, now, the flow-rate ratio of acetylene and argon gas is 1:3, insulation 6h post-reactor is cooled to room temperature naturally.With four probe method test resistance rate value be 6.476m Ω .mm.With the cross section of Electronic Speculum observing samples, recording the first amorphous carbon layer thickness is 100nm.
Step 2:
By the primary particle making in step 1, take phenolic resins as thermoplastic resin, ethanol is solvent, adds curing agent hexamethylenetetramine simultaneously, under 5%, 20 ℃ of condition that the quality of curing agent is phenolic resins, stirs 4h, tentatively obtains solidifying the product of polymerization reaction.Then the product that solidifies polymerization reaction is carried out to roasting, take argon gas as protective atmosphere, roasting temperature increasing schedule is as follows: 10 ℃/min is warming up to 300 ℃, insulation 6h, and 10 ℃/min is warming up to 1000 ℃, and insulation 6h, is cooled to room temperature.Collect the sample after roasting, adopt jet mill grinding machine to pulverize same time stage to sample, obtaining particle diameter is the hard carbon particle of D50=3.4 μ m.
Step 3: take argon gas as protective gas, argon flow amount 0.06NL/M, rises to 1000 ℃ with the heating rate of 10 ℃/min.When temperature rises to after 1000 ℃, pass into acetylene, now, the flow-rate ratio of acetylene and argon gas is 1:3, insulation 6h post-reactor is cooled to room temperature naturally.Adopt gas flow sizing machine, sample is carried out to classification, obtain silicon-silica-carbon composite of D50=3.6 μ m.
With the cross section of Electronic Speculum observing samples, recording the second amorphous carbon layer thickness is 100nm.
By the thing phase of XRD analysis " silicon-silica-carbon composite ", calculate the particle diameter of silicon crystallite (111 crystal face) with Scherrer formula, 1 is of a size of 25.6nm; 2 are of a size of raw material particle size; EDS analyzing total carbon mass content is 20%, elemental silicon mass content 4%.
Silicon-silica-carbon composite is as the application of negative material:
For obtain can commercial applications silicon based anode material, on the basis of silicon-silica-carbon composite of preparing at the present embodiment, by itself and mesocarbon micro mist (the mesocarbon micro mist that the model that Shanghai Shanshan Science and Technology Co., Ltd produces is MCP, commercially available obtaining) in mass ratio 3:7 fully mix 6h.Batch mixer is double helix cantilever conical mixer.Biased sample is crossed 150 mesh standard sieves, and power supply performance test is used.
Electrochemical property test method is identical with the method for testing of embodiment 1, and its test result is in table 1.
Embodiment 5
Step 1:
By the SiO of particle diameter D50=1 μ m 0.5powder (Shanghai Shan Shan new material research institute produces, the SiO0.5 powder that model is SS-SiO-3a, commercially available obtaining) 200g is placed in rotary furnace, rotary furnace internal diameter 8cm, long 0.5m.Take nitrogen as protective gas, nitrogen flow 0.3NL/M, prevents SiO 0.5powder oxidation.Rise to 1100 ℃ with the heating rate of 10 ℃/min.When temperature rises to after 1100 ℃, pass into acetylene, now, the flow-rate ratio of acetylene and nitrogen is 1:3, insulation 6h post-reactor is cooled to room temperature naturally.With four probe method test resistance rate value be 7.323m Ω .mm.With the cross section of Electronic Speculum observing samples, recording the first amorphous carbon layer thickness is 100nm.
Step 2:
By the primary particle making in step 1, take phenolic resins as coated presoma, both mass ratioes are 8:2, ethanol is solvent, adds curing agent hexamethylenetetramine simultaneously, and the quality of curing agent is phenolic resins 30%, under 60 ℃ of conditions, stir 3h, tentatively obtain solidifying the product of polymerization reaction.Then the product that solidifies polymerization reaction is carried out to roasting, take nitrogen as protective atmosphere, roasting temperature increasing schedule is as follows: 10 ℃/min is warming up to 300 ℃, insulation 10h, and 10 ℃/min is warming up to 1100 ℃, and insulation 6h, is cooled to room temperature.Collect the sample after roasting, adopt jet mill grinding machine to pulverize same time stage to sample, obtaining particle diameter is the hard carbon particle of D50=19 μ m.
Step 3:
Take nitrogen as protective gas, nitrogen flow 0.3NL/M, rises to 1100 ℃ with the heating rate of 10 ℃/min.When temperature rises to after 1100 ℃, pass into acetylene, now, the flow-rate ratio of acetylene and nitrogen is 1:3, insulation 6h post-reactor is cooled to room temperature naturally.Adopt gas flow sizing machine, sample is carried out to classification, the particle that obtains D50=19.2 μ m is silicon-silica-carbon composite.
With the cross section of Electronic Speculum observing samples, recording the second amorphous carbon layer thickness is 100nm.
By the thing phase of XRD analysis " silicon-silica-carbon composite ", calculate the particle diameter of silicon crystallite (111 crystal face) with Scherrer formula, 1 is of a size of 29.2nm; 2 are of a size of raw material particle size; EDS analyzing total carbon mass content is 20%, elemental silicon mass content 10%.
Silicon-silica-carbon composite is as the application of negative material:
For obtain can commercial applications silicon based anode material, on the basis of silicon-silica-carbon composite of preparing at the present embodiment, by itself and Delanium (Delanium that the model that Shanghai Shanshan Science and Technology Co., Ltd produces is 3H, commercially available obtaining) in mass ratio 3:7 fully mix 10h.Batch mixer is double helix cantilever conical mixer.Biased sample is crossed 150 mesh standard sieves, and power supply performance test is used.
Electrochemical property test method is identical with the method for testing of embodiment 1, and its test result is in table 1.
Embodiment 6
Step 1:
By the SiO of particle diameter D50=0.5 0.75(Shanghai Shan Shan new material research institute produces powder, the SiO that model is SS-SiO-3b 0.75powder, commercially available obtaining) 200g is placed in fluid bed, fluid bed internal diameter 4cm, long 1m.Take nitrogen as protective gas, nitrogen flow 0.1NL/M, prevents SiO 0.75powder oxidation.Rise to 900 ℃ with the heating rate of 5 ℃/min.When temperature rises to after 900 ℃, pass into acetylene, now, the flow-rate ratio of acetylene and nitrogen is 1:3, insulation 4h post-reactor is cooled to room temperature naturally.With four probe method test resistance rate value be 3.638m Ω .mm.With the cross section of Electronic Speculum observing samples, recording the first amorphous carbon layer thickness is 5nm.
Step 2:
By the primary particle making in step 1, take phenolic resins as thermoplastic resin, both mass ratioes are 8.8:1.8, ethanol is solvent, add curing agent hexamethylenetetramine simultaneously, the quality of curing agent is to stir 6h under 15%, 30 ℃ of condition of phenolic resins, tentatively obtains solidifying the product of polymerization reaction.Then the product that solidifies polymerization reaction is carried out to roasting, take nitrogen as protective atmosphere, roasting temperature increasing schedule is as follows: 5 ℃/min is warming up to 240 ℃, insulation 6h, and 6 ℃/min is warming up to 900 ℃, and insulation 4h, is cooled to room temperature.Collect the sample after roasting, adopt jet mill grinding machine to pulverize same time stage to sample, obtaining particle diameter is the hard carbon particle of D50=13 μ m.
Step 3: take nitrogen as protective gas, nitrogen flow 0.3NL/M, rises to 900 ℃ with the heating rate of 5 ℃/min.When temperature rises to after 900 ℃, pass into acetylene, now, the flow-rate ratio of acetylene and argon gas is 1:3, insulation 4h post-reactor is cooled to room temperature naturally.Adopt gas flow sizing machine, sample is carried out to classification, obtain silicon-silica-carbon composite of D50=13.2 μ m.With the cross section of Electronic Speculum observing samples, the second amorphous carbon layer thickness is 100nm.By the thing phase of XRD analysis " silicon-silica-carbon composite ", calculate the particle diameter of silicon crystallite (111 crystal face) with Scherrer formula, 1 is of a size of 20.6nm; 2 are of a size of raw material particle size; EDS analyzing total carbon mass content is 5%, elemental silicon mass content 9%.
" silicon-oxidation silico-carbo " composite material is as the application of negative material:
For obtain can commercial applications silicon based anode material, on the basis of silicon-silica-carbon composite of preparing at the present embodiment, by itself and Delanium (Shanghai Shanshan Science and Technology Co., Ltd produces, the Delanium that model is 3H, commercially available obtaining) in mass ratio 2:8 fully mix 6h.Batch mixer is double helix cantilever conical mixer.Biased sample is crossed 150 mesh standard sieves, and power supply performance test is used.
Electrochemical property test method is identical with the method for testing of embodiment 1, and its test result is in table 1.
Comparative example 1
By the SiO powder of particle diameter D50=100nm, (Shanghai Shan Shan new material research institute produces, model is the SiO powder of SS-SiO-3d, commercially available obtaining) be silicon source, do not adopt the vapor deposition reaction of step 1, directly carry out the technique of step 2, step 3 and " silicon-oxidation silico-carbo " composite material as the technique for applying of negative material all with embodiment 1.Electrochemical property test method is identical with the method for testing of embodiment 1, and its test result is in table 1.
Comparative example 2
By particle diameter D50=5 μ m(purchased from Wuqiang County photoelectricity Coating Materials factory) SiO 0.9powder is coated with hard carbon, and concrete steps are: take phenolic resins as thermoplastic resin, and SiO 0.9the mass ratio of powder and phenolic resins is 8.8:1.8, and ethanol is solvent, adds curing agent hexamethylenetetramine simultaneously, under 15%, 30 ℃ of condition that the quality of curing agent is phenolic resins, stirs 6h, tentatively obtains solidifying the product of polymerization reaction.Then the product that solidifies polymerization reaction is carried out to roasting, take nitrogen as protective atmosphere, roasting temperature increasing schedule is as follows: 5 ℃/min is warming up to 240 ℃, insulation 6h, and 6 ℃/min is warming up to 900 ℃, and insulation 4h, is cooled to room temperature.Collect the sample after roasting, adopt jet mill grinding machine to pulverize same time stage to sample, obtain the powder that particle diameter is D50=13 μ m.By itself and Delanium (3H, Shanghai Shanshan Science and Technology Co., Ltd produces, commercially available obtaining) in mass ratio 2:8 fully mix 6h.Batch mixer is double helix cantilever conical mixer.Biased sample is crossed 150 mesh standard sieves, and power supply performance test is used.
Electrochemical property test method is identical with the method for testing of embodiment 1, and its test result is in table 1.
Table 1 embodiment 1～6 and comparative example's 1～2 battery testing result table
Conclusion: the battery performance of the prepared lithium rechargeable battery of material of the present invention (initial discharge capacity, coulomb efficiency and recycle for a long time capacitance conservation rate) is significantly improved than existing negative material, the capability retention especially recycling for 300 weeks improves and reaches 10～20%.

Claims (13)

1. silicon-silica-carbon composite, is characterized in that: described silicon-silica-carbon composite comprises hard carbon particle and the second amorphous carbon layer successively along sphere diameter direction; The inner dispersion of described hard carbon particle has the coated primary particle of the first amorphous carbon layer, and described primary particle is that silicon oxide particle and inner dispersion have elemental silicon particle.
2. silicon-silica-carbon composite as claimed in claim 1, is characterized in that: the particle diameter of described silicon-silica-carbon composite is 3 μ m～20 μ m; The particle diameter of described hard carbon particle is 2 μ m～19.8 μ m; The particle diameter D50 of described elemental silicon particle is 5nm～30nm; The particle diameter D50 of described silicon oxide particle is 100nm～1 μ m; The thickness of the first described amorphous carbon layer is 10nm～100nm; The thickness of the second described amorphous carbon layer is 10nm～100nm; Described thickness is sphere diameter thickness; The total carbon mass content of described silicon-silica-carbon composite is preferably 5%～20%; The mass percent of described elemental silicon particle in silicon-silica-carbon composite is preferably 2%～15%.
3. the preparation method of silicon-silica-carbon composite as claimed in claim 1 or 2, is characterized in that: it comprises the following steps:
Step 1: under the protection of non-oxidizing gas, by the SiO of the submicron order in fluidized state xpowder and organic carbon source carry out chemical vapour deposition reaction, disproportionated reaction occur simultaneously, obtain the coated primary particle of the first amorphous carbon layer; Described organic carbon source is the organic carbon source that cracking obtains amorphous carbon;
Step 2: in solvent, coated the first amorphous carbon layer making in step 1 primary particle and thermoplastic resin are cured to polymerization reaction, then low temperature preroast, pyrolysis, disproportionated reaction occur simultaneously, then classification, obtains hard carbon particle;
Step 3: the hard carbon particle making in step 2 is carried out to chemical vapour deposition reaction with organic carbon source under fluidized state, obtain the coated hard carbon particle of the second amorphous carbon layer; Described organic carbon source is described in step 1.
4. preparation method as claimed in claim 3, is characterized in that: described SiO xthe particle diameter of powder is 100nm～1 μ m; Described SiO xin powder, X meets 0.5 < X≤1, preferably 0.7 < X < 0.9; In step 3, after obtaining the coated hard carbon particle of the second amorphous carbon layer, also comprise the step of classification processing; Described classification is processed and is preferably adopted shunting Ultramicro-powder gas flow sizing machine, Multi-stage airflow grader or reverse-flow gas flow sizing machine.
5. preparation method as claimed in claim 3, it is characterized in that: in step 1 and step 3, described chemical vapour deposition reaction and the temperature of disproportionated reaction are 700 ℃～1100 ℃, are preferably warming up to 700 ℃～1100 ℃ with the speed of 2 ℃/min～10 ℃/min; Finish post-reactor at described chemical vapour deposition reaction and be naturally cooled to room temperature; Described chemical vapour deposition reaction and the time of disproportionated reaction is 2 hours～and 6 hours; Described chemical vapour deposition reaction and the reaction end of disproportionated reaction are better to be determined with resistivity value, and wherein, described resistivity value is 0.2 Ω mm～10 Ω mm; Described resistivity value is preferably tested by four probe method.
6. preparation method as claimed in claim 3, is characterized in that: in step 1 neutralization procedure 3, described non-oxidizing gas is inert gas and/or hydrogen; Described inert gas is one or more in nitrogen, helium, argon gas, Krypton, xenon and radon gas; The flow of described non-oxidizing gas is 0.01NL/M～0.3NL/M; The organic carbon source of described cracking acquisition amorphous carbon is one or more in methane, ethane, ethene, acetylene, benzene and toluene; Described organic carbon source and the flow-rate ratio of non-oxidizing gas are (1:1)～(1:6).
7. preparation method as claimed in claim 3, is characterized in that: in step 2, described solvent is one or more in cyclohexane, ethanol, washing oil, quinoline, toluene and dimethylbenzene.
8. preparation method as claimed in claim 3, it is characterized in that: in step 2, described thermoplastic resin is carbon chain polymerization resin and/or heterochain polymer resin, preferably one or more in polyvinyl chloride, acrylic resin, Merlon, epoxy resin, phenolic resins, furfuryl alcohol and polyformaldehyde; The mass ratio of the primary particle that the first amorphous carbon layer of making in described step 1 is coated and described thermoplastic resin is (19:1)～(4:1).
9. preparation method as claimed in claim 3, is characterized in that: in step 2, described curing polymerization reaction is added curing agent; Described curing agent is one or more in hexamethylenetetramine, hexamethylene diamine, m-phenylene diamine (MPD), aniline-formaldehyde resin, phthalic anhydride, benzene sulfonic acid and p-methyl benzenesulfonic acid; The mass percent of described curing agent is 1%～30%, and described mass percent is the mass percent that curing agent accounts for thermoplastic resin total amount.
10. preparation method as claimed in claim 3, is characterized in that: in step 2, the temperature of described curing polymerization reaction is 20 ℃～60 ℃; The time of described curing polymerization reaction is 3h～24h; The temperature of described low temperature preroast is 150 ℃～300 ℃, is preferably warming up to 150 ℃～300 ℃ with the speed of 1 ℃/min～10 ℃/min; The time of described low temperature preroast is 2h～10h; The temperature of described pyrolysis is 800 ℃～1200 ℃, is preferably warming up to 800 ℃～1200 ℃ with the speed of 1 ℃/min～10 ℃/min; The time of described pyrolysis is 1h～6h.
11. silicon-silica-carbon composites as claimed in claim 1 or 2 are in the application of preparing in ion secondary battery cathode material lithium.
12. 1 kinds of ion secondary battery cathode material lithiums, is characterized in that: comprise graphite and silicon-silica-carbon composite as claimed in claim 1 or 2; Described graphite is preferably one or more in Delanium, middle phase graphite and native graphite; The particle diameter D50 of described graphite is preferably 6 μ m～20 μ m; The mass ratio of described silicon-silica-carbon composite and described graphite is preferably (1:9)～(3:7).
The preparation method of 13. ion secondary battery cathode material lithiums as claimed in claim 12, is characterized in that comprising the following steps: graphite sample mixed with described silicon-silica-carbon composite.
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