CN104282894B - A kind of preparation method of porous Si/C complex microsphere - Google Patents
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Abstract
The present invention relates to the preparation method of a kind of porous Si/C complex microsphere, belong to technical field of lithium ion battery electrode.Processing step includes: using the sodium alginate aqueous solution of dispersed silicon as aqueous phase, using the isooctane solution dissolved with emulsifying agent as oil phase, both are under agitation made to emulsify uniformly, it is subsequently added coagulant and makes sodium alginate drop cross-linked gel, freeze-drying again, carbonization obtains porous Si/C complex microsphere the most under an inert atmosphere.The porous Si/C complex microsphere that a process for preparing is used as lithium ion battery negative material and has good electrochemical cycle stability and high rate performance.The method have the advantages that, it is not necessary to expensive instrument and equipment, technique is simple, easy to operate, it is simple to large-scale production.
Description
Technical field
The present invention relates to the preparation method of a kind of porous Si/C complex microsphere, belong to technical field of lithium ion battery electrode.
Background technology
The fast development of electric automobile is the most urgent to the demand of height ratio capacity, long circulation life and high security power lithium-ion battery.In lithium ion battery negative material, with the incomparable capacity advantage of other material, (theoretical specific capacity is up to 4200 mAh × g to silicon-1) and high security obtained the extensive concern of researcher.But silicon-based anode volumetric expansion in cyclic process is up to 300%, easily cause material efflorescence, lose and make electrical contact with collector, cause its cycle performance to decline rapidly.One of method improving silicon based anode material performance at present is by silicon materials nanometer, prepares nanosphere, nanotube, nanofiber etc.；Two is to be placed in cushioning frame by silicon, disperses and buffer the volumetric expansion of silicon, wherein material with carbon element owing to its Volume Changes in charge and discharge process is relatively small, cyclical stability and electric conductivity more excellent, be silicon comparatively ideal cushioning frame material.
At document (1) Nature Materials,
2010, in 9:353-358, A. burnt dendroid carbon black granules is skeleton by Magasinki et al., utilize silane for silicon source at chemical vapor deposited silicon nano particle above, recycling propylene gas does carbon source, secondary chemical vapor carbon deposition, carries out granulation to primary particle simultaneously, i.e. obtains the silicon-carbon complex microsphere that average grain diameter is 20 microns.This material has good electrochemical cycle stability for lithium ion battery negative pole, and after circulating 100 weeks under the multiplying power of 1C, specific capacity can also be stablized at 1500 mAh × g-1.But the preparation process of this material relates to twice chemical gaseous phase deposition, and cost is high and power consumption is big, and using silane is gas silicon source, and toxicity is big, inflammable and explosive, and operating procedure is complicated simultaneously.
At document (2) The Journal of
Physical Chemistry C, 2011, in 115:14148-14154, Ya-Xia Yin et al. is prepared for Si-C composite material using sodium alginate as carbon source, owing to containing carboxyl in sodium alginate molecule, can form hydrogen bond with the hydroxyl of silicon face, it is beneficial to the dispersion of nano silica fume, it addition, there is high conductance after sodium alginate carbonization, there is loose structure simultaneously.Its preparation method is to utilize electrojet instrument to be ejected in copper chloride solution by the mixed liquor of silicon and sodium alginate to promote its quick-gelatinizing, and carbonization again after freeze-drying obtains the silicon-carbon complex microsphere that average grain diameter is 50 microns.This material is used for lithium ion battery negative, at 50 mA × g-1Current density under circulate 50 weeks after capacity from 2500 mAh × g-1Drop to 1000 mAh × g-1.The method needs electrojet instrument, and productivity is low, power consumption is high, adds production cost.
Summary of the invention
The method that it is an object of the invention to provide the preparation porous Si/C complex microsphere of a kind of simplicity, it is characterized in that, using the sodium alginate aqueous solution of dispersed silicon as aqueous phase, using the isooctane solution dissolved with emulsifying agent as oil phase, the two emulsification is made uniformly at stirring condition, being subsequently added coagulant and make sodium alginate drop cross-linked gel, then freeze-drying, carbonization obtains porous Si/C complex microsphere the most under an inert atmosphere.The technological process of the inventive method is as it is shown in figure 1, include step in detail below.
(1) preparation mass concentration be the sodium alginate aqueous solution of 5 ~ 10 g/L as aqueous phase, weigh silica flour according to the ratio that mass ratio is 1:2 ~ 4:5 of silica flour Yu sodium alginate, join in sodium alginate aqueous solution, stir make it be uniformly dispersed；Preparing the sorbester p17 isooctane solution that mass concentration is 30 ~ 50 g/L is 1:2 ~ 2:1 as oil phase, aqueous phase with the volume ratio of oil phase；Under the mixing speed of 500 ~ 1500 revs/min, in sorbester p17 isooctane solution, instill the sodium alginate soln being dispersed with silicon, emulsify 10 ~ 30 minutes；Then instill the Tween 80 aqueous solution that mass concentration is 40 ~ 70 g/L accounting for aqueous phase with oil phase cumulative volume 1% ~ 3%, continue emulsification 5 ~ 10 minutes；Then the copper chloride coagulant aqueous solution that mass concentration is 100 ~ 180 g/L accounting for aqueous phase with oil phase cumulative volume 1% ~ 5% is instilled so that it is gel solidification 10 ~ 30 minutes；Centrifugation, washed product, to remove isooctane, is placed in flash freezing in liquid nitrogen, then freeze-drying obtains compound powder in 20 ~ 30 hours by absolute ethanol washing 3 ~ 5 times.
(2) compound powder step (1) obtained is under an inert atmosphere, with 5 ~ 10oThe ramp of C/ minute is to 800 ~ 1000oC carburizing reagent 2 ~ 4 hours, then cools to room temperature with the furnace.One during wherein inert gas is nitrogen or argon gas.
(3) it is that 1:200 ~ 1:100 is placed in the hydrofluoric acid solution that mass fraction is 5 ~ 10% by the carbonized product of step (2) according to solid-to-liquid ratio, soak 0.5 ~ 1.5 hour, obtain suspension, centrifugation, absolute ethanol washing 3 ~ 5 times to remove hydrofluoric acid, 50 ~ 100oC is vacuum dried 10 ~ 20 hours, i.e. obtains porous Si/C complex microsphere.
The XRD spectra of porous Si/C complex microsphere is as in figure 2 it is shown, in material in addition to containing silicon and carbon, possibly together with the cuprous oxide being transformed by coagulant copper chloride；Using Germany's Supra 55 type field emission microscopy observation sample topography, the stereoscan photograph of porous Si/C complex microsphere is as it is shown on figure 3, compound is spheric granules, and particle diameter is between 2-15 micron, and silicon grain adheres to the surfaces externally and internally of the carbon film of softness；Using NEC's company JEM-2100 type high resolution transmission electron microscopy to observe the structure of silicon-carbon complex microsphere as shown in Figure 4, nano silicon particles is inlayed or adheres on carbon film.
Porous Si/C complex microsphere the inventive method synthesized, as lithium ion battery negative material, is mixed by the mass ratio of 60:30:10 with commercially available acetylene black conductor and sodium alginate binding agent, is coated on copper foil of affluxion body, in vacuum drying oven 80oC is dried, and compressing tablet is to the thickness of 30 ~ 70 mm, prepares the electrode slice of a diameter of 1 cm with sheet-punching machine, in 120oC vacuum (< 10 Pa) it is dried 24 hours.Using metal lithium sheet as to electrode, use Celgard 2400 barrier film, 1 mol × L-1LiPF6+EC+DMC+DEC
(EC/DMC/DEC volume ratio is 1:1:1) is electrolyte, at Germany M.Braun company Unlab type dry argon gas glove box (H2O < 1
ppm, O2< 1 ppm) in be assembled into experimental cell, use Wuhan indigo plant electricity CT2001A type cell tester to carry out electrochemical property test, discharge and recharge blanking voltage scope is 0.01 V ~ 1.5 V (vs. Li+/ Li), test temperature is 25oC, as shown in Figure 5 and Figure 6, the specific capacity head week of porous Si/C complex microsphere can reach 2280.5 mAh × g to test result-1, efficiency is 67% first, at 200 mA × g-1Current density under circulate 100 weeks after specific capacity still can reach 1100 mAh × g-1, and coulombic efficiency is always held at more than 98%；This material also has the high rate performance of excellence, at 2 A × g-1Current density under, specific capacity remains to reach 650 mAh × g-1。
Distinguishing feature and the advantage of the inventive method are: use simple emulsification-gelation process can obtain the Si/C complex microsphere with loose structure, use it for lithium ion battery negative material and have good electrochemical cycle stability and high rate performance.The inventive method need not the instrument and equipment of costliness, and technique is simple, easy to operate, it is simple to large-scale production.
Accompanying drawing explanation
Fig. 1 is the process flow diagram using the inventive method to prepare porous Si/C complex microsphere.
Fig. 2 is the XRD spectra of the porous Si/C complex microsphere of embodiment 1 preparation.Abscissa is angle, and unit is: degree (o)；Ordinate is diffracted intensity, and unit is: absolute unit (a.u.).
Fig. 3 be embodiment 1 preparation porous Si/C complex microsphere sweep transmitting stereoscan photograph.
Fig. 4 is the high-resolution-ration transmission electric-lens photo of the porous Si/C complex microsphere of embodiment 1 preparation.
Fig. 5 is electrochemistry cycle performance and the coulombic efficiency curve of the porous Si/C complex microsphere of embodiment 1 preparation.Abscissa is circulating cycle number, and unit is: week；Left side ordinate is specific discharge capacity, and unit is: MAH × gram-1 (mAh×g-1), right side ordinate is coulombic efficiency, and unit is: percentage (%).The specific discharge capacity of curve a porous Si/C complex microsphere and the relation curve of circulating cycle number；The coulombic efficiency of curve b porous Si/C complex microsphere and the relation curve of circulating cycle number.
Fig. 6 is the high rate performance curve of the porous Si/C complex microsphere of embodiment 1 preparation.Abscissa is circulating cycle number, and unit is: week；Ordinate is specific discharge capacity, and unit is: MAH × gram-1 (mAh×g-1)。
Detailed description of the invention
Embodiment 1: weigh 0.3 g sodium alginate and 0.17 g silica flour joins in beaker, add 60 mL deionized waters, magnetic agitation makes it be uniformly dispersed, weigh 1.2 g sorbester p17s to be dissolved in 40 mL isooctane solutions simultaneously, weigh 0.09 g Tween 80 to be dissolved in the 2 mL aqueous solution, weigh 0.269 gCuCl2It is dissolved in 2 mL water.Sorbester p17 isooctane solution is proceeded in there-necked flask, under the mechanical agitation of 500 revs/min, instills the sodium alginate soln being dispersed with silicon, emulsify 15 minutes, then instill the Tween 80 aqueous solution, be further continued for emulsifying 5 minutes, then instill CuCl2The aqueous solution so that it is gel solidification 15 minutes.By cured product centrifugation, and with absolute ethanol washing 4 times to remove isooctane, cured product is placed in flash freezing in liquid nitrogen, then moves to freeze drier is dried 25 hours.
Above-mentioned dried compound powder is laid in aluminum oxide porcelain boat, is placed in the thermal treatment zone of tube furnace, in a nitrogen atmosphere, according to 5oThe heating rate of C/ minute is raised to 800oC, is incubated and carries out carbonization in 4 hours.
Being placed in the hydrofluoric acid solution that 30 mL mass fractions are 5% by the silicon-carbon compound powder obtained after the 0.24 above-mentioned carbonization of g, soak 0.5 hour, centrifugation, absolute ethanol washing 4 times, to remove hydrofluoric acid, is subsequently placed in 50oThe vacuum drying oven of C is dried 20 hours, i.e. obtains porous Si/C complex microsphere.
The XRD spectra of porous Si/C complex microsphere is as in figure 2 it is shown, in material in addition to containing silicon and carbon, possibly together with the cuprous oxide being transformed by coagulant copper chloride；Using Germany's Supra 55 type field emission microscopy observation sample topography, the stereoscan photograph of porous Si/C complex microsphere is as it is shown on figure 3, compound is spheric granules, and particle diameter is between 2-15 micron, and silicon grain adheres to the surfaces externally and internally of the carbon film of softness；Using NEC's company JEM-2100 type high resolution transmission electron microscopy to observe the structure of silicon-carbon complex microsphere as shown in Figure 4, nano silicon particles is inlayed or adheres on carbon film.
Porous Si/C complex microsphere the inventive method synthesized, as lithium ion battery negative material, is mixed by the mass ratio of 60:30:10 with commercially available acetylene black conductor and sodium alginate binding agent, is coated on copper foil of affluxion body, in vacuum drying oven 80oC is dried, and compressing tablet is to the thickness of 30 ~ 70 mm, prepares the electrode slice of a diameter of 1 cm with sheet-punching machine, in 120oC vacuum (< 10 Pa) it is dried 24 hours.Using metal lithium sheet as to electrode, use Celgard 2400 barrier film, 1 mol × L-1LiPF6+EC+DMC+DEC
(EC/DMC/DEC volume ratio is 1:1:1) is electrolyte, at Germany M.Braun company Unlab type dry argon gas glove box (H2O < 1
ppm, O2< 1 ppm) in be assembled into experimental cell, use Wuhan indigo plant electricity CT2001A type cell tester to carry out electrochemical property test, discharge and recharge blanking voltage scope is 0.01 V ~ 1.5 V (vs. Li+/ Li), test temperature is 25oC, as shown in Figure 5 and Figure 6, the specific capacity head week of porous Si/C complex microsphere can reach 2280.5 mAh × g to test result-1, efficiency is 67% first, at 200 mA × g-1Current density under circulate 100 weeks after specific capacity still can reach 1100 mAh × g-1, and coulombic efficiency is always held at more than 98%；This material also has the high rate performance of excellence, at 2 A × g-1Current density under, specific capacity remains to reach 650 mAh × g-1。
Embodiment 2: weigh 0.3 g sodium alginate and 0.2 g silica flour joins in beaker, add 60 mL deionized waters, magnetic agitation makes it be uniformly dispersed, weigh 2.4 g sorbester p17s to be dissolved in 60 mL isooctane solutions simultaneously, weigh 0.17 g Tween 80 to be dissolved in the 3 mL aqueous solution, weigh 0.269 gCuCl2It is dissolved in 2.5 mL water.Sorbester p17 isooctane solution is proceeded in there-necked flask, under the mechanical agitation of 800 revs/min, instills the sodium alginate soln being dispersed with silicon, emulsify 20 minutes, then instill the Tween 80 aqueous solution, be further continued for emulsifying 8 minutes, then instill CuCl2The aqueous solution so that it is gel solidification 20 minutes.By cured product centrifugation, cured product, to remove isooctane, is placed in flash freezing in liquid nitrogen, then moves to be dried 20 hours in freeze drier by absolute ethanol washing 4 times.
Above-mentioned dried compound powder is laid in aluminum oxide porcelain boat, is placed in the thermal treatment zone of tube furnace, in a nitrogen atmosphere, according to 5oThe heating rate of C/ minute is raised to 900oC, is incubated and carries out carbonization in 3 hours.
Being placed in the hydrofluoric acid solution that 30 mL mass fractions are 10% by the silicon-carbon compound powder obtained after the 0.24 above-mentioned carbonization of g, soak 1 hour, centrifugation, absolute ethanol washing 4 times, to remove hydrofluoric acid, is placed in 70oThe vacuum drying oven of C is dried 18 hours, i.e. obtains porous Si/C complex microsphere.
Embodiment 3: weigh 0.4 g sodium alginate and 0.2 g silica flour joins in beaker, add 60 mL deionized waters, magnetic agitation makes it be uniformly dispersed, weigh 2.4 g sorbester p17s to be dissolved in 60 mL isooctane solutions simultaneously, weigh 0.17 g Tween 80 to be dissolved in the 3 mL aqueous solution, weigh 0.538 gCuCl2It is dissolved in 3 mL water.Sorbester p17 isooctane solution is proceeded in there-necked flask, under the mechanical agitation of 1000 revs/min, instills the sodium alginate soln being dispersed with silicon, emulsify 20 minutes, then instill the Tween 80 aqueous solution, be further continued for emulsifying 8 minutes, then instill CuCl2The aqueous solution so that it is gel solidification 20 minutes.By cured product centrifugation, cured product, to remove isooctane, is placed in flash freezing in liquid nitrogen, then moves to be dried 28 hours in freeze drier by absolute ethanol washing 5 times.
Above-mentioned dried compound powder is laid in aluminum oxide porcelain boat, is placed in the thermal treatment zone of tube furnace, in a nitrogen atmosphere, according to 5oThe heating rate of C/ minute is raised to 800oC, is incubated and carries out carbonization in 3 hours.
Being placed in the hydrofluoric acid solution that 30 mL mass fractions are 8% by the silicon-carbon compound powder obtained after the 0.255 above-mentioned carbonization of g, soak 1.5 hours, centrifugation, absolute ethanol washing 5 times, to remove hydrofluoric acid, is placed in 80oThe vacuum drying oven of C is dried 15 hours, i.e. obtains porous Si/C complex microsphere.
Embodiment 4: weigh 0.5 g sodium alginate and 0.35 g silica flour joins in beaker, add 60 mL deionized waters, magnetic agitation makes it be uniformly dispersed, weigh 4 g sorbester p17s to be dissolved in 80 mL isooctane solutions simultaneously, weigh 0.27 g Tween 80 to be dissolved in the 4 mL aqueous solution, weigh 0.897 gCuCl2It is dissolved in 5 mL water.Sorbester p17 isooctane solution is proceeded in there-necked flask, under the mechanical agitation of 1500 revs/min, instills the sodium alginate soln being dispersed with silicon, emulsify 30 minutes, then instill the Tween 80 aqueous solution, be further continued for emulsifying 10 minutes, then instill CuCl2The aqueous solution so that it is gel solidification 30 minutes.By cured product centrifugation, cured product, to remove isooctane, is placed in flash freezing in liquid nitrogen, moves to freeze drier and be dried 30 hours by absolute ethanol washing 5 times.
Above-mentioned dried compound powder is laid in aluminum oxide porcelain boat, is placed in the thermal treatment zone of tube furnace, in a nitrogen atmosphere, according to 5oThe heating rate of C/ minute is raised to 1000oC, is incubated and carries out carbonization in 2 hours.
Being placed in the hydrofluoric acid solution that 40 mL mass fractions are 5% by the silicon-carbon compound powder obtained after the 0.36 above-mentioned carbonization of g, soak 1.5 hours, centrifugation, absolute ethanol washing 5 times, to remove hydrofluoric acid, is placed in 90oThe vacuum drying oven of C is dried 10 hours, i.e. obtains porous Si/C complex microsphere.
Claims (3)
1. the preparation method of a porous Si/C complex microsphere, it is characterised in that comprise the technical steps that:
(1) preparation mass concentration be the sodium alginate aqueous solution of 5 ~ 10 g/L as aqueous phase, weigh silica flour according to the ratio that mass ratio is 1:2 ~ 4:5 of silica flour Yu sodium alginate, join in sodium alginate aqueous solution, stir make it be uniformly dispersed；Preparing the sorbester p17 isooctane solution that mass concentration is 30 ~ 50 g/L is 1:2 ~ 2:1 as oil phase, aqueous phase with the volume ratio of oil phase；Under the mixing speed of 500 ~ 1500 revs/min, in sorbester p17 isooctane solution, instill the sodium alginate soln being dispersed with silicon, emulsify 10 ~ 30 minutes；Then instill the Tween 80 aqueous solution that mass concentration is 40 ~ 70 g/L accounting for aqueous phase with oil phase cumulative volume 1% ~ 3%, continue emulsification 5 ~ 10 minutes；Then the coagulant aqueous solution that mass concentration is 100 ~ 180 g/L accounting for aqueous phase with oil phase cumulative volume 1% ~ 5% is instilled so that it is gel solidification 10 ~ 30 minutes；Centrifugation, washed product, to remove isooctane, is placed in flash freezing in liquid nitrogen, then freeze-drying obtains compound powder in 20 ~ 30 hours by absolute ethanol washing 3 ~ 5 times；
(2) compound powder step (1) obtained is under an inert atmosphere, with 5 ~ 10oThe ramp of C/ minute is to 800 ~ 1000oC carburizing reagent 2 ~ 4 hours, then cools to room temperature with the furnace；
(3) it is that 1:200 ~ 1:100 is placed in the hydrofluoric acid solution that mass fraction is 5 ~ 10% by the carbonized product of step (2) according to solid-to-liquid ratio, soak 0.5 ~ 1.5 hour, obtain suspension, centrifugation, absolute ethanol washing 3 ~ 5 times to remove hydrofluoric acid, 50 ~ 100oC is vacuum dried 10 ~ 20 hours, i.e. obtains porous Si/C complex microsphere.
Preparation method the most according to claim 1, it is characterised in that in step (1), described coagulant is copper chloride.
Preparation method the most according to claim 1, is characterized in that, in step (2), described inert atmosphere is the one in nitrogen or argon gas.
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| CN108565431B (en) * | 2018-04-24 | 2021-08-20 | 中国矿业大学 | Method for preparing silicon-carbon composite negative electrode material of lithium ion battery by taking konjac flour as carbon source |
| CN112802988B (en) * | 2019-11-13 | 2022-05-31 | 中国科学院大连化学物理研究所 | Electrode with chromatographic membrane structure for lithium-sulfur battery and application thereof |
| CN111755682A (en) * | 2020-07-06 | 2020-10-09 | 马鞍山科达普锐能源科技有限公司 | Silicon-carbon negative electrode material and preparation method thereof |
| CN114975943B (en) * | 2022-06-08 | 2023-06-16 | 陕西科技大学 | Preparation method for constructing gelatin/silicon nanoparticle microspheres based on emulsification self-assembly method |
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| CN103050668A (en) * | 2012-12-24 | 2013-04-17 | 中南大学 | Method for preparing Si/C composite cathode material for lithium ion battery |
| CN103107317A (en) * | 2013-01-17 | 2013-05-15 | 奇瑞汽车股份有限公司 | Si-C composite material and preparation method thereof and lithium ion battery containing same |
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| CN103050668A (en) * | 2012-12-24 | 2013-04-17 | 中南大学 | Method for preparing Si/C composite cathode material for lithium ion battery |
| CN103107317A (en) * | 2013-01-17 | 2013-05-15 | 奇瑞汽车股份有限公司 | Si-C composite material and preparation method thereof and lithium ion battery containing same |
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