CN1903793A - Carbon silicon composite material, its preparation method and use - Google Patents

Carbon silicon composite material, its preparation method and use Download PDF

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CN1903793A
CN1903793A CNA2005100871287A CN200510087128A CN1903793A CN 1903793 A CN1903793 A CN 1903793A CN A2005100871287 A CNA2005100871287 A CN A2005100871287A CN 200510087128 A CN200510087128 A CN 200510087128A CN 1903793 A CN1903793 A CN 1903793A
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silicon
gas
hours
carbon nano
solution
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舒杰
李泓
黄学杰
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Institute of Physics of CAS
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Institute of Physics of CAS
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Abstract

The present invention relates to a carbon-silicon composite material. It includes silicon matrix and carbon nano tube or nano carbon fibre grown on the matrix. The average grain size of the described silicon matrix is 100 nm-100 micrometer, the diameter of the described carbon nano tube or nano carbon fibre is 1-200 nm and its length is 1 nm-100 micrometer. The described carbon nano tube is single-wall, double-wall or multiwall. Said invention also provides its preparation method and concrete steps.

Description

A kind of silicon﹠amp and its production and use
Technical field
The present invention relates to a kind of silicon﹠amp, and its production and use.
Background technology
The contain amount of these two kinds of elements of silicon and carbon in universe is very abundant, occupy the 3rd and the 7th respectively, thereby these two kinds of material commercializations had considerable prospect, but in actual application, as as lithium ion battery negative material the time, though silicon has very high specific discharge capacity, but the specific conductivity of silicon is very low, and circulation time can produce huge volume change, 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 reversibility that carbon material 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 carbon material at present as lithium ion battery, but along with the problem of this material lower volume 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.
Summary of the invention
The objective of the invention is to overcome the defective that all can not satisfy the demand when prior art is used silicon materials or carbon material as the negative material of lithium ion battery separately, thereby providing a kind of has than bigger serface and big voidage, can give full play to the function of silicon and carbon, at the silicon﹠amp of silicon grain surface growth carbon nanotube or carbon nano fiber, and its production and use.
The objective of the invention is to realize by the following technical solutions:
The invention provides a kind of silicon﹠amp, it comprises silicon substrate, reaches carbon nanotubes grown or carbon nano fiber thereon; The median size of described silicon substrate is 100nm～100 μ m; The diameter of described carbon nanotube or carbon nano fiber is 1～200nm, and length is 10nm～100 μ m; Described carbon nanotube is a single wall, double-walled or many walls.
The pattern of described matrix silicon grain both can be irregular, also can be for rule, preferred geometric shape be a sphere.
Described carbon nanotube or carbon nano fiber both can have straight geometry appearance, also can have the geometry appearance of bending or spiral; Both vertically matrix silicon grain surface orientation growths also can the non-directional growth.
The invention provides a kind of preparation method of described silicon﹠amp, specifically comprise the steps:
1) preparation of catalyst solution
Use is selected from the catalyst solution of one or more solvent preparations 0.0001～0.1M in distilled water, ethanol, methyl alcohol, Virahol, ethylene glycol or the glycerol;
Described catalyzer is for being selected from Fe (NO 3) 39H 2O, FeSO 47H 2O, FeCl 36H 2O, Co (NO 3) 26H 2O, Co (CH 3COO) 24H 2O, Ni (NO 3) 26H 2O, (NH 4) 6Mo 7O 244H 2Among the O one or more;
2) catalyst cupport
To join as the silicon materials of body material in the catalyst solution that step 1) makes, the mass ratio of described catalyzer and silicon is 1: 1～1000, stirs 30 minutes～20 hours, leaves standstill 5～72 hours, separates, drying, obtains the silicon materials of catalyst cupport;
The median size of described silicon substrate is 100nm～100 μ m;
3) chemical vapour deposition
With step 2) material that obtains is placed in the thermally resistant container (as graphite boat, aluminium oxide boat), the tube furnace that the resistance to air loss of packing into then is good charges into the gas mixture of argon gas or argon gas and hydrogen, or carry out pre-treatment, temperature programming to 500 then～1200 ℃ temperature with ammonia; After being raised to target temperature, gas is converted to carbon-source gas (acetylene, ethene, methane or carbon monoxide) or is converted to the gas mixture of argon gas, nitrogen or hydrogen and above-mentioned carbon-source gas, constant temperature 20 minutes naturally cools to room temperature after carrying out chemical vapour deposition to 48 hours.
The invention provides the preparation method of another kind of described silicon﹠amp, specifically comprise the steps:
1) preparation of chemical plating solution
Use is selected from the Fe (NO of one or more solvent preparations 0.0001～0.1M in distilled water, ethanol, methyl alcohol, Virahol, ethylene glycol or the glycerol 3) 39H 2O, Co (NO 3) 26H 2O or Ni (NO 3) 26H 2O solution; Preparation contains the distilled water solution of trisodium citrate and sodium acetate; The concentration of described trisodium citrate and sodium acetate is 0.0001～1M; Then the former is added drop-wise among the latter, stirs, obtain mixed solution A;
Use distilled water that sodium hydroxide and sodium borohydride are mixed with reductant solution B; Concentration sodium hydroxide 1.5～15M wherein, the concentration of sodium borohydride is 0.0001～1M;
2) load of catalyzer
To join as the silicon materials of body material in the mixed solution A that step 1) makes, stir, be warming up to 25～95 ℃, the pH=4 of regulator solution～12 drip the reductant solution B that step 1) prepares then, wait to drip, continue to stir 10 minutes～2 hours, separate, drying obtains the silicon materials of catalyst cupport; The ratio of the silicon materials that add, solution A, solution B is 1g: 40～100ml: 10～50ml;
The median size of described silicon substrate is 100nm～100 μ m;
3) chemical vapour deposition
With step 2) material that obtains is placed on (as graphite boat, aluminium oxide boat) in the thermally resistant container, and the tube furnace that the resistance to air loss of packing into then is good charges into the gas mixture of argon gas or argon gas and hydrogen, temperature programming to 500 then～1200 ℃ temperature; After being raised to target temperature, gas is converted to carbon-source gas (acetylene, ethene, methane or carbon monoxide) or is converted to the gas mixture of argon gas, nitrogen or hydrogen and above-mentioned carbon-source gas, constant temperature 20 minutes naturally cools to room temperature after carrying out chemical vapour deposition to 48 hours.
The invention provides the preparation method of another described silicon﹠amp, specifically comprise the steps:
1) mixing of catalyzer
One or more that are selected from Fe, Co, Ni, Mo metal-powder are mixed (can with hand mill, ball milling or vibration mill) with silicon grain as body material, mixed 5 minutes～50 hours, the mass ratio of metal and body material is 1: 1～1000;
The median size of described silicon substrate is 100nm～100 μ m;
2) chemical vapour deposition
The material that step 1) is obtained is placed on (as graphite boat, aluminium oxide boat) in the thermally resistant container, and the tube furnace that the resistance to air loss of packing into then is good charges into the gas mixture of argon gas or argon gas and hydrogen, temperature programming to 700 then～1200 ℃ temperature; After being raised to target temperature, gas is converted to carbon-source gas (acetylene, ethene, methane or carbon monoxide) or is converted to the gas mixture of argon gas, nitrogen or hydrogen and above-mentioned carbon-source gas, constant temperature 20 minutes naturally cools to room temperature after carrying out chemical vapour deposition to 48 hours.
The invention provides also a kind of preparation method of described silicon﹠amp, specifically comprise the steps:
1) contains the preparation of catalyst elements alloy
One or more that are selected from Fe, Co, Ni, Mo metal-powder are mixed with silicon grain as body material, carried out ball milling then 30 minutes～500 hours, rotating speed is 100～3000rpm, and the mass ratio of metal and body material is 1: 0.001～1000;
The median size of described silicon substrate is 100nm～100 μ m;
2) chemical vapour deposition
The material that step 1) is obtained is placed on (as graphite boat, aluminium oxide boat) in the thermally resistant container, and the tube furnace that the resistance to air loss of packing into then is good charges into the gas mixture of argon gas or argon gas and hydrogen, temperature programming to 700 then～1200 ℃ temperature; After being raised to target temperature, gas is converted to carbon-source gas (acetylene, ethene, methane or carbon monoxide) or is converted to the gas mixture of argon gas, nitrogen or hydrogen and above-mentioned carbon-source gas, constant temperature 20 minutes naturally cools to room temperature after carrying out chemical vapour deposition to 48 hours.
Use aforesaid method can obtain silicon﹠amp of the present invention, it is for the micro-nano with lint ball outward appearance of 1-dimention nano carbon fiber or carbon nanotube or the matrix material of receiving in the silicon grain surface growth with micron or nano-scale.This silicon/carbon micro-nano and Na Na matrix material, carbon nano-tube on silicon grain, form the composite structure of cage mounted, utilized the superior electroconductibility of carbon nanotube on the one hand, make it can remedy the problem of silicon grain poorly conductive, because carbon nanotube is grown directly upon and makes on the silicon grain that both contacts are better, be not easy because the separation of the effect of external force on the other hand, this and simple two-phase are mixed with basic difference.Thereby with it as material in some field, especially the application facet of lithium ion battery negative material can obtain very ideal effect.And the matrix material that adopts these two kinds of material preparations can be accomplished cheap, again can sustainable development.
In addition, this matrix material combines the matrix silicon materials and has stable structure, epontic CNT (carbon nano-tube) or carbon nano fiber have the advantage than bigger serface and big voidage, have avoided simple carbon nanotube to reunite easily when using simultaneously again, are difficult for the dispersive shortcoming.Thereby as support of the catalyst, the aspects such as electrode materials in chemical power source and the ultracapacitor have shown good dynamic performance, thermostability, chemical stability and structural stability.
The present invention be advantageous in that: at the 1-dimention nano carbon fiber and the carbon nanotube (single wall of core silicon face growth, double-walled or many walls) diameter, length, length-to-diameter ratio, density can be by the particle diameter of catalyzer catalyzer when the matrix carbon area load, content, the kind of the carrier gas of being adopted of distribution and chemical vapour deposition, flow, the ratio of different carrier gas compositions, the temperature and time of reaction is regulated and control.Technology of the present invention is simple, and good reproducibility, required plant and instrument all are chemistry and material industry equipment commonly used.The prepared product purity height that goes out, geometry is controlled, and steady quality is suitable for large-scale industrialization production.
Silicon﹠amp provided by the invention in energy storage and switching device, can be used as the negative material of lithium ion battery, also as the carrier of various fuel-cell catalysts.
Description of drawings
Fig. 1 is the field emission scan electron microscopic pattern of the silicon/carbon composite of embodiment 1 preparation;
Fig. 2 is that the silicon/carbon composite of embodiment 1 preparation amplifies 32500 times field emission scan electron microscopic pattern.
Embodiment
Embodiment 1: take by weighing 0.001g Fe powder and 10g silicon grain (its median size is 5 μ m), ground 5 hours, material with gained is placed in the graphite boat then, reinstall in the tube furnace, charge into argon gas, flow is 20sccm, after the temperature programming to 800 ℃, gas is converted to the gas mixture of methane and hydrogen, its ratio is 1: 20 (v/v), total flux is 300sccm, and constant temperature was converted to argon gas with gas after carrying out chemical vapour deposition in 20 minutes, naturally cool to room temperature, products therefrom is silicon/multi-wall carbon nano-tube composite material, and wherein the mean diameter of multi-walled carbon nano-tubes is 8nm, and length is 60 μ m.Pattern in its emission scan electron microscopic on the scene as shown in Figure 1, the pattern in the emission scan electron microscopic of the field of high-amplification-factor as shown in Figure 2, as seen this silicon﹠amp is the matrix material with lint ball outward appearance, and good dispersity.
The negative material of described material as lithium ion battery used.The preparation method of negative pole is described below: silicon/multi-wall carbon nano-tube composite material, carbon black mixes the formation slurry at normal temperatures and pressures with the cyclohexane solution of polyvinylidene difluoride (PVDF), evenly be coated on the Copper Foil substrate as collector, the about 70 μ m. of the film thickness of gained with the film that obtains at 150 ℃ down after the oven dry, at 20Kg/cm 2Under compress, continue 150 ℃ of oven dry 12 hours down.Oven dry back silicon/multi-wall carbon nano-tube composite material, the weight percent of carbon black and polyvinylidene difluoride (PVDF) is 80: 5: 15, then film being cut to area is 1cm 2Thin rounded flakes as negative pole.
With commodity positive electrode material LiCoO 2Mix formation slurry (active material: acetylene black: PVDF=75: 15: 10) at normal temperatures and pressures with the cyclohexane solution of acetylene black and 10% polyvinylidene difluoride (PVDF) (PVDF), evenly be coated on the aluminum substrates, about 50～60 μ m of the film thickness of gained are as the positive pole of battery.Electrolytic solution is 1mol LiPF 6Be dissolved in the mixed solvent of 1L EC and DMC (volume ratio 1: 1).With all battery materials, comprise positive pole, negative pole, battery case, barrier film, dry back is added electrolytic solution and is assembled into Experimental cell in the argon filling glove box or in the drying room.
Experimental cell is tested by being subjected to computer-controlled auto charge and discharge instrument to carry out charge and discharge cycles.The charging stopping potential is 4.2V, and discharge cut-off voltage is 2.0V.Studies have shown that described silicon/multi-wall carbon nano-tube composite material is as negative active core-shell material, its reversible capacity at 0.1C is 950mAh/g, and the reversible capacity of 1C is 560mAh/g, has shown dynamic behavior preferably.
Embodiment 2: take by weighing 0.001g Fe powder and 10g silicon grain (its median size is 10 μ m), ground 5 hours, material with gained is placed in the aluminium sesquioxide boat then, reinstall in the tube furnace, charge into argon gas, chemical vapor deposition processes is with embodiment 1, the time of chemical vapour deposition is 2 hours, silicon/multi-wall carbon nano-tube composite material, wherein the mean diameter of multi-walled carbon nano-tubes is 15nm, length is 160 μ m.
As carrying out the preparation of anodal and negative pole as described in the embodiment 1, and assembled battery tests, and Experimental cell is tested by being subjected to computer-controlled auto charge and discharge instrument to carry out charge and discharge cycles.The charging stopping potential is 4.2V, and discharge cut-off voltage is 2.0V.Studies have shown that described silicon/multi-wall carbon nano-tube composite material is as negative active core-shell material, its reversible capacity at 0.1C is 930mAh/g, and the reversible capacity of 1C is 560mAh/g, has shown dynamic behavior preferably.
Embodiment 3: take by weighing 0.001g Fe powder and 10g silicon grain (its median size is 100nm), ground 5 hours, material with gained is placed in the aluminium sesquioxide boat then, reinstall in the tube furnace, charge into the gas mixture of argon gas and hydrogen, its ratio is 85: 15 (v/v), after the temperature programming to 700 ℃, gas is converted to ethene, flow is 50sccm, after constant temperature carried out chemical vapour deposition in 2 hours, gas is converted to nitrogen, naturally cools to room temperature, products therefrom is silicon/multi-wall carbon nano-tube composite material, wherein the mean diameter of multi-walled carbon nano-tubes is 17nm, and length is 70 μ m.
As carrying out the preparation of anodal and negative pole as described in the embodiment 1, and assembled battery tests, and Experimental cell is tested by being subjected to computer-controlled auto charge and discharge instrument to carry out charge and discharge cycles.The charging stopping potential is 4.2V, and discharge cut-off voltage is 2.0V.Studies have shown that described silicon/multi-wall carbon nano-tube composite material is as negative active core-shell material, its reversible capacity at 0.1C is 880mAh/g, and the reversible capacity of 1C is 570mAh/g, has shown dynamic behavior preferably.
Embodiment 4: take by weighing 0.001g Ni powder and 5.9g silicon grain (its median size is 5 μ m), ground 5 hours, material with gained is placed in the graphite boat then, reinstall in the tube furnace, charge into argon gas, chemical vapor deposition processes is with embodiment 1, the time of chemical vapour deposition is 50 minutes, products therefrom is silicon/multi-wall carbon nano-tube composite material, and wherein the mean diameter of multi-walled carbon nano-tubes is 5nm, and length is 80 μ m.
As carrying out the preparation of anodal and negative pole as described in the embodiment 1, and assembled battery tests, and Experimental cell is tested by being subjected to computer-controlled auto charge and discharge instrument to carry out charge and discharge cycles.The charging stopping potential is 4.2V, and discharge cut-off voltage is 2.0V.Studies have shown that described silicon/multi-wall carbon nano-tube composite material is as negative active core-shell material, its reversible capacity at 0.1C is 790mAh/g, and the reversible capacity of 1C is 680mAh/g, has shown dynamic behavior preferably.
Embodiment 5: take by weighing 0.001gCo powder and 10g silicon grain (its median size is 100 μ m), ground 5 hours, material with gained is placed in the graphite boat then, reinstall in the tube furnace, charge into argon gas, chemical vapor deposition processes is with embodiment 1, the time of chemical vapour deposition is 50 minutes, products therefrom is silicon/Single Walled Carbon Nanotube matrix material, and wherein the mean diameter of Single Walled Carbon Nanotube is 1nm, and length is 70 μ m.
As carrying out the preparation of anodal and negative pole as described in the embodiment 1, and assembled battery tests, and Experimental cell is tested by being subjected to computer-controlled auto charge and discharge instrument to carry out charge and discharge cycles.The charging stopping potential is 4.2V, and discharge cut-off voltage is 2.0V.Studies have shown that described silicon/Single Walled Carbon Nanotube matrix material is as negative active core-shell material, its reversible capacity at 0.1C is 1000mAh/g, and the reversible capacity of 1C is 880mAh/g, has shown dynamic behavior preferably.
Embodiment 6: take by weighing 0.001g Mo powder and 10g silicon grain (its median size is 50 μ m), ground 5 hours, material with gained is placed in the graphite boat then, reinstall in the tube furnace, charge into argon gas, chemical vapor deposition processes is with embodiment 1, the time of chemical vapour deposition is 50 minutes, products therefrom is silicon/multi-wall carbon nano-tube composite material, and wherein the mean diameter of multi-walled carbon nano-tubes is 8nm, and length is 100 μ m.
As carrying out the preparation of anodal and negative pole as described in the embodiment 1, and assembled battery tests, and Experimental cell is tested by being subjected to computer-controlled auto charge and discharge instrument to carry out charge and discharge cycles.The charging stopping potential is 4.2V, and discharge cut-off voltage is 2.0V.Studies have shown that described silicon/multi-wall carbon nano-tube composite material is as negative active core-shell material, its reversible capacity at 0.1C is 860mAh/g, and the reversible capacity of 1C is 580mAh/g, has shown dynamic behavior preferably.
Embodiment 7: take by weighing 0.001gMo powder and 10g silicon grain (its median size is 100 μ m), ground 50 hours, material with gained is placed in the graphite boat then, reinstall in the tube furnace, charge into argon gas, chemical vapor deposition processes is with embodiment 1, the time of chemical vapour deposition is 48 hours, products therefrom is silicon/multi-wall carbon nano-tube composite material, and wherein the mean diameter of multi-walled carbon nano-tubes is 200nm, and length is 20 μ m.
As carrying out the preparation of anodal and negative pole as described in the embodiment 1, and assembled battery tests, and Experimental cell is tested by being subjected to computer-controlled auto charge and discharge instrument to carry out charge and discharge cycles.The charging stopping potential is 4.2V, and discharge cut-off voltage is 2.0V.Studies have shown that described silicon/multi-wall carbon nano-tube composite material is as negative active core-shell material, its reversible capacity at 0.1C is 960mAh/g, and the reversible capacity of 1C is 780mAh/g, has shown dynamic behavior preferably.
Embodiment 8: take by weighing 0.001g Fe powder and 0.001gMo powder and 10g silicon grain (its median size is 5 μ m), ground 15 minutes, material with gained is placed in the graphite boat then, reinstall in the tube furnace, charge into argon gas, chemical vapor deposition processes is with embodiment 1, the time of chemical vapour deposition is 50 minutes, products therefrom is silicon/multi-wall carbon nano-tube composite material, and wherein the mean diameter of multi-walled carbon nano-tubes is 15nm, and length is 46 μ m.
As carrying out the preparation of anodal and negative pole as described in the embodiment 1, and assembled battery tests, and Experimental cell is tested by being subjected to computer-controlled auto charge and discharge instrument to carry out charge and discharge cycles.The charging stopping potential is 4.2V, and discharge cut-off voltage is 2.0V.Studies have shown that described silicon/multi-wall carbon nano-tube composite material is as negative active core-shell material, its reversible capacity at 0.1C is 890mAh/g, and the reversible capacity of 1C is 630mAh/g, has shown dynamic behavior preferably.
Embodiment 9: take by weighing 0.001gFe powder and 0.001gMo powder and 10g silicon grain (its median size is 5 μ m), ground 5 hours, material with gained is placed in the graphite boat then, reinstall in the tube furnace, charge into argon gas, chemical vapor deposition processes is with embodiment 1, the time of chemical vapour deposition is 2 hours, products therefrom is silicon/multi-wall carbon nano-tube composite material, and wherein the mean diameter of multi-walled carbon nano-tubes is 1nm, and length is 100 μ m.
As carrying out the preparation of anodal and negative pole as described in the embodiment 1, and assembled battery tests, and Experimental cell is tested by being subjected to computer-controlled auto charge and discharge instrument to carry out charge and discharge cycles.The charging stopping potential is 4.2V, and discharge cut-off voltage is 2.0V.Studies have shown that described silicon/multi-wall carbon nano-tube composite material is as negative active core-shell material, its reversible capacity at 0.1C is 980mAh/g, and the reversible capacity of 1C is 780mAh/g, has shown dynamic behavior preferably.
Embodiment 10: take by weighing 1g Fe powder and 1g silicon grain (its median size is 5 μ m), ground 5 hours, the material with gained is placed in the graphite boat then, reinstalls in the tube furnace, charge into argon gas, flow is 20sccm, after the temperature programming to 500 ℃, gas is converted to the gas mixture (1: 6 of hydrogen and carbon monoxide, v/v), total flux is 300sccm, and constant temperature naturally cooled to room temperature after carrying out chemical vapour deposition in 50 minutes; Promptly get product silicon/carbon nano-fiber composite material, the mean diameter of carbon nanofiber is 6nm, and length is 50 μ m.
As carrying out the preparation of anodal and negative pole as described in the embodiment 1, and assembled battery tests, and Experimental cell is tested by being subjected to computer-controlled auto charge and discharge instrument to carry out charge and discharge cycles.The charging stopping potential is 4.2V, and discharge cut-off voltage is 2.0V.Studies have shown that described silicon/carbon nano-fiber composite material is as negative active core-shell material, its reversible capacity at 0.1C is 1050mAh/g, and the reversible capacity of 1C is 780mAh/g, has shown dynamic behavior preferably.
Embodiment 11: take by weighing 0.001g Fe powder and 10g silicon grain (its median size is 5 μ m), ground 20 hours, material with gained is placed in the graphite boat then, reinstall in the tube furnace, charge into argon gas, flow is 20sccm, charges into argon gas, after the temperature programming to 900 ℃, gas is converted to methane, flow is 100sccm, and constant temperature was converted to argon gas with gas after carrying out chemical vapour deposition in 48 hours, naturally cool to room temperature, products therefrom is silicon/Single Walled Carbon Nanotube matrix material, and wherein the mean diameter of Single Walled Carbon Nanotube is 10.3nm, and length is 60 μ m.
As carrying out the preparation of anodal and negative pole as described in the embodiment 1, and assembled battery tests, and Experimental cell is tested by being subjected to computer-controlled auto charge and discharge instrument to carry out charge and discharge cycles.The charging stopping potential is 4.2V, and discharge cut-off voltage is 2.0V.Studies have shown that described silicon/Single Walled Carbon Nanotube matrix material is as negative active core-shell material, its reversible capacity at 0.1C is 1050mAh/g, and the reversible capacity of 1C is 860mAh/g, has shown dynamic behavior preferably.
Embodiment 12: take by weighing 0.001g Fe powder and 10g silicon grain (its median size is 5 μ m), ground 5 hours, material with gained is placed in the graphite boat then, reinstall in the tube furnace, charge into argon gas, flow is 20sccm, after the temperature programming to 1200 ℃, gas is converted to the gas mixture of methane and hydrogen, its ratio is 3: 2 (v/v), total flux is 100sccm, and constant temperature was converted to argon gas with gas after carrying out chemical vapour deposition in 50 minutes, naturally cool to room temperature, products therefrom is silicon/double-walled carbon nano-tube matrix material, and wherein the mean diameter of double-walled carbon nano-tube is 5.5nm, and length is 80 μ m.
As carrying out the preparation of anodal and negative pole as described in the embodiment 1, and assembled battery tests, and Experimental cell is tested by being subjected to computer-controlled auto charge and discharge instrument to carry out charge and discharge cycles.The charging stopping potential is 4.2V, and discharge cut-off voltage is 2.0V.Studies have shown that described silicon/double-walled carbon nano-tube matrix material is as negative active core-shell material, its reversible capacity at 0.1C is 1000mAh/g, and the reversible capacity of 1C is 800mAh/g, has shown dynamic behavior preferably.
Embodiment 13: take by weighing 0.0001mol Fe (NO 3) 39H 2O puts into beaker, adds 1000ml distilled water, stirring and dissolving; And then take by weighing 0.0001mol trisodium citrate and 0.0001mol sodium acetate, and add the distilled water of 1000ml, stirring and dissolving; Then the former is added drop-wise among the latter, stirs the solution that obtains being reduced; Take by weighing 60g sodium hydroxide again and join in the 1000ml distilled water, take by weighing the 0.0001mol sodium borohydride again and join above-mentioned basic solution, obtain reductant solution.20g silica flour (median size is 10 μ m) is joined to be reduced in the solution and stirs, and be warming up to 95 ℃, begin to drip sodium borohydride solution simultaneously, and control pH=11, continue to stir 10 minutes separation, drying; The gained material is placed in the aluminium oxide boat, and the tube furnace of packing into then charges into argon gas, flow is 80sccm, after the temperature programming to 900 ℃, gas is converted to the gas mixture of methane and hydrogen, its ratio is 5: 20 (v/v), total flux is 100sccm, and constant temperature was converted to argon gas with gas after carrying out chemical vapour deposition in 40 minutes, naturally cool to room temperature, products therefrom is silicon/multi-wall carbon nano-tube composite material, and wherein the mean diameter of multi-walled carbon nano-tubes is 18nm, and length is 75 μ m.
As carrying out the preparation of anodal and negative pole as described in the embodiment 1, and assembled battery tests, and Experimental cell is tested by being subjected to computer-controlled auto charge and discharge instrument to carry out charge and discharge cycles.The charging stopping potential is 4.2V, and discharge cut-off voltage is 2.0V.Studies have shown that described silicon/multi-wall carbon nano-tube composite material is as negative active core-shell material, its reversible capacity at 0.1C is 970mAh/g, and the reversible capacity of 1C is 770mAh/g, has shown dynamic behavior preferably.
Embodiment 14: take by weighing 0.01mol Fe (NO 3) 39H 2O puts into beaker, adds 10ml distilled water, stirring and dissolving; And then take by weighing 0.01mol trisodium citrate and 0.01mol sodium acetate, and add the distilled water of 10ml, stirring and dissolving; Then the former is added drop-wise among the latter, stirs the solution that obtains being reduced; Take by weighing 6g sodium hydroxide again and join in the 10ml distilled water, take by weighing the 0.01mol sodium borohydride again and join above-mentioned basic solution, obtain reductant solution.0.5g silica flour (median size is 10 μ m) is joined to be reduced in the solution and stirs, and be warming up to 70 ℃, begin to drip sodium borohydride solution simultaneously, and control pH=8, continue to stir 2 hours separation, drying; The gained material is placed in the aluminium oxide boat, and the tube furnace of packing into then charges into argon gas, flow is 80sccm, after the temperature programming to 900 ℃, with gas be converted to hydrogen and carbon monoxide gas mixture (1: 6, v/v), total flux is 100sccm, constant temperature naturally cooled to room temperature after carrying out chemical vapour deposition in 40 minutes, promptly got product silicon/carbon nano-fiber composite material, the mean diameter of carbon nanofiber is 12nm, and length is 35 μ m.
As carrying out the preparation of anodal and negative pole as described in the embodiment 1, and assembled battery tests, and Experimental cell is tested by being subjected to computer-controlled auto charge and discharge instrument to carry out charge and discharge cycles.The charging stopping potential is 4.2V, and discharge cut-off voltage is 2.0V.Studies have shown that described silicon/carbon nano-fiber composite material is as negative active core-shell material, its reversible capacity at 0.1C is 930mAh/g, and the reversible capacity of 1C is 770mAh/g, has shown dynamic behavior preferably.
Embodiment 15: take by weighing 0.001mol Fe (NO 3) 39H 2O puts into beaker, adds 100ml ethanol, stirring and dissolving; And then take by weighing 0.001mol trisodium citrate and 0.001mol sodium acetate, and add the ethanol of 100ml, stirring and dissolving; Then the former is added drop-wise among the latter, stirs the solution that obtains being reduced; Take by weighing 6g sodium hydroxide again and join in the 20ml ethylene glycol, take by weighing the 0.01mol sodium borohydride again and join above-mentioned basic solution, obtain reductant solution.2g silica flour (median size is 10 μ m) is joined to be reduced in the solution and stirs, and be warming up to 70 ℃, begin to drip sodium borohydride solution simultaneously, and control pH=4, continue to stir 2 hours separation, drying; The gained material is placed in the aluminium oxide boat, and the tube furnace of packing into then charges into argon gas, flow is 80sccm, after the temperature programming to 700 ℃, gas is converted to methane, flow is 100sccm, after constant temperature carried out chemical vapour deposition in 20 minutes, gas is converted to argon gas, naturally cools to room temperature, products therefrom is silicon/Single Walled Carbon Nanotube matrix material, wherein the mean diameter of Single Walled Carbon Nanotube is 5nm, and length is 50nm.
As carrying out the preparation of anodal and negative pole as described in the embodiment 1, and assembled battery tests, and Experimental cell is tested by being subjected to computer-controlled auto charge and discharge instrument to carry out charge and discharge cycles.The charging stopping potential is 4.2V, and discharge cut-off voltage is 2.0V.Studies have shown that described silicon/Single Walled Carbon Nanotube matrix material is as negative active core-shell material, its reversible capacity at 0.1C is 900mAh/g, and the reversible capacity of 1C is 750mAh/g, has shown dynamic behavior preferably.
Embodiment 16: take by weighing 0.01mol Fe (NO 3) 39H 2O puts into beaker, adds 100ml distilled water, stirring and dissolving; And then take by weighing 0.2mol trisodium citrate and 0.5mol sodium acetate, and add the distilled water of 50ml, stirring and dissolving; Then the former is added drop-wise among the latter, stirs the solution that obtains being reduced; Take by weighing 6g sodium hydroxide again and join in the 40ml distilled water, take by weighing the 0.05mol sodium borohydride again and join above-mentioned basic solution, obtain reductant solution.2g silica flour (median size is 10 μ m) is joined to be reduced in the solution and stirs, and be warming up to 70 ℃, begin to drip sodium borohydride solution simultaneously, and control pH=12, continue to stir 10 minutes separation, drying; The gained material is placed in the aluminium oxide boat, and the tube furnace of packing into then charges into argon gas, flow is 80sccm, after the temperature programming to 900 ℃, gas is converted to the gas mixture of methane and hydrogen, its ratio is 3: 2 (v/v), total flux is 100sccm, and constant temperature was converted to argon gas with gas after carrying out chemical vapour deposition in 40 minutes, naturally cool to room temperature, products therefrom is silicon/double-walled carbon nano-tube matrix material, and wherein the mean diameter of double-walled carbon nano-tube is 3.5nm, and length is 800nm.
As carrying out the preparation of anodal and negative pole as described in the embodiment 1, and assembled battery tests, and Experimental cell is tested by being subjected to computer-controlled auto charge and discharge instrument to carry out charge and discharge cycles.The charging stopping potential is 4.2V, and discharge cut-off voltage is 2.0V.Studies have shown that described silicon/double-walled carbon nano-tube matrix material is as negative active core-shell material, its reversible capacity at 0.1C is 970mAh/g, and the reversible capacity of 1C is 800mAh/g, has shown dynamic behavior preferably.
Embodiment 17: take by weighing 0.01mol Co (NO 3) 26H 2O puts into beaker, adds 100ml methyl alcohol, stirring and dissolving; And then take by weighing 0.2mol trisodium citrate and 0.5mol sodium acetate, and add 50ml Virahol, stirring and dissolving; Then the former is added drop-wise among the latter, stirs the solution that obtains being reduced; Take by weighing 6g sodium hydroxide again and join in the 20ml distilled water, take by weighing the 0.01mol sodium borohydride again and join above-mentioned basic solution, obtain reductant solution.2g silica flour (median size is 10 μ m) is joined to be reduced in the solution and stirs, and be warming up to 75 ℃, begin to drip sodium borohydride solution simultaneously, and control pH=10, continue to stir 30 minutes separation, drying; The gained material is placed in the aluminium oxide boat, and the tube furnace of packing into then charges into argon gas, flow is 80sccm, after the temperature programming to 900 ℃, gas is converted to the gas mixture of methane and hydrogen, its ratio is 3: 2 (v/v), total flux is 100sccm, and constant temperature was converted to argon gas with gas after carrying out chemical vapour deposition in 40 minutes, naturally cool to room temperature, products therefrom is silicon/double-walled carbon nano-tube matrix material, and wherein the mean diameter of double-walled carbon nano-tube is 6.5nm, and length is 120 μ m.
As carrying out the preparation of anodal and negative pole as described in the embodiment 1, and assembled battery tests, and Experimental cell is tested by being subjected to computer-controlled auto charge and discharge instrument to carry out charge and discharge cycles.The charging stopping potential is 4.2V, and discharge cut-off voltage is 2.0V.Studies have shown that described silicon/double-walled carbon nano-tube matrix material is as negative active core-shell material, its reversible capacity at 0.1C is 970mAh/g, and the reversible capacity of 1C is 790mAh/g, has shown dynamic behavior preferably.
Embodiment 18: take by weighing 0.01mol Ni (NO 3) 26H 2O puts into beaker, adds 100ml methyl alcohol, stirring and dissolving; And then take by weighing 0.2mol trisodium citrate and 0.5mol sodium acetate, and add 50ml methyl alcohol, stirring and dissolving; Then the former is added drop-wise among the latter, stirs the solution that obtains being reduced; Take by weighing 6g sodium hydroxide again and join in the 20ml methyl alcohol, take by weighing the 0.01mol sodium borohydride again and join above-mentioned basic solution, obtain reductant solution.2g silica flour (median size is 10 μ m) is joined to be reduced in the solution and stirs, and keep it to equate being 25 ℃, beginning to drip sodium borohydride solution simultaneously, and control pH=9, continue to stir 30 minutes, separate, drying with room temperature; The gained material is placed in the aluminium oxide boat, and the tube furnace of packing into then charges into argon gas, flow is 80sccm, after the temperature programming to 1200 ℃, gas is converted to the gas mixture of methane and hydrogen, its ratio is 3: 2 (v/v), total flux is 100sccm, and constant temperature was converted to argon gas with gas after carrying out chemical vapour deposition in 48 hours, naturally cool to room temperature, products therefrom is silicon/double-walled carbon nano-tube matrix material, and wherein the mean diameter of double-walled carbon nano-tube is 5nm, and length is 160 μ m.
As carrying out the preparation of anodal and negative pole as described in the embodiment 1, and assembled battery tests, and Experimental cell is tested by being subjected to computer-controlled auto charge and discharge instrument to carry out charge and discharge cycles.The charging stopping potential is 4.2V, and discharge cut-off voltage is 2.0V.Studies have shown that described silicon/double-walled carbon nano-tube matrix material is as negative active core-shell material, its reversible capacity at 0.1C is 1000mAh/g, and the reversible capacity of 1C is 900mAh/g, has shown dynamic behavior preferably.
Embodiment 19: take by weighing 0.001mol Co (NO 3) 26H 2O and 0.000015mol (NH 4) 6Mo 7O 244H 2O in beaker, adds 100ml ethanol, and stirring and dissolving adds the 1g silica flour then, and its median size is 10 μ m, stirs 2 hours, leave standstill about 72 hours after, separation, drying; The gained material is placed in the graphite boat, the tube furnace of packing into then, charge into argon gas and hydrogen gas mixture (200: 5, v/v), total flux is 300sccm, after the temperature programming to 500 ℃, with gas be converted to hydrogen and carbon monoxide gas mixture (1: 4, v/v), total flux is 300sccm, constant temperature naturally cooled to room temperature after carrying out chemical vapour deposition in 20 minutes; Promptly get product silicon/carbon nano-fiber composite material, the mean diameter of carbon nanofiber is 10nm, and length is 20 μ m.
The negative material of described material as lithium ion battery used.The preparation method of negative pole such as embodiment 1.
With commodity positive electrode material LiFePO 4Mix formation slurry (active material: acetylene black: PVDF=75: 15: 10) at normal temperatures and pressures with the cyclohexane solution of acetylene black and 10% polyvinylidene difluoride (PVDF) (PVDF), evenly be coated on the aluminum substrates, about 20～60 μ m of the film thickness of gained are as the positive pole of battery.Electrolytic solution is 1mol LiPF 6Be dissolved in the mixed solvent of 1L EC and DMC (volume ratio 1: 1).With all battery materials, comprise positive pole, negative pole, battery case, barrier film, dry back is added electrolytic solution and is assembled into Experimental cell in the argon filling glove box or in the drying room.
Experimental cell is tested by being subjected to computer-controlled auto charge and discharge instrument to carry out charge and discharge cycles.The charging stopping potential is 4.2V, and discharge cut-off voltage is 2.0V.Studies have shown that described silicon/carbon nano-fiber composite material is as negative active core-shell material, its reversible capacity at 0.1C is 550mAh/g, and the reversible capacity of 1C is 300mAh/g, has shown dynamic behavior preferably.
Embodiment 20: take by weighing 0.003mol Co (NO 3) 26H 2O and 0.000045mol (NH 4) 6Mo 7O 244H 2O in beaker, adds in the 100ml ethanol, and stirring and dissolving adds the 1g silicon grain then, and its median size is 20 μ m, stirs 30 minutes, leave standstill about 24 hours after, separation, drying; Chemical vapor deposition processes is with embodiment 19, and the time of chemical vapour deposition is 2h, and products therefrom is silicon/carbon nano-fiber composite material, and the mean diameter of carbon nano fiber is 50nm, and length is 100 μ m.
As carrying out the preparation of anodal and negative pole as described in the embodiment 19, and assembled battery tests, and Experimental cell is tested by being subjected to computer-controlled auto charge and discharge instrument to carry out charge and discharge cycles.The charging stopping potential is 4.2V, and discharge cut-off voltage is 2.0V.Studies have shown that described silicon/carbon nano-fiber composite material is as negative active core-shell material, its reversible capacity at 0.1C is 920mAh/g, and the reversible capacity of 1C is 750mAh/g, has shown dynamic behavior preferably.
Embodiment 21: take by weighing 0.012mol Co (NO 3) 26H 2O and 0.00018mol (NH 4) 6Mo 7O 244H 2O in beaker, adds 120ml ethanol, and stirring and dissolving adds the 1g silicon grain then, and its median size is 1cm, stirs 1 hour, leave standstill about 72 hours after, separation, drying; Chemical vapor deposition processes is with embodiment 19, wherein the total flux of hydrogen and carbon mono oxide mixture is 500sccm, and the time of chemical vapour deposition is 2 hours, and products therefrom is silicon/carbon nano-fiber composite material, the mean diameter of carbon nano fiber is 200nm, and length is 100 μ m.
Take by weighing embodiment 21 gained silicon/double-walled carbon nano-tube matrix material 0.5g, adding is dissolved with 0.2g K 2PtCl 6The 200ml ethylene glycol solution in; fully stir after 1 hour; refluxed about 6 hours under argon shield in 160 ℃; after naturally cooling to room temperature; product is washed repeatedly with ethanol, and products therefrom is silicon/double-walled carbon nano-tube matrix material loaded with nano Pt, and the Pt charge capacity is 14.5wt.%; the Pt high dispersing is in its surface, and its mean diameter is 4.9nm.With K in the above-mentioned solution 2PtCl 6Content bring up to 0.8g, then the Pt charge capacity on silicon/multi-wall carbon nano-tube composite material surface can reach 18wt.%, the mean diameter of Pt is 6.9nm, be used for proton exchange and touch fuel cell, its catalytic activity is 0.35 times of the Pt/Vulcan XC-72 catalyzer (charge capacity is 60wt.%) produced of U.S. ETEK company; Be used for dimethyl ether fuel battery, its catalytic activity is 0.6 times of the Pt/Vulcan XC-72 catalyzer (charge capacity is 60wt.%) produced of U.S. ETEK company.。
Embodiment 22: take by weighing 0.01786mol FeSO 47H 2O adds 178.6ml methyl alcohol in beaker, stirring and dissolving adds the 1g silicon grain then, and its median size is 1 μ m, stirs 30min, leave standstill about 24 hours after, separate, drying; The gained dried feed is placed in the aluminium sesquioxide boat, packs into then in the tube furnace, charge into argon gas, flow is 100sccm, after the temperature programming to 1000 ℃, gas is converted to methane, flow is 100sccm, after constant temperature carried out chemical vapour deposition in 48 hours, gas is converted to argon gas, naturally cools to room temperature, products therefrom is silicon/Single Walled Carbon Nanotube matrix material, wherein the mean diameter of Single Walled Carbon Nanotube is 1nm, and length is 100 μ m.
Silicon/Single Walled Carbon Nanotube matrix material of embodiment 22 is black with conductive acetylene, polyvinylidene difluoride (PVDF) mixes with mass ratio and is pressed into and is prepared into electrode on the nickel foam at 85: 5: 10, with 6M KOH is electrolytic solution, when 0.9V, obtaining the high specific electrical capacity is 110F/g, power density is 12kW/g, energy density is 4.3Wh/g, shows good electrical double layer characteristic, is a kind of very potential super capacitor material.
Embodiment 23: take by weighing 0.01786mol FeSO 47H 2O adds 1786ml ethylene glycol in beaker, stirring and dissolving adds the 1000g silicon grain then, and its median size is 1 μ m, stirs 20h, leave standstill about 24 hours after, separate, drying; Chemical vapor deposition processes is with embodiment 22, and the time of chemical vapour deposition is 1 hour, and products therefrom is silicon/Single Walled Carbon Nanotube matrix material, and wherein the mean diameter of Single Walled Carbon Nanotube is 1.2nm, and length is 80nm.
Take by weighing embodiment 23 gained silicon/double-walled carbon nano-tube matrix material 0.5g, adding is dissolved with 0.2g K 2PtCl 6The 200ml ethylene glycol solution in; fully stir after 1 hour; refluxed about 6 hours under argon shield in 160 ℃; after naturally cooling to room temperature; product is washed repeatedly with ethanol, and products therefrom is silicon/double-walled carbon nano-tube matrix material loaded with nano Pt, and the Pt charge capacity is 6wt.%; the Pt high dispersing is in its surface, and its mean diameter is 5.6nm.With K in the above-mentioned solution 2PtCl 6Content bring up to 0.8g, then the Pt charge capacity on silicon/multi-wall carbon nano-tube composite material surface can reach 24wt.%, the mean diameter of Pt is 8.6nm, be used for proton exchange and touch fuel cell, its catalytic activity is 0.75 times of the Pt/Vulcan XC-72 catalyzer (charge capacity is 60wt.%) produced of U.S. ETEK company.
Embodiment 24: take by weighing 0.00027mol FeCl 36H 2O and 0.00025mol Co (CH 3COO) 24H 2O adds 60ml ethanol in beaker, stirring and dissolving adds the 1g silicon grain then, and its median size is 1 μ m, stirs 2 hours, leave standstill about 72 hours after, separation, drying; The gained dried feed is placed in the graphite boat, packs into then in the tube furnace, charge into argon gas, flow is 100sccm, after the temperature programming to 1200 ℃, gas is converted to the gas mixture of methane and hydrogen, its ratio is 3: 2 (v/v), total flux is 100sccm, and constant temperature was converted to argon gas with gas after carrying out chemical vapour deposition in 30 minutes, naturally cool to room temperature, products therefrom is silicon/double-walled carbon nano-tube matrix material, and wherein the mean diameter of double-walled carbon nano-tube is 2.5nm, and length is 60 μ m.
As carrying out the preparation of anodal and negative pole as described in the embodiment 19, and assembled battery tests, and Experimental cell is tested by being subjected to computer-controlled auto charge and discharge instrument to carry out charge and discharge cycles.The charging stopping potential is 4.2V, and discharge cut-off voltage is 2.0V.Studies have shown that described silicon/double-walled carbon nano-tube matrix material is as negative active core-shell material, its reversible capacity at 0.1C is 970mAh/g, and the reversible capacity of 1C is 860mAh/g, has shown dynamic behavior preferably.
Embodiment 25: take by weighing 0.00054mol FeCl 36H 2O and 0.0005mol Co (CH 3COO) 24H 2O adds 120ml ethanol in beaker, stirring and dissolving adds the 1g silicon grain then, and its median size is 5 μ m, stirs 2 hours, leave standstill about 72 hours after, separation, drying; Chemical vapor deposition processes is with embodiment 24, and the time of chemical vapour deposition is 1 hour, and products therefrom is silicon/double-walled carbon nano-tube matrix material, and wherein the mean diameter of double-walled carbon nano-tube is 6nm, and length is 100 μ m.
Take by weighing embodiment 25 gained silicon/double-walled carbon nano-tube matrix material 0.5g, adding is dissolved with 0.2g K 2PtCl 6The 200ml ethylene glycol solution in; fully stir after 1 hour; refluxed about 6 hours under argon shield in 160 ℃; after naturally cooling to room temperature; product is washed repeatedly with ethanol, and products therefrom is silicon/double-walled carbon nano-tube matrix material loaded with nano Pt, and the Pt charge capacity is 12wt.%; the Pt high dispersing is in its surface, and its mean diameter is 6.7nm.With K in the above-mentioned solution 2PtCl 6Content bring up to 0.8g, then the Pt charge capacity on silicon/multi-wall carbon nano-tube composite material surface can reach 22wt.%, the mean diameter of Pt is 7.2nm, be used for proton exchange and touch fuel cell, its catalytic activity is 0.2 times of the Pt/Vulcan XC-72 catalyzer (charge capacity is 60wt.%) produced of U.S. ETEK company.
Embodiment 26: take by weighing 0.0009mol Ni (NO 3) 26H 2O adds 100ml methyl alcohol in beaker, stirring and dissolving adds the 1g silicon grain then, and its median size is 20 μ m, stirs 30 minutes, leave standstill about 48 hours after, separation, drying; The gained dried feed is placed in the graphite boat, pack into then in the tube furnace, after vacuumizing, charge into the gas mixture of argon gas and hydrogen, its ratio is 92: 8 (v/v), total flux is 100sccm, after temperature programming to the 400 ℃ temperature, gas is converted to ammonia, flow is 50sccm, constant temperature was converted to acetylene with gas after carrying out pre-treatment in 20 minutes, and flow is 20sccm, after constant temperature carried out chemical vapour deposition in 20 minutes under uniform temp, gas is converted to argon gas, naturally cools to room temperature, products therefrom is novel carbon wool ball material, be silicon/multi-wall carbon nano-tube composite material, the wherein carbon nano-tube oriented silicon face that is grown in, its mean diameter is 50nm, length is 50 μ m.
As carrying out the preparation of anodal and negative pole as described in the embodiment 19, and assembled battery tests, and Experimental cell is tested by being subjected to computer-controlled auto charge and discharge instrument to carry out charge and discharge cycles.The charging stopping potential is 4.2V, and discharge cut-off voltage is 2.0V.Studies have shown that described silicon/multi-wall carbon nano-tube composite material is as negative active core-shell material, its reversible capacity at 0.1C is 940mAh/g, and the reversible capacity of 1C is 840mAh/g, has shown dynamic behavior preferably.
Embodiment 27: take by weighing 0.0004mol Ni (NO 3) 26H 2O adds 50ml methyl alcohol in beaker, stirring and dissolving adds the 1g silicon grain then, and its median size is 20 μ m, stirs 30 minutes, leave standstill about 48 hours after, separation, drying; Chemical vapor deposition processes is with embodiment 26, and the time of chemical vapour deposition is 1 hour, and products therefrom is silicon/multi-wall carbon nano-tube composite material, the wherein carbon nano-tube oriented silicon face that is grown in, and its mean diameter is 20nm, length is 100 μ m.
As carrying out the preparation of anodal and negative pole as described in the embodiment 19, and assembled battery tests, and Experimental cell is tested by being subjected to computer-controlled auto charge and discharge instrument to carry out charge and discharge cycles.The charging stopping potential is 4.2V, and discharge cut-off voltage is 2.0V.Studies have shown that described silicon/multi-wall carbon nano-tube composite material is as negative active core-shell material, its reversible capacity at 0.1C is 990mAh/g, and the reversible capacity of 1C is 880mAh/g, has shown dynamic behavior preferably.
Embodiment 28: take by weighing 0.001mol Fe (NO 3) 39H 2O adds the 100ml Virahol in beaker, stirring and dissolving adds the 1g silicon grain then, and its median size is 2 μ m, stirs 30 minutes, leave standstill about 72 hours after, separation, drying; The gained dried feed is placed in the graphite boat, pack into then in the tube furnace, charge into the gas mixture of argon gas and hydrogen, its ratio is 200: 28 (v/v), total flux is 100sccm, after the temperature programming to 500 ℃, gas is converted to the gas mixture of argon gas and acetylene, and its ratio is 100: 9 (v/v), and total flux is 190sccm, after constant temperature carried out chemical vapour deposition in 50 minutes, naturally cool to room temperature, products therefrom is silicon/multi-wall carbon nano-tube composite material, and wherein multi-walled carbon nano-tubes is the non-directional growth at silicon face, its mean diameter is 50nm, and length is 20 μ m.
Take by weighing embodiment 28 gained silicon/multi-wall carbon nano-tube composite material 0.5g, adding is dissolved with 0.2g K 2PtCl 6The 200ml ethylene glycol solution in; fully stir after 1 hour; refluxed about 6 hours under argon shield in 160 ℃; after naturally cooling to room temperature; product is washed repeatedly with ethanol, and products therefrom is silicon/multi-wall carbon nano-tube composite material loaded with nano Pt, and the Pt charge capacity is 12wt.%; the Pt high dispersing is in its surface, and its mean diameter is 3.5nm.With K in the above-mentioned solution 2PtCl 6Content bring up to 0.8g, then the Pt charge capacity on silicon/multi-wall carbon nano-tube composite material surface can reach 25wt.%, the mean diameter of Pt is 3.7nm, be used for direct methanol fuel cell, it is suitable to the Pt/Vulcan XC-72 catalyzer (charge capacity is 60wt.%) that the catalytic activity and the U.S. ETEK company of methanol electrooxidation are produced.
Embodiment 29: take by weighing 0.0002mol Fe (NO 3) 39H 2O adds the 20ml Virahol in beaker, stirring and dissolving adds the 1g silicon grain then, and its median size is 20 μ m, stirs 30 minutes, leave standstill about 72 hours after, separation, drying; Chemical vapor deposition processes is with embodiment 28, and the time of chemical vapour deposition is 2 hours, and products therefrom is silicon/multi-wall carbon nano-tube composite material, and wherein the mean diameter of multi-walled carbon nano-tubes is 10nm, and length is 100 μ m.
As carrying out the preparation of anodal and negative pole as described in the embodiment 19, and assembled battery tests, and Experimental cell is tested by being subjected to computer-controlled auto charge and discharge instrument to carry out charge and discharge cycles.The charging stopping potential is 4.2V, and discharge cut-off voltage is 2.0V.Studies have shown that described silicon/multi-wall carbon nano-tube composite material is as negative active core-shell material, its reversible capacity at 0.1C is 980mAh/g, and the reversible capacity of 1C is 800mAh/g, has shown dynamic behavior preferably.
Embodiment 30: take by weighing 0.0006mol Fe (NO 3) 39H 2O adds the 60ml Virahol in beaker, stirring and dissolving adds the 1g silicon grain then, and its median size is 20 μ m, stirs 30 minutes, leave standstill about 48 hours after, separation, drying; Chemical vapor deposition processes is with embodiment 28, and the time of chemical vapour deposition is 30 minutes, and products therefrom is silicon/multi-wall carbon nano-tube composite material, and wherein the mean diameter of multi-walled carbon nano-tubes is 30nm, and length is 50 μ m.
As carrying out the preparation of anodal and negative pole as described in the embodiment 19, and assembled battery tests, and Experimental cell is tested by being subjected to computer-controlled auto charge and discharge instrument to carry out charge and discharge cycles.The charging stopping potential is 4.2V, and discharge cut-off voltage is 2.0V.Studies have shown that described silicon/multi-wall carbon nano-tube composite material is as negative active core-shell material, its reversible capacity at 0.1C is 1000mAh/g, and the reversible capacity of 1C is 890mAh/g, has shown dynamic behavior preferably.
Embodiment 31: take by weighing 0.0002molg Fe (NO 3) 39H 2O adds the 20ml Virahol in beaker, stirring and dissolving adds the 1g silicon grain then, and its median size is 10 μ m, stirs after 30 minutes, leave standstill about 24 hours after, separation, drying; Chemical vapor deposition processes is with embodiment 28, and the time of chemical vapour deposition is 20 minutes, and products therefrom is silicon/multi-wall carbon nano-tube composite material, and wherein the mean diameter of multi-walled carbon nano-tubes is 10nm, and length is 5 μ m.
As carrying out the preparation of anodal and negative pole as described in the embodiment 19, and assembled battery tests, and Experimental cell is tested by being subjected to computer-controlled auto charge and discharge instrument to carry out charge and discharge cycles.The charging stopping potential is 4.2V, and discharge cut-off voltage is 2.0V.Studies have shown that described silicon/multi-wall carbon nano-tube composite material is as negative active core-shell material, its reversible capacity at 0.1C is 950mAh/g, and the reversible capacity of 1C is 770mAh/g, has shown dynamic behavior preferably.
Embodiment 32: take by weighing 0.0001mol Fe (NO 3) 39H 2O adds 20ml ethylene glycol in beaker, stirring and dissolving adds the 1g silicon grain then, and its median size is 10 μ m, stirs after 30 minutes, leave standstill about 24 hours after, separation, drying; Chemical vapor deposition processes is with embodiment 28, and the time of chemical vapour deposition is 20 minutes, and products therefrom is silicon/multi-wall carbon nano-tube composite material, and wherein the mean diameter of multi-walled carbon nano-tubes is 10nm, and length is 500nm.
As carrying out the preparation of anodal and negative pole as described in the embodiment 19, and assembled battery tests, and Experimental cell is tested by being subjected to computer-controlled auto charge and discharge instrument to carry out charge and discharge cycles.The charging stopping potential is 4.2V, and discharge cut-off voltage is 2.0V.Studies have shown that described silicon/multi-wall carbon nano-tube composite material is as negative active core-shell material, its reversible capacity at 0.1C is 938mAh/g, and the reversible capacity of 1C is 596mAh/g, has shown dynamic behavior preferably.
Embodiment 33: take by weighing 0.0001mol Fe (NO 3) 39H 2O adds the 20ml glycerol in beaker, stirring and dissolving adds the 1g silicon grain then, and its median size is 10 μ m, stirs after 30 minutes, leave standstill about 24 hours after, separation, drying; Chemical vapor deposition processes is with embodiment 28, and the time of chemical vapour deposition is 20 minutes, and products therefrom is silicon/multi-wall carbon nano-tube composite material, and wherein the mean diameter of multi-walled carbon nano-tubes is 10nm, and length is 100nm.
As carrying out the preparation of anodal and negative pole as described in the embodiment 19, and assembled battery tests, and Experimental cell is tested by being subjected to computer-controlled auto charge and discharge instrument to carry out charge and discharge cycles.The charging stopping potential is 4.2V, and discharge cut-off voltage is 2.0V.Studies have shown that described silicon/multi-wall carbon nano-tube composite material is as negative active core-shell material, its reversible capacity at 0.1C is 1100mAh/g, and the reversible capacity of 1C is 960mAh/g, has shown dynamic behavior preferably.
Embodiment 34: take by weighing 0.0006mol Fe (NO 3) 39H 2O and 0.0004mol Ni (NO 3) 26H 2O adds 60ml methyl alcohol in beaker, stirring and dissolving adds the 0.06g silicon grain then, and its median size is 50 μ m, stirs 2 hours, leave standstill about 60 hours after, separation, drying; The gained dried feed is placed in the graphite boat, in the tube furnace of packing into then, charges into the gas mixture of argon gas and hydrogen, its ratio is 85: 15 (v/v), after the temperature programming to 700 ℃, gas is converted to ethene, flow is 50sccm, after constant temperature carried out chemical vapour deposition in 2 hours, gas is converted to nitrogen, naturally cools to room temperature, products therefrom is silicon/multi-wall carbon nano-tube composite material, wherein the mean diameter of multi-walled carbon nano-tubes is 20nm, and length is 100 μ m.
As carrying out the preparation of anodal and negative pole as described in the embodiment 19, and assembled battery tests, and Experimental cell is tested by being subjected to computer-controlled auto charge and discharge instrument to carry out charge and discharge cycles.The charging stopping potential is 4.2V, and discharge cut-off voltage is 2.0V.Studies have shown that described silicon/multi-wall carbon nano-tube composite material is as negative active core-shell material, its reversible capacity at 0.1C is 970mAh/g, and the reversible capacity of 1C is 840mAh/g, has shown dynamic behavior preferably.
Embodiment 35: take by weighing 0.0006mol Fe (NO 3) 39H 2O and 0.0004mol Ni (NO 3) 26H 2O in beaker, add 60ml methyl alcohol, ethanol and glycerol (3: 2: 1, v/v), stirring and dissolving adds the 6g silicon grain then, its median size is 50 μ m, stirs 2 hours, leave standstill about 60 hours after, separation, drying; Chemical vapor deposition processes is with embodiment 34, and products therefrom is silicon/multi-wall carbon nano-tube composite material, and wherein the multi-walled carbon nano-tubes mean diameter is 20nm, and length is 100 μ m.
As carrying out the preparation of anodal and negative pole as described in the embodiment 19, and assembled battery tests, and Experimental cell is tested by being subjected to computer-controlled auto charge and discharge instrument to carry out charge and discharge cycles.The charging stopping potential is 4.2V, and discharge cut-off voltage is 2.0V.Studies have shown that described silicon/multi-wall carbon nano-tube composite material is as negative active core-shell material, its reversible capacity at 0.1C is 928mAh/g, and the reversible capacity of 1C is 720mAh/g, has shown dynamic behavior preferably.
Embodiment 36: take by weighing 1g Fe powder and 1000g silicon grain (median size is 20 μ m), with 3000rpm ball milling 30min, obtain alloying pellet, chemical vapor deposition processes is with embodiment 34, products therefrom is silicon/multi-wall carbon nano-tube composite material, wherein the multi-walled carbon nano-tubes mean diameter is 2nm, and length is 20nm.
As carrying out the preparation of anodal and negative pole as described in the embodiment 19, and assembled battery tests, and Experimental cell is tested by being subjected to computer-controlled auto charge and discharge instrument to carry out charge and discharge cycles.The charging stopping potential is 4.2V, and discharge cut-off voltage is 2.0V.Studies have shown that described silicon/multi-wall carbon nano-tube composite material is as negative active core-shell material, its reversible capacity at 0.1C is 960mAh/g, and the reversible capacity of 1C is 800mAh/g, has shown dynamic behavior preferably.
Embodiment 37: take by weighing 1000g Ni powder and 1g silicon grain (median size is 1 μ m), with 300rpm ball milling 100 hours, obtain alloying pellet, the gained dried feed is placed in the graphite boat, pack into then in the tube furnace, charge into the gas mixture of argon gas and hydrogen, its ratio is 100: 28 (v/v), total flux is 100sccm, after the temperature programming to 1200 ℃, gas is converted to the gas mixture of argon gas and acetylene, its ratio is 100: 9 (v/v), total flux is 100sccm, and constant temperature naturally cooled to room temperature after carrying out chemical vapour deposition in 20 minutes, products therefrom is silicon/multi-wall carbon nano-tube composite material, wherein multi-walled carbon nano-tubes is the non-directional growth at silicon face, and its mean diameter is 5nm, and length is 20 μ m.
As carrying out the preparation of anodal and negative pole as described in the embodiment 19, and assembled battery tests, and Experimental cell is tested by being subjected to computer-controlled auto charge and discharge instrument to carry out charge and discharge cycles.The charging stopping potential is 4.2V, and discharge cut-off voltage is 2.0V.Studies have shown that described silicon/multi-wall carbon nano-tube composite material is as negative active core-shell material, its reversible capacity at 0.1C is 940mAh/g, and the reversible capacity of 1C is 810mAh/g, has shown dynamic behavior preferably.
Embodiment 38: take by weighing 1g Ni powder and 1g silicon grain (median size is 10 μ m), with 100rpm ball milling 500 hours, obtain alloying pellet, the gained dried feed is placed in the graphite boat, pack into then in the tube furnace, charge into argon gas, flow is 100sccm, after the temperature programming to 900 ℃, gas is converted to the gas mixture of methane and hydrogen, and its ratio is 5: 2 (v/v), and total flux is 100sccm, after constant temperature carried out chemical vapour deposition in 48 hours, gas is converted to argon gas, naturally cools to room temperature, products therefrom is silicon/double-walled carbon nano-tube matrix material, wherein the mean diameter of double-walled carbon nano-tube is 25nm, and length is 100 μ m.
As carrying out the preparation of anodal and negative pole as described in the embodiment 19, and assembled battery tests, and Experimental cell is tested by being subjected to computer-controlled auto charge and discharge instrument to carry out charge and discharge cycles.The charging stopping potential is 4.2V, and discharge cut-off voltage is 2.0V.Studies have shown that described silicon/double-walled carbon nano-tube matrix material is as negative active core-shell material, its reversible capacity at 0.1C is 990mAh/g, and the reversible capacity of 1C is 840mAh/g, has shown dynamic behavior preferably.
Embodiment 39: take by weighing 1g Ni powder, 1g Co powder, 1g Mo powder and 100g silicon grain (median size is 5 μ m), with 300rpm ball milling 200 hours, obtain alloying pellet, the gained material is placed in the graphite boat, the tube furnace of packing into then, charge into the gas mixture (100: 17 of argon gas and hydrogen, v/v), total flux is 100sccm, after the temperature programming to 500 ℃, gas is converted to the gas mixture (1: 4 of hydrogen and carbon monoxide, v/v), total flux is 300sccm, and constant temperature naturally cooled to room temperature after carrying out chemical vapour deposition in 50 minutes; Promptly get product silicon/carbon nano-fiber composite material, the mean diameter of carbon nanofiber is 21nm, and length is 80 μ m.
As carrying out the preparation of anodal and negative pole as described in the embodiment 19, and assembled battery tests, and Experimental cell is tested by being subjected to computer-controlled auto charge and discharge instrument to carry out charge and discharge cycles.The charging stopping potential is 4.2V, and discharge cut-off voltage is 2.0V.Studies have shown that described silicon/carbon nano-fiber composite material is as negative active core-shell material, its reversible capacity at 0.1C is 1000mAh/g, and the reversible capacity of 1C is 890mAh/g, has shown dynamic behavior preferably.
Embodiment 40: take by weighing 1g Ni powder, 4g Mo powder and 100g silicon grain (median size is 5 μ m), with 1500rpm ball milling 50 hours, obtain alloying pellet, the gained material is placed in the graphite boat, the tube furnace of packing into then, charge into the gas mixture (100: 17 of argon gas and hydrogen, v/v), total flux is 100sccm, after the temperature programming to 1000 ℃, gas is converted to the gas mixture (1: 4 of hydrogen and carbon monoxide, v/v), total flux is 300sccm, and constant temperature naturally cooled to room temperature after carrying out chemical vapour deposition in 5 hours; Promptly get product silicon/carbon nano-fiber composite material, the mean diameter of carbon nanofiber is 13nm, and length is 60 μ m.
As carrying out the preparation of anodal and negative pole as described in the embodiment 19, and assembled battery tests, and Experimental cell is tested by being subjected to computer-controlled auto charge and discharge instrument to carry out charge and discharge cycles.The charging stopping potential is 4.2V, and discharge cut-off voltage is 2.0V.Studies have shown that described silicon/carbon nano-fiber composite material is as negative active core-shell material, its reversible capacity at 0.1C is 1000mAh/g, and the reversible capacity of 1C is 840mAh/g, has shown dynamic behavior preferably.

Claims (9)

1, a kind of silicon﹠amp, it comprises silicon substrate, reaches carbon nanotubes grown or carbon nano fiber thereon; The median size of described silicon substrate is 100nm～100 μ m; The diameter of described carbon nanotube or carbon nano fiber is 1～200nm, and length is 10nm～100 μ m; Described carbon nanotube is a single wall, double-walled or many walls.
2, silicon﹠amp as claimed in claim 1 is characterized in that: the geometric shape of described matrix silicon grain is for spherical.
3, silicon﹠amp as claimed in claim 1 is characterized in that: described carbon nanotube or carbon nano fiber have straight geometry appearance, or have the geometry appearance of bending or spiral.
4, the preparation method of the described silicon﹠amp of a kind of claim 1 specifically comprises the steps:
1) preparation of catalyst solution
Use is selected from the catalyst solution of one or more solvent preparations 0.0001～0.1M in distilled water, ethanol, methyl alcohol, Virahol, ethylene glycol or the glycerol;
Described catalyzer is for being selected from Fe (NO 3) 39H 2O, FeSO 47H 2O, FeCl 36H 2O, Co (NO 3) 26H 2O, Co (CH 3COO) 24H 2O, Ni (NO 3) 26H 2O, (NH 4) 6Mo 7O 244H 2Among the O one or more;
2) catalyst cupport
To join as the silicon materials of body material in the catalyst solution that step 1) makes, the mass ratio of described catalyzer and silicon is 1: 1～1000, stirs 30 minutes～20 hours, leaves standstill 5～72 hours, separates, drying, obtains the silicon materials of catalyst cupport;
The median size of described silicon substrate is 100nm～100 μ m;
3) chemical vapour deposition
With step 2) material that obtains is placed in the thermally resistant container, and the tube furnace of packing into then charges into the gas mixture of argon gas or argon gas and hydrogen, or carries out pre-treatment, temperature programming to 500 then～1200 ℃ temperature with ammonia; After being raised to target temperature, gas being converted to carbon-source gas or being converted to the gas mixture of argon gas, nitrogen or hydrogen and carbon-source gas, constant temperature 20 minutes naturally cools to room temperature after carrying out chemical vapour deposition to 48 hours.
5, the preparation method of the described silicon﹠amp of a kind of claim 1 specifically comprises the steps:
1) preparation of chemical plating solution
Use is selected from the Fe (NO of one or more solvent preparations 0.0001～0.1M in distilled water, ethanol, methyl alcohol, Virahol, ethylene glycol or the glycerol 3) 39H 2O, Co (NO 3) 26H 2O or Ni (NO 3) 26H 2O solution; Preparation contains the distilled water solution of trisodium citrate and sodium acetate; The concentration of described trisodium citrate and sodium acetate is 0.0001～1M; Then the former is added drop-wise among the latter, stirs, obtain mixed solution A;
Use distilled water that sodium hydroxide and sodium borohydride are mixed with reductant solution B; Concentration sodium hydroxide 1.5～15M wherein, the concentration of sodium borohydride is 0.0001～1M;
2) load of catalyzer
To join as the silicon materials of body material in the mixed solution A that step 1) makes, stir, be warming up to 25～95 ℃, the pH=4 of regulator solution～12 drip the reductant solution B that step 1) prepares then, wait to drip, continue to stir 10 minutes～2 hours, separate, drying obtains the silicon materials of catalyst cupport; The ratio of the silicon materials that add, solution A, solution B is 1g: 40～100ml: 10～50ml;
The median size of described silicon substrate is 100nm～100 μ m;
3) chemical vapour deposition
With step 2) material that obtains is placed in the thermally resistant container, and the tube furnace that the resistance to air loss of packing into then is good charges into the gas mixture of argon gas or argon gas and hydrogen, temperature programming to 500 then～1200 ℃ temperature; After being raised to target temperature, gas being converted to carbon-source gas or being converted to the gas mixture of argon gas, nitrogen or hydrogen and carbon-source gas, constant temperature 20 minutes naturally cools to room temperature after carrying out chemical vapour deposition to 48 hours.
6, the preparation method of the described silicon﹠amp of a kind of claim 1 specifically comprises the steps:
1) mixing of catalyzer
One or more that are selected from Fe, Co, Ni, Mo metal-powder are mixed with silicon grain as body material, mixed 5 minutes～50 hours, the mass ratio of metal and body material is 1: 1～1000;
The median size of described silicon substrate is 100nm～100 μ m;
2) chemical vapour deposition
The material that step 1) is obtained is placed in the thermally resistant container, and the tube furnace that the resistance to air loss of packing into then is good charges into the gas mixture of argon gas or argon gas and hydrogen, temperature programming to 700 then～1200 ℃ temperature; After being raised to target temperature, gas being converted to carbon-source gas or being converted to the gas mixture of argon gas, nitrogen or hydrogen and carbon-source gas, constant temperature 20 minutes naturally cools to room temperature after carrying out chemical vapour deposition to 48 hours.
7, the preparation method of the described silicon﹠amp of a kind of claim 1 specifically comprises the steps:
1) contains the preparation of catalyst elements alloy
One or more that are selected from Fe, Co, Ni, Mo metal-powder are mixed with silicon grain as body material, carried out ball milling then 30 minutes～500 hours, rotating speed is 100～3000rpm, and the mass ratio of metal and body material is 1: 0.001～1000;
The median size of described silicon substrate is 100nm～100 μ m;
2) chemical vapour deposition
The material that step 1) is obtained is placed in the thermally resistant container, and the tube furnace that the resistance to air loss of packing into then is good charges into the gas mixture of argon gas or argon gas and hydrogen, temperature programming to 700 then～1200 ℃ temperature; After being raised to target temperature, gas being converted to carbon-source gas or being converted to the gas mixture of argon gas, nitrogen or hydrogen and carbon-source gas, constant temperature 20 minutes naturally cools to room temperature after carrying out chemical vapour deposition to 48 hours.
8, the described silicon﹠amp of one of claim 1～3 in energy storage and switching device as the purposes of the negative material of lithium ion battery.
9, the described silicon﹠amp of one of claim 1～3 is as the purposes of the carrier of various fuel-cell catalysts.
CNA2005100871287A 2005-07-26 2005-07-26 Carbon silicon composite material, its preparation method and use Pending CN1903793A (en)

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