CN103346302A - Lithium battery silicon-carbon nanotube composite cathode material as well as preparation method and application thereof - Google Patents
Lithium battery silicon-carbon nanotube composite cathode material as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a lithium battery silicon-carbon nanotube composite cathode material as well as a preparation method and application of the lithium battery silicon-carbon nanotube composite cathode material. The preparation method of the lithium battery silicon-carbon nanotube composite cathode material comprises the following steps of: mixing and uniformly stirring an organic carbon source and nanometer silicon based on the mass ratio of (0.4-9): 1, adding a catalyst to obtain mixed slurry, drying by a closed circulation spray dryer to obtain a precursor, insulating the precursor for 1-5 hours at the temperature of 300-700 DEG C to obtain a sample, feeding the sample in a tube furnace, increasing the temperature to 500-900 DEG C under the mixed gas of gaseous organic carbon source and N2 and Ar2, and naturally cooling to obtain the lithium battery silicon-carbon nanotube composite cathode material. The lithium battery silicon-carbon nanotube composite cathode material has excellent electrochemical properties, high first charge-discharge efficiency up to more than 2000mAh/g, reversible specific capacity of about 1100mAh/g after cycle of 50 weeks, and good specific capacity and cycle performance, and the problems of low first efficiency, large irreversible capacity loss and poor conductivity of silicon when being used to prepare a lithium ion battery cathode are successfully solved.
Description
Technical field
The invention belongs to the lithium battery material preparation field, be specifically related to a kind of lithium battery silicon-carbon nanotube composite negative pole material and preparation method thereof and application.
Background technology
Lithium ion battery because of its have energy density big, have extended cycle life and advantages of environment protection becomes a kind of desirable regenerative resource.Electrode material is one of key factor that determines the lithium ion battery combination property.Present business-like carbon negative pole material is near its theoretical capacity (372mAh/g), and being difficult to has room for promotion again, compares with carbon negative pole material, and the theoretical specific capacity of elemental silicon is up to 4200mAh/g, thereby becomes present research focus.
The doff lithium mechanism of silicon-based anode material is that silicon and lithium generation chemical reaction generate Li at present
xThe Si compound forms 7 kinds of Li altogether according to different lithium-inserting amounts
xSi compound, and each different Li
xThe Si compound all has different crystal structures.Therefore, along with the difference of removal lithium embedded amount and current potential in the charge and discharge process will produce various alloy cpd, thereby cause the variation of material structure and cause the pole piece efflorescence to be lost efficacy.Particularly in the doff lithium process, the volumetric expansion effect of elemental silicon is up to 300%, and its first charge-discharge efficiency and stable circulation performance far can not reach the requirement of commercial applicationization.
Carbon nano-tube (CNTs) has excellent conducting performance and mechanical strength, by carbon nano-tube and nano silicon material is compound will be conducive to electrically contacting and cross-link intensity between the enhanced activity material, thereby effectively improve the conductivity of nano silica-base material and the expansion cushion space between the particle, to improving silica-base material efficient and improve cyclical stability and have important facilitation first.
In recent years, people have carried out a lot of significant exploratory developments for carbon nano-tube and active lithium storage materials compound, for example at document (T.Cetinkaya, M.O.Guler, H.Akbulut.Microelectron.Eng.108:169 – 176 (2013)) in, the researcher carries out high-energy ball milling with multi-walled carbon nano-tubes and nano-silicon, obtain the silicon-carbon nanometer tube composite materials of excellent performance, but this high-energy ball milling is just with silicon nanoparticle and the simple mechanical mixture of carbon nano-tube, and the appearance structure of destructible raw material is not suitable for suitability for industrialized production in mechanical milling process.Application number is that 201110378735.4 patent application discloses a kind of lithium ion battery silicon-carbon cathode material and preparation method thereof, and this invention is silicon-carbon cathode material more than the 500mAh/g by Si-C composite material and native graphite class material being mixed with out a kind of specific capacity.Wherein, Si-C composite material deposits to the nano silica fume particle surface by carbon nano-tube and/or carbon nano-fiber and/or is embedded into and forms nuclear between the nano silica fume particle, and nuclear the surface be coated with carbon-coating, this process need is through repeatedly pulverizing, coat processing, complex process.
Summary of the invention
For overcoming the deficiencies in the prior art part, primary and foremost purpose of the present invention is to provide a kind of lithium battery silicon-carbon nanotube composite negative pole material, and this lithium battery silicon-carbon nanotube composite negative pole material specific capacity first reaches more than the 2000mAh/g.
Another object of the present invention is to provide the preparation method of above-mentioned lithium battery silicon-carbon nanotube composite negative pole material.
A further object of the present invention is to provide the application of above-mentioned lithium battery silicon-carbon nanotube composite negative pole material.
For achieving the above object, the present invention adopts following technical scheme:
A kind of preparation method of lithium battery silicon-carbon nanotube composite negative pole material comprises the steps:
(1) organic carbon source and catalyst are dissolved in obtain solution A in the solvent; Other joins it in nano-silicon liquid after getting solvent and adding the dispersant dissolving, and ultrasonic 0.5～2h obtains solution B; Then solution B is joined in the solution A, obtain mixed slurry; Wherein solvent is ethanol or ethylene glycol in the nano-silicon liquid;
(2) mixed slurry that step (1) is obtained stirs 0.5～3h, adds solid masses content to 10～30% of solvent adjustment mixed slurry then, with the dry powder process of mixed slurry, obtains precursor A again;
(3) precursor A that step (2) is obtained is warming up to 300～700 ℃ in inert gas, is cooled to room temperature behind insulation 1～5h, obtains precursor B;
(4) precursor B that step (3) is obtained is warming up to 500～900 ℃ in the gaseous mixture of gaseous state organic carbon source and inert gas, is cooled to room temperature behind insulation 0.5～5h, obtains described lithium battery silicon-carbon nanotube composite negative pole material.
Preparation method of the present invention has generated RESEARCH OF PYROCARBON in the heat treatment of step (3), in the heat treatment of step (4), generated carbon nano-tube, and the catalyst that step (1) adds in dry run can so that the carbon nano-tube of follow-up vapour deposition all can be grown on internal voids and the surface of silicon-carbon microballoon, combination tightr.The generation of carbon nano-tube and RESEARCH OF PYROCARBON has solved the volumetric expansion effect height of elemental silicon in the prior art, first charge-discharge efficiency is low and the problem of stable circulation performance difference, main cause is: at first, carbon nano-tube and RESEARCH OF PYROCARBON can effectively be alleviated the volumetric expansion effect of silicon in the removal lithium embedded process, suppress the efflorescence of active material; Secondly, carbon nano-tube and RESEARCH OF PYROCARBON can provide the passage of electric transmission, can improve the conductivity of active material silicon.
The lithium battery silicon-carbon nanotube composite negative pole material of preparation method's gained of the present invention has outstanding chemical property: first charge-discharge efficiency height, specific capacity height and good cycle.The nano-silicon of this lithium battery silicon-carbon nanotube composite negative pole material is embedded in the carbon net matrix of organic carbon source pyrolysis formation, and inner and surperficial all growth of matrix has unordered carbon nano-tube, and particle size is less than 5 μ m.
Preferably, the mass ratio of the organic carbon source described in the step (1) and nano-silicon is (0.4～9): 1; Catalyst amount is 1%～3% of nano-silicon quality described in the step (1), and dispersant dosage is 1% of nano-silicon quality; Described in the step (1) in the nano-silicon liquid nano-silicon mass content be 10%, the particle diameter of nano-silicon is 50～200nm.
When having given play to the high power capacity characteristics of nano-silicon, also can keep good cycle performance, the organic carbon source described in the step (1) and nano-silicon are by (0.4～9): 1 mass ratio carries out proportioning, and the particle diameter of nano-silicon is preferably 50～200nm.
Preferably, the organic carbon source described in the step (1) is phenolic resins, citric acid or hard pitch; Catalyst described in the step (1) is nickel acetate, nickelous sulfate or ferric acetate; Solvent described in the step (1) is one or both in absolute ethyl alcohol, ethylene glycol and the oxolane; Dispersant described in the step (1) is polyvinylpyrrolidone, polymine, Polyetherimide or lauryl sodium sulfate.
The solvent that above-mentioned steps (1) is used has can dissolve organic carbon source and catalyst or dispersant and have that boiling point is low, the characteristic of volatile characteristic fully, and the amount of solvent can be dissolved in organic carbon source and catalyst or dispersant in the solvent at least fully.
Dispersant in this external step (1) is all for having the oleophylic hydrophilic radical simultaneously, and the material that surface tension is significantly descended, and can effectively stop the reunion between the silicon nanoparticle, plays good dispersion effect; Ultrasonic purpose is that supersonic frequency does not need special restriction to did not influence of the present invention for better dispersing nanometer silicon in step (1).
Preferably, drying mode described in the step (2) is for to carry out drying by the closed cycle spray dryer, the rotating speed of atomizer is 20000～35000r/min in the described closed cycle spray dryer, and its inlet temperature is 105～120 ℃, and outlet temperature is 80～90 ℃; Mixing speed described in the step (2) is 500～2000r/min, and described solvent is absolute ethyl alcohol, ethylene glycol or oxolane.
Compare with common drying mode, use the powder of closed cycle spray drying preparation, nano-silicon can be scattered in the organic carbon source uniformly, and powder granule size homogeneous comparatively.And the solid masses content of mixed slurry is 10～30%, and this solids content neither can be too high and cause charging aperture to stop up, again can too low waste long time, be more suitable for the closed cycle spray drying process.
Preferably, the inert gas described in the step (3) is the nitrogen of purity 99.999% or the argon gas of purity 99.999%, and its heating rate is 1～5 ℃/min.
Preferably, the gaseous state organic carbon source is more than one in acetylene, methane, natural gas and the liquefied petroleum gas in the gaseous mixture described in the step (4), and inert gas is nitrogen or argon gas, and the mass ratio of gaseous state organic carbon source and inert gas is 3:7～8:2; Wherein the heating rate of gaseous mixture is 1～5 ℃/min.
Above-mentioned lithium battery silicon-carbon nanotube composite negative pole material is applied to the preparation of anode plate for lithium ionic cell; The preparation method of described anode plate for lithium ionic cell may further comprise the steps:
(1) lithium battery silicon-carbon nanotube composite negative pole material, binding agent and conductive agent are pressed (70～80): (20～10): 10 weight ratio is mixed, and obtains slurry;
(2) slurry that step (1) is obtained is coated on the Copper Foil, and dry 5～24h, and roll-in then, section obtain described anode plate for lithium ionic cell.
Preferably, the weight ratio of described lithium battery silicon-carbon nanotube composite negative pole material, binding agent and conductive agent is 80:10:10.
Preferably, described binding agent is binding agent LA132 or polyvinylidene fluoride; Described conductive agent is conductive black, conducting liquid or nano-sized carbon.
Described binding agent LA132 is a water system binding agent that the happy company in mattress ground, Chengdu produces; Described conducting liquid is the conducting liquid of commercially available routine, and the particle diameter of described nano-sized carbon is less than 100nm.
Preferably, the coating thickness described in the step (2) is 100～180 microns; The thickness of described roll-in is 75～150 microns; Described drying mode is vacuumize, and its temperature is 50～100 ℃.
In the preparation process of lithium battery silicon-carbon nanotube composite negative pole material of the present invention, conditions such as the kind of applied dispersant, organic carbon source, presoma sintering temperature and spray-dired technology all can produce a very large impact structure, size and the pattern of prepared silicon-carbon nanotube composite negative pole material, and the structure of product, size and pattern can produce influence greatly to the performance of lithium cell cathode material, and then have influence on first charge-discharge efficiency, specific capacity and the cycle performance of lithium battery silicon-carbon nanotube composite negative pole material.Therefore, in the present invention, inventor preferred by to process conditions such as the kind of dispersant kind, organic carbon source, spray-dired technology, sintering temperatures obtained the lithium battery silicon-carbon nanotube composite negative pole material of a kind of first charge-discharge efficiency height, specific capacity height, good cycle.
Find that by detecting the lithium battery silicon-carbon nanotube composite negative pole material of preparation method's gained of the present invention specific capacity first reaches more than the 2000mAh/g, being higher than present business-like graphite theoretical capacity far away is 372mAh/g.
Compared with prior art the present invention has following advantage and beneficial effect:
(1) lithium battery silicon-carbon nanotube composite negative pole material preparation technology of the present invention simple, with low cost, be suitable for suitability for industrialized production.
(2) chemical property of lithium battery silicon-carbon nanotube composite negative pole material of the present invention is outstanding, the first charge-discharge efficiency height, the specific capacity height (reaches more than the 2000mAh/g first, present business-like graphite theoretical capacity is 372mAh/g), good cycle, solved successfully that the efficient first that silicon exists is low, irreversible capacity loss big and the problem of poor electric conductivity when the application of actual fabrication lithium ion battery negative.
Description of drawings
Fig. 1 is the SEM collection of illustrative plates of the lithium battery silicon-carbon nanotube composite negative pole material of embodiment 1 preparation;
Fig. 2 is the XRD collection of illustrative plates of the lithium battery silicon-carbon nanotube composite negative pole material of embodiment 1 preparation;
Fig. 3 is the charge-discharge performance figure of simulated battery 1;
Fig. 4 is the charge-discharge performance figure of simulated battery 2;
Fig. 5 is the charge-discharge performance figure of simulated battery 3;
Fig. 6 is the charge-discharge performance figure of simulated battery 4.
Embodiment
The present invention is described in further detail below in conjunction with embodiment and accompanying drawing, but embodiments of the present invention are not limited thereto.
Embodiment 1
(1) preparation lithium battery silicon-carbon nanotube composite negative pole material, concrete steps are as follows:
(1) takes by weighing 14.25g citric acid (C respectively
6H
8O
7H
2O) and 0.05g nickel acetate (C
4H
6O
4NiH
2O) be dissolved in the 100mL absolute ethyl alcohol, obtain solution A; Take by weighing and join in the 20g nano-silicon liquid (silicone content is 2g) after 0.02g polyethylene of dispersing agent pyrrolidones is dissolved in absolute ethyl alcohol, and ultrasonic 30min obtains solution B, solution B is poured in the solution A, obtain mixed slurry;
(2) mixed slurry that under the mixing speed of 1000r/min step (1) is obtained stirs 1h, adding absolute ethyl alcohol then regulates the solids content of mixed slurry and is about the 15%(quality), under stirring condition, mixed slurry pumped by peristaltic pump and carry out centrifugal closed cycle spray drying to atomizer and obtain precursor A; Wherein charging rate is 15mL/min, and inlet temperature is 105 ℃, and outlet temperature is 80 ℃, and the atomizer rotating speed is 30000r/min;
(3) precursor A of step (2) gained is put into crucible, be transferred in the tube furnace, be incubated 3h after feeding the nitrogen of purity 99.999% and being warming up to 500 ℃ with the speed of 3 ℃/min, naturally cool to room temperature then, obtain precursor B;
(4) transfer to the precursor B of step (3) gained in the tube furnace again, feed the gaseous mixture (wherein the nitrogen mass content is 30%) of acetylene and nitrogen, and be warming up to 700 ℃ and be incubated 3h with the speed of 3 ℃/min, naturally cool to room temperature then, obtain described lithium battery silicon-carbon nanotube composite negative pole material.
(2) product that will finally obtain carries out the SEM pattern and detects mutually with the XRD thing, SEM pattern testing result as shown in Figure 1, XRD thing phase testing result is as shown in Figure 2.Can see from Fig. 1, cover unordered tube at the silicon-carbon microsphere surface.And can see that from the XRD thing phase testing result of Fig. 2 the standard card JCPDSno.041-1487 of this collection of illustrative plates and carbon nano-tube and the standard card JCPDSno.027-1402 of silicon match, show that having generated unordered tube in the product that detects is carbon nano-tube.
(3) preparation lithium battery cathode plate, concrete steps are as follows:
(1) be 15% with the prepared lithium battery silicon-carbon of 1.875g step () nanotube composite negative pole material, 2.5g binding agent LA132(binding agent solids content) and the conductive black of 0.25g evenly mix the furnishing slurry;
(2) slurry that step (1) is made is coated on the Copper Foil, and coating thickness is 100 microns, and is prepared into anode plate for lithium ionic cell 1 in 110 ℃ of following vacuumizes 8 hours, roll-in (thickness is 80 microns).
Embodiment 2
(1) preparation lithium battery silicon-carbon nanotube composite negative pole material, concrete steps are as follows:
(1) takes by weighing 2.85g phenolic resins and 0.05g nickel acetate (C respectively
4H
6O
4NiH
2O) be dissolved in the 100mL absolute ethyl alcohol, obtain solution A; Take by weighing and join in the 40g nano-silicon liquid (silicone content is 4g) after 0.04g polyethylene of dispersing agent imines is dissolved in absolute ethyl alcohol, and ultrasonic 60min obtains solution B, solution B is poured in the solution A, obtain mixed slurry;
(2) mixed slurry that under the mixing speed of 1200r/min step (1) is obtained stirs 1h, adding absolute ethyl alcohol then regulates the solids content of mixed slurry and is about the 20%(quality), mixed slurry pumped by peristaltic pump carry out centrifugal closed cycle spray drying to the atomizer and obtain precursor A; Wherein charging rate is 15mL/min, and inlet temperature is 110 ℃, and outlet temperature is 82 ℃, and the atomizer rotating speed is 20000r/min;
(3) precursor A of step (2) gained is put into crucible, be transferred in the tube furnace, be incubated 5h after feeding the argon gas of purity 99.999% and being warming up to 300 ℃ with the speed of 4 ℃/min, naturally cool to room temperature then, obtain precursor B;
(4) transfer to the precursor B of step (3) gained in the tube furnace again, feed the gaseous mixture (wherein the argon gas mass content is 50%) of methane and argon gas, and be warming up to 500 ℃ and be incubated 5h with the speed of 2 ℃/min, naturally cool to room temperature then, obtain described lithium battery silicon-carbon nanotube composite negative pole material.
(2) preparation lithium battery cathode plate, concrete steps are as follows:
(1) be 15% with the prepared lithium battery silicon-carbon of 1.875g step () nanotube composite negative pole material, 2.5g binding agent LA132(binding agent solids content) and the conductive black of 0.25g evenly mix the furnishing slurry;
(2) slurry that step (1) is made is coated on the Copper Foil, and coating thickness is 100 microns, and is prepared into anode plate for lithium ionic cell 2 in 110 ℃ of following vacuumizes 8 hours, roll-in (thickness is 80 microns).
Embodiment 3
(1) preparation lithium battery silicon-carbon nanotube composite negative pole material, concrete steps are as follows:
(1) takes by weighing the 2.45g hard pitch respectively and the 0.05g ferric acetate is dissolved in oxolane and the absolute ethyl alcohol, obtain solution A; Take by weighing and join in the 40g nano-silicon liquid (silicone content is 4g) after 0.04g dispersant Polyetherimide is dissolved in absolute ethyl alcohol, and ultrasonic 1.5h obtains solution B, solution B is poured in the solution A, obtain mixed slurry;
(2) mixed slurry that under the mixing speed of 800r/min step (1) is obtained stirs 2h, adding oxolane then regulates the solids content of mixed slurry and is about the 25%(quality), mixed slurry pumped by peristaltic pump carry out centrifugal closed cycle spray drying to the atomizer and obtain precursor A; Wherein charging rate is 15mL/min, and inlet temperature is 115 ℃, and outlet temperature is 85 ℃, and the atomizer rotating speed is 35000r/min;
(3) precursor A of step (2) gained is put into crucible, be transferred in the tube furnace, be incubated 1h after feeding the nitrogen of purity 99.999% and being warming up to 900 ℃ with the speed of 5 ℃/min, naturally cool to room temperature then, obtain precursor B;
(4) transfer to the precursor B of step (3) gained in the tube furnace again, feed the gaseous mixture (wherein the nitrogen mass content is 70%) of natural gas and nitrogen, and be warming up to 900 ℃ and be incubated 1h with the speed of 5 ℃/min, naturally cool to room temperature then, obtain described lithium battery silicon-carbon nanotube composite negative pole material.
(2) preparation lithium battery cathode plate, concrete steps are as follows:
(1) be 15% with the prepared lithium battery silicon-carbon of 1.875g step () nanotube composite negative pole material, 2.5g binding agent LA132(binding agent solids content) and the conductive black of 0.25g evenly mix the furnishing slurry;
(2) slurry that step (1) is made is coated on the Copper Foil, and coating thickness is 100 microns, and is prepared into anode plate for lithium ionic cell 3 in 110 ℃ of following vacuumizes 8 hours, roll-in (thickness is 80 microns).
Embodiment 4(comparative example)
(1) preparation lithium battery silicon-carbon composite cathode material, concrete steps are as follows:
(1) takes by weighing 14.25g citric acid (C respectively
6H
8O
7H
2O) and the 0.05g nickel acetate be dissolved in the 100mL absolute ethyl alcohol, obtain solution A; Take by weighing and join in the 20g nano-silicon liquid (silicone content is 2g) after 0.02g dispersant lauryl sodium sulfate is dissolved in absolute ethyl alcohol, and ultrasonic 2h obtains solution B, solution B is poured in the solution A, obtain mixed slurry;
(2) mixed slurry that under the mixing speed of 2000r/min step (1) is obtained stirs 2h, add absolute ethyl alcohol then and regulate the solids content of mixed slurry and be about 15%, mixed slurry is pumped by peristaltic pump carried out centrifugal closed cycle spray drying to the atomizer and obtain precursor A; Wherein charging rate is 15mL/min, and inlet temperature is 120 ℃, and outlet temperature is 90 ℃, and the atomizer rotating speed is 30000r/min;
(3) precursor A of step (2) gained is put into crucible, be transferred in the tube furnace, be incubated 3h after feeding the nitrogen of purity 99.999% and being warming up to 500 ℃ with the speed of 3 ℃/min, naturally cool to room temperature then, obtain the lithium battery silicon-carbon composite cathode material.
(2) preparation lithium battery cathode plate, concrete steps are as follows:
(1) be 15% with the prepared lithium battery silicon-carbon of 1.875g step () nanotube composite negative pole material, 2.5g binding agent LA132(binding agent solids content) and the conductive black of 0.25g evenly mix the furnishing slurry;
(2) slurry that step (1) is made is coated on the Copper Foil, and coating thickness is 100 microns, and is prepared into anode plate for lithium ionic cell 4 in 110 ℃ of following vacuumizes 8 hours, roll-in (thickness is 80 microns).
In above-described embodiment 1～4 in the preparation of lithium battery cathode plate, binding agent all is chosen as binding agent LA138 and conductive agent is conductive black, the weight ratio of each raw material is identical, and it is all identical with roll-in thickness to the lithium battery cathode plate coating thickness, only compare for the effect to above-described embodiment better, rather than to binding agent and conductive agent kind, raw material weight than and the restriction of lithium battery cathode plate thickness.
Effect embodiment
With embodiment 1 to 4 resulting anode plate for lithium ionic cell respectively with the three component mixed solvent EC:DMC:EMC=1:1:1(volume ratio v/v/v of 1mol/L LiPF6), solution is electrolyte, microporous polypropylene membrane is barrier film, and the lithium sheet is for to be assembled into simulated battery 1～4 to electrode.
Simulated battery is carried out 1～4 carries out the cycle performance test, with LAND CT2001A(Wuhan Jin Nuo Electronics Co., Ltd.) be battery test system, carry out the constant current charge-discharge test with the current density of 100mA/g, voltage range is 0.01～2.0V.
Fig. 3 is the charge-discharge performance figure of simulated battery 1, the lithium ion battery specific capacity height of simulated battery 1 as seen from the figure, and discharge first and charge ratio capacity are respectively and are 2168.7mAh/g and 1584.1mAh/g, and cycle efficieny is 73% first.Circulated for 50 weeks, specific capacity also remains on more than the 1172mAh/g, good cycle.
Fig. 4 is the charge-discharge performance figure of simulated battery 2, the lithium ion battery specific capacity height of simulated battery 2 as seen from the figure, and discharge first and charge ratio capacity are respectively and are 2106.8mAh/g and 1567.3mAh/g, and cycle efficieny is 74% first.Circulated for 50 weeks, specific capacity also remains on more than the 1137mAh/g, good cycle.
Fig. 5 is the charge-discharge performance figure of simulated battery 3, the lithium ion battery specific capacity height of simulated battery 3 as seen from the figure, and discharge first and charge ratio capacity are respectively and are 2005.3mAh/g and 1440.3mAh/g, and cycle efficieny is 72% first.Circulated for 50 weeks, specific capacity also remains on more than the 1067mAh/g, good cycle.
Fig. 6 is the charge-discharge performance figure of simulated battery 4, and simulated battery 4 discharge and charge ratio capacity first is respectively and is 2201.3mAh/g and 1674.4mAh/g as seen from the figure, and cycle efficieny is 76% first.Circulated for 50 weeks, specific capacity only has 580mAh/g, and cycle performance is relatively poor.
The reason that the charge-discharge performance of simulated battery 1～3 is better than simulated battery 4 is, among the preparation method of embodiment 1 to 3, in the heat treatment of step (3), generated RESEARCH OF PYROCARBON, in the heat treatment of step (4), generated carbon nano-tube, and the catalyst that step (1) adds in dry run can so that the carbon nano-tube of follow-up vapour deposition all can be grown on internal voids and the surface of silicon-carbon microballoon, combination tightr.And in the anode plate for lithium ionic cell 1～3 in the contained silicon-carbon nanometer tube composite materials unordered carbon nano-tube and RESEARCH OF PYROCARBON played very crucial effect: at first, carbon nano-tube and RESEARCH OF PYROCARBON can effectively be alleviated the volumetric expansion effect of silicon in the removal lithium embedded process, suppress the efflorescence of active material; Secondly, carbon nano-tube and RESEARCH OF PYROCARBON can provide the passage of electric transmission, can improve the conductivity of active material silicon.
Above-described embodiment is preferred implementation of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spiritual essence of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. the preparation method of a lithium battery silicon-carbon nanotube composite negative pole material is characterized in that, comprises the steps:
(1) organic carbon source and catalyst are dissolved in obtain solution A in the solvent; Other joins it in nano-silicon liquid after getting solvent and adding the dispersant dissolving, and ultrasonic 0.5～2h obtains solution B; Then solution B is joined in the solution A, obtain mixed slurry; Wherein solvent is ethanol or ethylene glycol in the nano-silicon liquid;
(2) mixed slurry that step (1) is obtained stirs 0.5～3h, adds solid masses content to 10～30% of solvent adjustment mixed slurry then, with the dry powder process of mixed slurry, obtains precursor A again;
(3) precursor A that step (2) is obtained is warming up to 300～700 ℃ in inert gas, is cooled to room temperature behind insulation 1～5h, obtains precursor B;
(4) precursor B that step (3) is obtained is warming up to 500～900 ℃ in the gaseous mixture of gaseous state organic carbon source and inert gas, is cooled to room temperature behind insulation 0.5～5h, obtains described lithium battery silicon-carbon nanotube composite negative pole material.
2. preparation method according to claim 1, it is characterized in that, the mass ratio of the organic carbon source described in the step (1) and nano-silicon is (0.4～9): 1, and described catalyst amount is 1%～3% of nano-silicon quality, dispersant dosage is 1% of nano-silicon quality; The nano-silicon mass content is 10% in the nano-silicon liquid described in the step (1), and the particle diameter of nano-silicon is 50～200nm.
3. preparation method according to claim 1 is characterized in that, the organic carbon source described in the step (1) is phenolic resins, citric acid or hard pitch; Catalyst described in the step (1) is nickel acetate, nickelous sulfate or ferric acetate; Solvent described in the step (1) is one or both in absolute ethyl alcohol, ethylene glycol, oxolane and the acetone; Dispersant described in the step (1) is polyvinylpyrrolidone, polymine, Polyetherimide, lauryl sodium sulfate or silane coupler.
4. preparation method according to claim 1, it is characterized in that, drying mode described in the step (2) is for to carry out drying by the closed cycle spray dryer, the rotating speed of atomizer is 20000～35000r/min in the described closed cycle spray dryer, its inlet temperature is 105～120 ℃, and outlet temperature is 80～90 ℃;
Mixing speed described in the step (2) is 500～2000r/min, and described solvent is absolute ethyl alcohol, ethylene glycol or oxolane.
5. preparation method according to claim 1 is characterized in that, the inert gas described in the step (3) is the nitrogen of purity 99.999% or the argon gas of purity 99.999%, and its heating rate is 1～5 ℃/min.
6. preparation method according to claim 1, it is characterized in that, the gaseous state organic carbon source is more than one in acetylene, methane, natural gas and the liquefied petroleum gas in the gaseous mixture described in the step (4), inert gas is nitrogen or argon gas, and the mass ratio of gaseous state organic carbon source and inert gas is 3:7～8:2; Wherein the heating rate of gaseous mixture is 1～5 ℃/min.
7. the application of a lithium battery silicon-carbon nanotube composite negative pole material is characterized in that, described lithium battery silicon-carbon nanotube composite negative pole material is used for the preparation of anode plate for lithium ionic cell; The preparation method of described anode plate for lithium ionic cell may further comprise the steps:
(1) lithium battery silicon-carbon nanotube composite negative pole material, binding agent and conductive agent are pressed (70～80): (20～10): 10 weight ratio is mixed, and obtains slurry;
(2) slurry that step (1) is obtained is coated on the Copper Foil, and dry 5～24h, and roll-in then, section obtain described anode plate for lithium ionic cell.
8. the application of lithium battery silicon-carbon nanotube composite negative pole material according to claim 7 is characterized in that, the weight ratio of described lithium battery silicon-carbon nanotube composite negative pole material, binding agent and conductive agent is 80:10:10.
9. the application of lithium battery silicon-carbon nanotube composite negative pole material according to claim 7 is characterized in that, described binding agent is binding agent LA132 or polyvinylidene fluoride; Described conductive agent is conductive black, conducting liquid or nano-sized carbon.
10. the application of lithium battery silicon-carbon nanotube composite negative pole material according to claim 7 is characterized in that, the coating thickness described in the step (2) is 100～180 microns; The thickness of described roll-in is 75～150 microns; Described drying mode is vacuumize, and its temperature is 50～100 ℃.
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