CN101604753A - Carbon-silicon composite material and its production and use - Google Patents
Carbon-silicon composite material and its production and use Download PDFInfo
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Abstract
The present invention relates to a kind of carbon-silicon composite material and its production and use, belong to technical field of lithium-ion battery.Technical problem solved by the invention is can cushion silicon oxide particles when improving the electronic conductivity of silicium cathode material to expand and shrink caused stress.Carbon-silicon composite material of the present invention is crossed under at least a effect among catalyst Fe, Co, Ni, Cu, Mg, Mn, Ti, Sn, Si, Zr, Zn, Ge, Pb and the In at metallic element by silica-base material, and the growth carbon nano-fiber obtains on the surface of silica-base material particle; Carbon nano-fiber is with the growth of the form of rattan and be centered around the surface of silica-base material particle.Adopt the electronic conductivity height of the negative pole of this material preparation, thereby can obtain having the battery of excellent initial charge/flash-over characteristic, can be used for driving the vehicles such as mobile communication apparatus, miniaturized electronics, electric motor car and hybrid electric vehicle etc.
Description
Technical field
The present invention relates to a kind of carbon-silicon composite material and its production and use, belong to technical field of lithium-ion battery.
Background technology
In 21 century,, introduced the new model of the information technology that can carry out multimedia interaction communication, as notebook computer, mobile phone and DMB phone along with the semi-conductive development of portable telecommunication apparatus miniaturization.Answer the demand of multi-function electronic device, developed high power capacity with high-tension secondary cell and developed relevant electrode material.Since the nineties in 20th century early stage Sony developed its first based on the lithium rechargeable battery of graphite and since putting on market, the energy density of secondary cell and capacity increase rapidly.Yet, still develop than itself having the more secondary cell of high power capacity, higher charge/discharge capacity and more systemic circulation stability seeking.Because the capacity of battery depends on the charge/discharge performance of negative material, so the improvement of negative material has become the main bottleneck of development secondary cell.
The contain amount of element silicon in universe is very abundant, occupy the 3rd, and silicon materials have very high specific discharge capacity, but the conductivity of silicon is very low, and circulation time can produce huge change in volume, make the non-constant of cycle performance of material, this has limited the application of silicon materials in lithium ion battery negative material; In contrast, the invertibity that material with carbon element has extraordinary lithium ion to embed and deviate from, but its capacity is lower comparatively speaking, this can not satisfy the requirement of growing society to high-specific energy battery, although extensively adopt the negative material of material with carbon element at present as lithium ion battery, but along with the problem of this material low capacity of the development of society becomes urgent gradually, thereby the material that needs to seek a kind of high energy, cheapness replaces negative material commonly used at present.Proposed to use electric conducting material to construct the electrical conductivity network, also proposed on the surface of active material, to be coated with carbon.Yet in charge/discharge cycle, the silicium cathode active material carries out taking off the embedding reaction with the alloying reaction and the lithium of lithium repeatedly.Silicon oxide particles expands repeatedly and shrinks, and makes intergranular electrical conductivity network be disconnected gradually.Therefore, the internal resistance of cell increases, and is difficult to realize gratifying cycle characteristics.
Someone is with element such as Cr, and B or P are added in the silicon materials, but the electrical conductivity network between silicon oxide particles also can disconnect gradually.Also have when using ball mill that silicon materials and carbon nano-tube are mixed, the intergranular electrical conductivity network of silicon materials also disconnects gradually, can not obtain gratifying cycle characteristics.The somebody directly is formed at the film of Si, Sn or Ge or their oxide on the collector, but film can expand on the thickness direction of battery lead plate, and this can make electrode assemblie bending or collector fracture, thereby capacity is descended greatly.
Summary of the invention
The problem to be solved in the present invention provides a kind of new carbon-silicon composite material, can cushion silicon oxide particles when improving the electronic conductivity of silicium cathode material and expand and shrink caused stress.
In order to address the above problem, technical scheme of the present invention is:
The invention provides a kind of carbon-silicon composite material, comprise amorphous silicon oxidation composition granule SiO
XAnd carbon nano-fiber of silicon oxide particles surface combination (CNF) and metallic element, 0.05＜x＜1.95 wherein, metallic element is the catalyst elements that is used to promote carbon nanofibers grow, is selected from least a (preferably among Fe, Co, Ni, Cu, the Mg at least a) of Fe, Co, Ni, Cu, Mg, Mn, Ti, Sn, Si, Zr, Zn, Ge, Pb and In.Carbon nano-fiber is as resilient coating, absorbs because of silicon oxide particles to expand and shrink caused stress.
Silica-base material SiO of the present invention
XRequiring is not the pure silicon or the SiO of crystal formation
2, should be Si oxide unbodied, incomplete oxidation, the scope of 0.05＜x＜1.95 all can realize the present invention.Can obtain or adopt existing chemistry, physical method Si or SiO by purchase to crystal formation
2Be treated to amorphous silicon oxidation thing.
Carbon-silicon composite material of the present invention is by under the catalytic action of metallic element, and the growth carbon nano-fiber obtains on the surface of silica-base material particle; Carbon nano-fiber is with the growth of the form of rattan and be centered around the surface of silica-base material particle.
At least one end of carbon nano-fiber and the surface combination of silicon oxide particles, yet, the two ends of carbon nano-fiber can with the surface combination of silicon oxide particles.
With SiO
XBe the 100wt% meter, the 0.01wt%～10wt% of metallic element, preferred 1wt%～3wt%.
The carbon nanofibers grow amount is 5～200wt%, and the preferred growth amount is 20～100wt%.
The carbon nano-fiber diameter is the fine fibre of 1nm～40nm, length 10nm～200 μ m.Preferably: carbon nano-fiber is for comprising the fine fibre of diameter 1nm～40nm and the big fiber of diameter 50～200nm simultaneously.
Described silica-base material refers to mainly with silicon or Si oxide SiO
xBe the electro-chemical activity phase material, perhaps silicon and Si oxide SiO
xHave or do not have the compound material of other materials of electro-chemical activity with other, complex method can be a mechanical mixture, mechanical ball milling, chemistry coating etc.Such as graphite and amorphous Si O
xCompound, wherein graphite and amorphous Si O
xWeight ratio can be the graphite of 1～50wt% and the amorphous Si O of 50～99wt%
x
SiO
x(0.05＜x＜1.95) can be the amorphous Si O that utilizes the preparation of oscillatory type ball milling under inert atmosphere for the silicon substrate of representative
x(0.05＜x＜1.95), geometric shape are irregular shape or sphere, and preferred spherical, average grain diameter is 100nm～100 μ m.
Can also comprise electric conducting materials such as conducting polymer in the described carbon-silicon composite material, as long as electric conducting material does not damage the function of carbon-silicon composite material.
Second technical problem to be solved by this invention provides the preparation method of above-mentioned carbon-silicon composite material, specifically comprises the steps:
1) preparation of catalyst solution
At least a acetate with Fe, Co, Ni, Cu, Mg, Mn, Ti, Sn, Si, Zr, Zn, Ge, Pb and In, be dissolved in one or more the solvent that is selected from distilled water, ethanol, methyl alcohol, isopropyl alcohol, ethylene glycol or the glycerol, form catalyst solution.
The selection of acetate is based on a large amount of test of inventor, and other salt can not be contained big fiber and fibrillose composite material simultaneously.The concentration 0.0001M of catalyst solution～0.1M can implement, when concentration is big, and the carbon nano-fiber content height that the composite material of preparation generates, man-hour is short; Concentration hour preparation is with prolonging the man-hour of the fiber needs of content.
Choice of Solvent is based on the solvent that the solubility of considering compound and solvent and electro-chemical activity compatibility are mutually selected solution.
2) catalyst cupport
With silica-base material SiO
x(0.05＜x＜1.95) join in the catalyst solution that step 1) makes, and stir 30 minutes-20 hours, leave standstill 5～72 hours, stir dryly, and 100 ℃ of vacuumize 12 hours obtains the silica-base material of catalyst cupport.Silicon oxide particles SiO for every 100wt%
X, the amount of the catalyst granules of load is 0.01wt%～10wt%, preferred 1wt%～3wt%;
Catalyst may reside in the surface of silicon oxide particles at least; Yet it also may reside in the inside of silicon oxide particles.
3) chemical vapour deposition (CVD)
With step 2) silica-base material of the catalyst cupport that obtains is placed in the heatproof container, the tube furnace of packing into then, charge into non-carrier of oxygen: the gaseous mixture of helium or helium and hydrogen or nitrogen, carry out preliminary treatment, temperature programming to 500 then～1200 ℃ temperature, gas is converted to carbon-source gas or is converted to the gaseous mixture of non-carrier of oxygen (helium, nitrogen or hydrogen) and carbon-source gas, constant temperature 20 minutes naturally cools to room temperature promptly after carrying out chemical vapour deposition (CVD) to 48 hours.Described carbon-source gas be carbon monoxide, methane, acetylene and or ethene at least a.
Preferably: Ni is a catalyst elements, and methyl alcohol is solvent.
Carbon-silicon composite material of the present invention is by the effect in catalyst elements, and the growth carbon nano-fiber obtains on the surface of silicon oxide particles.At least one end of carbon nano-fiber and the surface combination of silicon oxide particles.Yet, the two ends of carbon nano-fiber can with the surface combination of silicon oxide particles.When catalyst elements was not separated with silicon oxide particles, catalyst elements loaded on the silicon oxide particles, and carbon nanofibers grow is on catalyst elements.In other words, the stiff end of carbon nano-fiber on catalyst elements, the binding site of catalyst elements between carbon nano-fiber and silicon oxide particles.Schematic diagram is seen Fig. 1.When catalyst elements is separated with silicon oxide particles, an end of carbon nano-fiber and the surface combination of silicon oxide particles, the other end combines with catalyst elements.The carbon-silicon composite material that promptly obtains, catalyst elements are positioned at the free end of carbon nano-fiber.Schematic diagram is seen Fig. 2.In prepared carbon-silicon composite material, can exist catalyst elements simultaneously at the carbon nano-fiber stiff end with in the free-ended two kinds of situations of carbon nano-fiber.In addition, have the carbon nano-fiber of catalyst elements and can combine simultaneously at its stiff end with a silicon oxide particles at the carbon nano-fiber that its free end has a catalyst elements.
Beneficial effect of the present invention: because the silicon oxide particles surface combination of carbon nano-fiber and SiOx (0.05＜x＜1.95) representative, adopt the electronic conductivity height of the negative pole of this material preparation, thereby can obtain having the battery of excellent initial charge/flash-over characteristic.Carbon nano-fiber with and silicon oxide particles be not simple mechanical mixture, but chemical bond.Therefore, though when charge/discharge between the stage of reaction silicon oxide particles expand repeatedly and when shrinking, contacting also between carbon nano-fiber and the silicon oxide particles kept always.And carbon nano-fiber is as resilient coating, absorbs because of silicon oxide particles to expand and shrink caused stress.Therefore, use carbon-silicon composite material of the present invention to prepare to have the battery of excellent charge/discharge cycle characteristics.
Description of drawings
Fig. 1 is the material structure schematic diagram of the binding site of catalyst elements between carbon nano-fiber and silicon oxide particles, wherein 10 composite material granulars that refer to silicon oxide particles, catalyst elements, carbon nano-fiber (catalyst elements is between carbon nano-fiber and silicon oxide particles); 11 represent silicon oxide particles, and 12 represent catalyst elements, and 13 represent carbon nano-fiber;
Fig. 2 is the free-ended material structure schematic diagram that catalyst elements is positioned at carbon nano-fiber, 20 composite material granulars (catalyst elements is positioned at the free end of carbon nano-fiber) that refer to silicon oxide particles, catalyst elements, carbon nano-fiber wherein, 21 represent silicon oxide particles, 22 represent catalyst elements, and 23 represent carbon nano-fiber;
Fig. 3 is 5000 times of amplification SEM photos of the carbon-silicon composite material of embodiment 1;
Fig. 4 is 40000 times of amplification SEM photos of the carbon-silicon composite material of embodiment 1;
Fig. 5 is 80000 times of amplification SEM photos of the carbon-silicon composite material of embodiment 1;
Fig. 6 is the TEM photo of the carbon-silicon composite material of embodiment 1;
Fig. 7 is the cycle performance curve of the carbon-silicon composite material of embodiment 1.
Embodiment
The invention provides a kind of be used for lithium secondary battery and the silicium cathode active material compound amorphous silicon of carbon nano-fiber.This carbon-silicon composite material comprises amorphous silicon oxidation composition granule SiO
XAnd carbon nano-fiber of silicon oxide particles surface combination (CNF) and metallic element, 0.05＜x＜1.95 wherein, metallic element is the catalyst elements that is used to promote carbon nanofibers grow, is selected from least a (preferably Fe, Co, Ni, Cu, the Mg) of Fe, Co, Ni, Cu, Mg, Mn, Ti, Sn, Si, Zr, Zn, Ge, Pb and In.Carbon nano-fiber is as resilient coating, absorbs because of silicon oxide particles to expand and shrink caused stress.With SiO
XBe the 100wt% meter, the 0.01wt%～10wt% of metallic element, preferred 1wt%～3wt%.The carbon nanofibers grow amount is 5～200wt%, and the preferred growth amount is 20～100wt%
Carbon nano-fiber is grown and is centered around with the form of rattan and is selected from amorphous Si O
xOr graphite and amorphous Si O
xCompound basis material the surface around.
From the viewpoint of the electronic conductivity that improves composite anode active material, carbon nano-fiber preferably includes the fine fibre of diameter 1nm～40nm.More preferably comprise the fine fibre of diameter 1nm～40nm and the big fiber (largefiber) of diameter 50～200nm simultaneously.The decisive factor of carbon nano-fiber diameter mainly is the particle diameter decision by catalyst, and the particle diameter of catalyst is directly determined by the preparation method.The present invention has selected appropriate catalyst presoma salt for use, makes the interaction of the anion of presoma salt and solvent prepare can to generate big fiber to generate fibrillose effect again simultaneously.
The length 10nm of carbon nano-fiber～200 μ m, bending or helical form.Fibre length and fibre diameter can be observed or tem observation waits and measures according to SEM.
Can also comprise electric conducting materials such as conducting polymer in the described carbon-silicon composite material, as long as electric conducting material does not damage the function of carbon-silicon composite material.
The preparation method of above-mentioned carbon-silicon composite material specifically comprises the steps:
1) preparation of catalyst solution
At least a acetate of Fe, Co, Ni, Cu, Mg, Mn, Ti, Sn, Si, Zr, Zn, Ge, Pb and In is mixed with the catalyst solution of 0.0001M～0.1M, and solvent is selected from one or more in distilled water, ethanol, methyl alcohol, isopropyl alcohol, ethylene glycol or the glycerol.
The selection of acetate is based on a large amount of test of inventor, and other salt can not be contained big fiber and fibrillose composite material simultaneously.The concentration 0.0001M of catalyst solution～0.1M can implement, the carbon nano-fiber content height that generates during the composite material of the big preparation of concentration, and man-hour is short, and concentration hour preparation is with prolonging the man-hour that the fiber of content needs.
Choice of Solvent is based on the solvent that the solubility of considering compound and solvent and electro-chemical activity compatibility are mutually selected solution.
The catalyst that is used to prepare carbon nano-fiber is known.For example, adopted transition metal, as Fe, Co and Ni (Catal.Rev.-Sci.Eng., 42 (4) pp481～510 (2000)).In the present invention, used at least a metallic catalyst that is selected among Fe, Co, Ni, Cu, the Mg, the presoma salt of catalyst is the acetate form preferably.
Particularly preferred example is that Ni, presoma salt are that acetate, solvent are preferably methyl alcohol as catalyst elements wherein.This is because the following fact, the acetate deliquescence that should not absorb water, and the difficulty that can avoid the mensuration of surperficial dispersity and dispersion amount to bring, and presoma salt adopts acetate, maceration extract adopts the dispersion effect of nickel under the condition of methyl alcohol better.
2) catalyst cupport
Silica-base material joined in the catalyst solution that step 1) makes described catalyst and SiO
xMass ratio be 1: 1～1000, stirred 30 minutes～20 hours, left standstill 5～72 hours, stir dryly, 100 ℃ of vacuumize 12 hours obtains the silica-base material of catalyst cupport.
Described silica-base material refers to mainly with silicon or Si oxide SiO
xBe the electro-chemical activity phase material, perhaps silicon and Si oxide and other have or do not have the compound material of other materials of electro-chemical activity, and complex method can be a mechanical mixture, and mechanical ball milling, chemistry coat etc.Such as graphite and amorphous Si O
xCompound, wherein graphite and amorphous Si O
xWeight ratio can be the graphite of 1～50wt% and the amorphous Si O of 50～99wt%
x
Silica-base material SiO of the present invention
XRequiring is not the pure silicon or the SiO of crystal formation
2, should be Si oxide unbodied, incomplete oxidation, the scope of 0.05＜x＜1.95 all can realize the present invention.Can obtain or adopt existing chemistry, physical method Si or SiO by purchase to crystal formation
2Be treated to amorphous silicon oxidation thing.Such as the amorphous Si O that can under inert atmosphere, utilize the preparation of oscillatory type ball milling
x(0.05＜x＜1.95), geometric shape are irregular shape or sphere, and preferred spherical, wherein the average grain diameter of silicon substrate material is 100nm～100 μ m.
Catalyst elements may reside in the surface of silicon oxide particles at least; Yet it also may reside in the inside of silicon oxide particles.
3) chemical vapour deposition (CVD)
With step 2) silica-base material of the catalyst cupport that obtains is placed in the heatproof container, the tube furnace of packing into then, charge into the gaseous mixture of helium or helium and hydrogen, or carry out preliminary treatment with nitrogen, temperature programming to 500 then～1200 ℃ temperature, gas is converted to carbon-source gas or is converted to the gaseous mixture of helium, nitrogen or hydrogen and carbon-source gas, constant temperature 20 minutes naturally cools to room temperature promptly after carrying out chemical vapour deposition (CVD) to 48 hours.
In the present invention, the metallic catalyst of the carbon nano-fiber that is used to grow is evenly dispersed in the surface of basis material by infusion process.By chemical vapour deposition technique, make the carbon nano-fiber with following structure: the carbon nano-fiber that is obtained comprises that diameter is the fine fibre of 10～30nm and the big fiber of diameter 50～120nm ((large fiber).Because the carbon nano-fiber of growth centers on negative active core-shell material with the form of rattan, can go out the volumetric expansion of alleviating negative active core-shell material in the process in the embedding/embedding of lithium ion.
Can adopt carbon source, be used for gas-phase reaction, optimization methane or ethanol under the high temperature as carbon monoxide, methane, acetylene and/or ethene.The increment of carbon nano-fiber can be 5～200wt% with respect to the basis material amount.The preferred growth amount of carbon nano-fiber can be 20～100wt% with respect to mer weight.When the amount of carbon nano-fiber is too small, can not obtains to improve electrode conductivuty sometimes fully and improve the charge of battery and the effect of cycle characteristics.In addition, when the amount of carbon nano-fiber was excessive, the active material density and the capacity of electrode diminished, although no problem aspect the charge of electrode conductivuty and battery and cycle characteristics.
Carbon-silicon composite material of the present invention is by the effect in catalyst elements, and the growth carbon nano-fiber obtains on the surface of silicon oxide particles.At least one end of carbon nano-fiber and the surface combination of silicon oxide particles.Yet, the two ends of carbon nano-fiber can with the surface combination of silicon oxide particles.
When catalyst elements was not separated with silicon oxide particles, catalyst elements loaded on the silicon oxide particles, and carbon nanofibers grow is on catalyst elements.In other words, the stiff end of carbon nano-fiber on catalyst elements, the binding site of catalyst elements between carbon nano-fiber and silicon oxide particles.Schematic diagram is seen Fig. 1.
When catalyst elements is separated with silicon oxide particles, an end of carbon nano-fiber and the surface combination of silicon oxide particles, the other end combines with catalyst elements.The carbon-silicon composite material that promptly obtains, catalyst elements are positioned at the free end of carbon nano-fiber.Schematic diagram is seen Fig. 2.
In prepared carbon-silicon composite material, can exist catalyst elements simultaneously at the carbon nano-fiber stiff end with in the free-ended two kinds of situations of carbon nano-fiber.In addition, have the carbon nano-fiber of catalyst elements and can combine simultaneously at its stiff end with a silicon oxide particles at the carbon nano-fiber that its free end has a catalyst elements.
The catalyst that is used to prepare carbon nano-fiber is known.For example, adopted transition metal, as Fe, Co and Ni (Catal.Rev.-Sci.Eng., 42 (4) pp481～510 (2000)).In the present invention, used at least a metallic catalyst that is selected among Fe, Co, Ni, Cu, the Mg, the presoma salt of catalyst is the acetate form preferably.
For metal catalyst particles being supported on the surface of silicon substrate material, can adopt gel-sol method, the precipitation method, hydrothermal method, spraying heating, spray drying process and/or ball-milling method.And the basis material that contains metallic particles can be produced by introducing further oxidation or reduction process.Yet preferred infusion process does not also require further oxidation or reduction process.
The solubility of considering compound and solvent and electro-chemical activity compatibility are mutually selected the solvent of solution.The mixture that preferred solvent is selected from for example water, organic solvent and is made of water and organic solvent.As organic solvent, can use for example ethanol, isopropyl alcohol, toluene, benzene, hexane and oxolane etc.For the silicon oxide particles of every 100wt%, the preferred 0.01wt%～10wt% of the amount of the catalyst granules of load, more preferably 1wt%～3wt% on silicon oxide particles.When the amount of catalyst granules is too small, need the carbon nano-fiber of growing for a long time sometimes, production efficiency is reduced.On the other hand, when the amount of catalyst granules is excessive, the catalyst elements cohesion, the result grows carbon nano-fiber inhomogeneous and that fibre diameter is big.This makes the conductivity of electrode and active material density descend.In some cases, the ratio of electro-chemical activity phase becomes relatively too little, and this makes and is difficult to use composite anode active material to make the high-capacity electrode material.
Can understand the present invention more accurately by following preparation embodiment and comparative example.Yet scope of the present invention also is not limited by the following examples.
The preparation of embodiment 1 carbon-silicon composite material of the present invention
At 100g dissolve with methanol 5g nickel acetate tetrahydrate.The solution that obtains like this be ground into particle diameter 3 μ m or littler silica (SiO) 35g and mix, the mixture of silicon oxide particle and solution was stirred 1 hour, remove with evaporimeter then and anhydrate, make silicon oxide particle load nickel acetate in its surface.
The silicon oxide particle of load nickel acetate is placed the quartz reaction container, and in the presence of helium, temperature is risen to 550 ℃.Then, the mist replacement of helium of using the methane gas by the hydrogen of 50 volume % and 50 volume % to constitute, the inside that keeps reaction vessel is 550 ℃ of growths 90 minutes, to comprise the fine fibre of the about 20nm of fibre diameter and the big fiber of 100nm in the silicon oxide particle superficial growth.Then, use the helium replacement mist, and with the inside cool to room temperature of reaction vessel.The amount of the carbon nano-fiber that grows out is the silicon oxide particle of 30 weight portions/100 weight portions.Discovery loads on the nickel particle that nickel nitrate on the silicon oxide particle is reduced into the about 100nm of particle diameter.Observe fibre diameter and the fibre length and the nickel particle grain size of carbon nano-fiber respectively by SEM.The weight of the carbon nano-fiber that grows out of the weight change measurement of rear oxidation silicon grain with it before the carbon nanofibers grow.SEM observes confirmation, except the fiber of the about 100nm of diameter, also confirms to exist diameter 20～30nm or littler fine fibre.
5000 times of enlarged photographs of the carbon silicon compound particle that obtains as shown in Figure 3.Fig. 4 represents 40000 times of enlarged photographs of the compound particle that obtains.80000 times of enlarged photographs of part as shown in Figure 5 among Fig. 3.Can confirm by Fig. 5: on the SiOx particle, grown carbon nano-fiber.From Fig. 5 and in conjunction with observing the TEM of compound particle such as Fig. 6:, the existence of thick carbon nano-fiber and fine carbon nano-fiber is arranged on the surface of active material particle.Cycle performance curve piece Fig. 7.
The preparation of embodiment 2 carbon-silicon composite materials of the present invention
Replace 5g four hydration nickel acetates to be dissolved in the 100g methanol solution 3.5g four hydration nickel acetates, in addition, all the other are operated similarly to Example 1, are set the electrode material B into rechargeable nonaqueous electrolytic battery.Roughly the nickel particles with embodiment 1 is identical for the particle diameter of the nickel particles of appendix on silicon oxide particle.Fibre diameter, the fibre length of carbon nano-fiber of growth is all roughly identical with embodiment 1, is 20% with respect to the part by weight of active material particle.Here, in SEM observed, except that the fiber of the about 80nm of fibre diameter, also confirming to have fibre diameter was the existence of the following microfibre of 30nm.
The preparation of embodiment 3 carbon-silicon composite materials of the present invention
Replace 5g four hydration nickel acetates to be dissolved in the 100g methanol solution 1.7g four hydration nickel acetates, in addition, all the other are operated similarly to Example 1, are set the electrode material C into rechargeable nonaqueous electrolytic battery.Roughly the nickel particles with embodiment 1 is identical for the particle diameter of the nickel particles of appendix on silicon oxide particle.Fibre diameter, the fibre length of carbon nano-fiber of growth is all roughly identical with embodiment 1, is 15% with respect to the part by weight of active material particle.Here, in SEM observed, except that the fiber of the about 80nm of fibre diameter, also confirming to have fibre diameter was the existence of the following microfibre of 30nm.
Electrical property is estimated
In the electrode material that embodiment 1-3 makes, mix the binding agent and the deionized water that constitute by sodium carboxymethylcellulose, with allotment mixture slip.This slip is coated on the Cu paper tinsel that thickness is 15um, and the calendering of dry back just obtains battery lead plate.In 100 ℃ drier, make this battery lead plate intensive drying, just obtain work electrode.With lithium metal foil as work electrode to electrode, just produce the button-shaped lithium ion battery of 2016 types that controlled by work electrode.Electrolyte is to contain 1mol/L LiPF
6DEC+EC volume ratio (DEC: EC=1: solution 1), barrier film polypropylene Celgard2400.The simulated battery assembling process is finished in being filled with the glove box of high-purity hydrogen.
As a comparison, with the silicon oxide particle that is crushed to below the 3 μ m, size mixing with 65: 20: 15 mass ratio as the acetylene black (AB) of conductive agent with as the sodium carboxymethylcellulose (CMC) of binding agent, be set electrode material D into rechargeable nonaqueous electrolytic battery.
Electrochemical property test adopts Guangzhou to hold up a day battery performance testing device, and the charge and discharge current density is 180mA/g, and the charging/discharging voltage window is 0.02-1.5V, and the test environment temperature is 25 ± 2 ℃.
For the button-shaped lithium ion battery that obtains, with charge/discharge tachometric survey initial discharge capacity and the initial charge/discharge capacity of 0.05C.The initial discharge capacity that records is shown in table 1.In addition, the ratio meter of initial discharge capacity and initial charge capacity be can be regarded as percentage, thereby obtains initial charge/discharging efficiency.
For the button-shaped lithium ion battery that obtains, measure the initial discharge capacity under the charge/discharge speed of 0.05C and carrying out the discharge capacity after the charge/discharge operational cycle repeatedly 20 times.The discharge capacity after 20 circulations and the ratio meter of initial discharge capacity be can be regarded as percentage, thereby obtain capability retention.Its result of comparative example and embodiment is as shown in table 1.
Table 1
| Negative pole | Nickel content | CNTs content | Initial discharge capacity | Initial charge/discharge efficient | The capacity sustainment rate | |
| Embodiment 1 | ??A | ??3％ | ??30％ | ??793mAh/g | ??70％ | ??74％ |
| Embodiment 2 | ??B | ??2％ | ??20％ | ??1153mAh/g | ??66％ | ??65％ |
| Embodiment 3 | ??C | ??1％ | ??15％ | ??1299mAh/g | ??63％ | ??45％ |
| Comparative example | ??D | ??0 | ??0 | ??1713mAh/g | ??61％ | ??31％ |
Show from table 1 result, in the battery of the electrode material that has utilized 1-3 to make, whichsoever embodiment is aspect the initial stage of units activity substance weight discharge capacity, efficiency for charge-discharge and capability retention, good than the comparative example 1 that does not contain carbon nano-fiber.Under the expansion of the active biomass that comparative example 1 produces discharging and recharging and the effect of contraction, ditch electrical conductivity network is cut off between active material particle surface and the carbon nano-fiber, thereby cycle characteristics generation degeneration, the value of initial charge/discharging efficiency and capability retention is minimum.
For the battery that uses the composite anode active material that obtains among the embodiment 2,3, compare with embodiment 1, improve a lot in the initial stage of units activity substance weight discharge capacity, initial charge/discharging efficiency and cycle characteristics descend, may be owing to the amount of the carbon nano-fiber that forms on the surface of active material with respect to active material reduces, improve discharge capacity first, cause intergranular conductivity to weaken, carrying out repeatedly of the expansion of the active material that produces along with discharging and recharging and contraction slowly loses interparticle conductivity.
Composite anode active material of the present invention has the negative active core-shell material of the rechargeable nonaqueous electrolytic battery of high power capacity as expection.Adopt the lithium ion battery non-environmental-pollution of this composite negative pole material preparation, can be used for driving traffic soil tools such as mobile communication apparatus, miniaturized electronics, electric motor car and hybrid electric vehicle etc.Composite anode active material of the present invention has extra high conductivity cyclical stability, and preferably being suitable for use as needs excellent initial charge/flash-over characteristic and cycle characteristics and because of the gas generated negative active core-shell material that reduces in the rechargeable nonaqueous electrolytic battery highly reliably.
Claims (10)
1. carbon-silicon composite material is characterized in that: be made up of silica-base material and epontic carbon nano-fiber thereof and metallic element; Described silica-base material contains amorphous silicon oxidation composition granule SiO
x, 0.05＜x＜1.95, described metallic element is at least a among Fe, Co, Ni, Cu, Mg, Mn, Ti, Sn, Si, Zr, Zn, Ge, Pb and the In; At least a among preferred Fe, Co, Ni, Cu, the Mg.
2. carbon-silicon composite material according to claim 1 is characterized in that: described carbon-silicon composite material is by under the catalyst action of metallic element, and the growth carbon nano-fiber obtains on the surface of silica-base material particle.
3. carbon-silicon composite material according to claim 2 is characterized in that: carbon nano-fiber is with the growth of the form of rattan and be centered around the surface of silica-base material particle, at least one end of carbon nano-fiber and the surface combination of silicon oxide particles.
4. carbon-silicon composite material according to claim 1 is characterized in that: with SiO
xBe the 100wt% meter, the amount of metallic element is 0.01wt%～10wt%, preferred 1wt%～3wt%.
5. carbon-silicon composite material according to claim 4 is characterized in that: the carbon nano-fiber diameter is the fine fibre of 1nm～40nm, length 10nm～200 μ m.
6. carbon-silicon composite material according to claim 5 is characterized in that: carbon nano-fiber is for comprising the fine fibre of diameter 1nm～40nm and the big fiber of diameter 50～200nm simultaneously.
7. carbon-silicon composite material according to claim 1 is characterized in that: described silica-base material is SiO
xWith the compound of graphite, wherein graphite and amorphous Si O
xWeight ratio be the graphite of 1～50wt% and the amorphous Si O of 50～99wt%
x
8. carbon-silicon composite material according to claim 1 is characterized in that: also comprise conducting polymer in the described carbon-silicon composite material.
9. prepare the method for the described carbon-silicon composite material of claim 1, comprise the steps:
1) preparation of catalyst solution
With in distilled water, ethanol, methyl alcohol, isopropyl alcohol, ethylene glycol or the glycerol one or more is solvent, and at least a acetate of Fe, Co, Ni, Cu, Mg, Mn, Ti, Sn, Si, Zr, Zn, Ge, Pb and In is dissolved as catalyst solution;
2) catalyst cupport
Silica-base material is joined in the catalyst solution of step 1 gained the silica-base material that stir, leave standstill, drying obtains catalyst cupport;
3) chemical vapour deposition (CVD)
With step 2) silica-base material of the catalyst cupport that obtains purges in non-oxygen atmosphere, be warming up to 500～1200 ℃ of temperature then, be converted to carbon-source gas and carry out chemical vapour deposition (CVD), cooling promptly, described carbon-source gas contain carbon monoxide, methane, acetylene and or ethene at least a.
10. the preparation method of carbon-silicon composite material according to claim 6, it is characterized in that: described catalyst elements is Ni, solvent is a methyl alcohol.
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