CN1884056A - Carbon material and nano silicon composite materials and method for preparing same and use thereof - Google Patents
Carbon material and nano silicon composite materials and method for preparing same and use thereof Download PDFInfo
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- CN1884056A CN1884056A CNA2006100274416A CN200610027441A CN1884056A CN 1884056 A CN1884056 A CN 1884056A CN A2006100274416 A CNA2006100274416 A CN A2006100274416A CN 200610027441 A CN200610027441 A CN 200610027441A CN 1884056 A CN1884056 A CN 1884056A
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Abstract
The invention discloses a preparing method of carbon material or nanometer silicon composite material and material through composite sintering method in the electrochemical technological domain, which is characterized the following: possessing stable structure with even particle diameter less than 1 mm; avoiding agglomeration among large amount of nanometer particles due to stronger action of surface to surface; displaying high reversible capacity and excellent circulating property.
Description
Technical field
The invention belongs to technical field of electrochemistry, be specifically related to a kind of method for preparing carbon material and nano silicon composite materials, more particularly, the present invention relates to a kind of is carrier by the mixed calcining preparation with the carbon material particle, is the method for the nano composite material of coating with the nano level silica flour.The invention still further relates to the application of the carbon material and nano silicon composite materials that obtains by aforesaid method, promptly as lithium ion battery negative material.
Background technology
As everyone knows, silicon has caused increasing insider's concern as promising lithium ion battery negative material, major cause is that the termination current potential of lithium insertion silicon not only can be controlled at more than the 0.2V, and the reversible insertion amount of lithium in silicon is big, theoretical insertion amount reaches 4000mAh/g, can significantly improve the capacity and the safety performance of battery.But lithium is inserting and is taking off in the process of inserting, and volume change is bigger, even can reach 600%, and therefore the electrode particle is easy to take place efflorescence and structure deteriorate in working cycle, and capacity descends rapidly.
At present, main by alloying (Netz A, et al, J Power Source.2003,119-121:95), carrier disperses (Hwang S, et al, J Electrochem Solid-State Lett.2001,4:A97), finishing (Yoshio M, et al, J Electrochem Soc.2002,149:A1598) etc. method is improved cycle performance, but these methods do not obtain positive effect.The variation that recent findings adopts nanoparticle can slow down volume in the charge and discharge process improves stability of structure and cycle performance, cycle index can reach 100 times (Bensenhard J O, et al, J Power Sources.1997,68:87).Yet because easily reunite between the nanoparticle, thereby lost the peculiar effect of nanoparticle gradually, cycle performance is still undesirable for a long time.
Meanwhile, carbon material is a kind of as graphite material, when being used as lithium ion battery negative material, and the cycle performance excellence, but capacity is only near graphite theoretical capacity 372mAh/g.Obviously, its capacity awaits further raising.
Summary of the invention
In order to overcome the problems referred to above of the prior art, the present inventor has carried out research extensively and profoundly in the carrier field of dispersions of nano-silicon, found that and adopt the mixed calcining method (to mix earlier, calcining again) the nano-silicon particle can be dispersed in the carbon material carrier surface, thermal treatment at high temperature can improve the two bonded stability, it is good to form Stability Analysis of Structures, even particle distribution, security, capacity height, embedding lithium and take off the carbon material and nano silicon composite materials of embedding good reversibility.And to adopt carbon material and nano silicon composite materials be lithium ion battery negative material, is assembled into lithium ion battery.
Therefore, an object of the present invention is to provide a kind of method for preparing carbon material and nano silicon composite materials, this method makes the nano-silicon that is dispersed in carbon material surface embed and take off in the embedding process at lithium, can not reunite, improve the reversible capacity of carbon material, kept carbon material cycle performance excellent characteristics simultaneously.
Another object of the present invention provides a kind of carbon material and nano silicon composite materials of being produced by the inventive method.
Another object of the present invention provides a kind of application of the carbon material and nano silicon composite materials of being produced by the inventive method, and this matrix material can be used as lithium ion battery negative material.
One aspect of the present invention provides a kind of method for preparing carbon material and nano silicon composite materials, and the concrete steps of this method are as follows:
(1) ultra-sonic dispersion: carbon material and nano-silicon are added in the organic solvent, stir under the room temperature (1 minute-24 hours), and then continuous ultrasound disperses the regular hour (can 1 minute-24 hours), and nano-silicon is dispersed in the carbon material carrier.Here the weight ratio of carbon material and nano-silicon is 1-100: 1, and consumption of organic solvent is carbon material and nano-sized carbon gross weight 0.01-100 a times.
(2) drying: will be warming up to 20-100 ℃ in step (1) the gained mixing liquid, continuously stirring 5 minutes-96 hours makes the organic solvent volatilization clean, obtains carbon material/nano-silicon dried powder.
(3) calcining: the mixed powder of step (2) gained was calcined 1 minute～96 hours under 100～1200 ℃ in inert atmosphere or reducing atmosphere.
The present invention provides a kind of carbon material and nano silicon composite materials on the other hand, and wherein carbon material is synthetic graphite, natural graphite or low temperature decolorizing carbon, and the median size of carbon material is 0.01 ~ 1000 micron, and the particle diameter of nano-silicon is 1 ~ 500 nanometer.The particle diameter of matrix material is the 0.1-1000 micron.
These and other purposes of the present invention, feature and advantage will become clearer after reading whole specification sheets in conjunction with the accompanying drawings.
Detailed Description Of The Invention
In carbon material and nano silicon composite materials preparation method of the present invention, the carbon material in the step (1) is synthetic graphite, natural graphite or low temperature decolorizing carbon, and the median size of carbon material is 0.01 ~ 1000 micron.
In carbon material and nano silicon composite materials preparation method of the present invention, step (1) relates to the ultra-sonic dispersion of nano-silicon.Used nano-silicon can be the technical grade nano-silicon in this step, also can be HIGH-PURITY SILICON.Say from cost, be preferably the technical grade nano-silicon.The particle diameter of nano-silicon is 1nm-500nm, and preferred 5nm-200nm is more preferably within the 10nm-100nm scope.The shape of nano-silicon can be nanometer ball, nano wire, nanometer rod, nanofiber, nanotube etc., preferred nanometer ball.Preferred 0.1 micron-20 microns of the carbon material particle diameter that is used for this step, more preferably 2 microns-15 microns.The consumption of carrier carbon material is based on every gram nano-silicon 1-100 gram, preferred 8-50 gram, more preferably 10-30 gram.Ultrasonic time 1 minute-24 hours was preferably 2 hours-20 hours, more preferably was controlled at 6-12 hour.The organic solvent that is used for this step comprises rudimentary easy volatile organic solvents such as methyl alcohol, ethanol or ether.The consumption of organic solvent is carbon material and nano-silicon gross weight 0.01～100 times.Preferred 1-50 doubly.
In carbon material and nano silicon composite materials preparation method of the present invention, step (2) relates to the drying of step (1) gained mixing liquid.The evaporable temperature is decided by used organic solvent kind.With methyl alcohol is example, and volatilization temperature is controlled at 10-30 ℃.Keep stirring in the organic solvent volatilization process, the volatilization time was controlled at 5 minutes-96 hours, and preferred 30 minutes-48 hours, more preferably 6 hours-24 hours.
In silicon of the present invention/silicon/charcoal core-shell structure nanometer composite material preparation method, step (3) relates to the high-temperature calcination of the resultant carbon material of step (2)/nano-silicon dried powder.This step calcining temperature is at 100-1200 ℃, preferred 400-900 ℃.Calcining is at inert atmosphere (for example Ar, Ne, He, Xe, N
(2)Or reducing atmosphere (H for example
2/ Ar gas mixture) carries out under the condition.Calcination time can be 1 minute～96 hours, preferred 1 hour-24 hours.Through high-temperature calcination, the carrier-bound stability of nano-silicon and carbon material is improved.
The present invention's used wording " matrix material " in term " carbon material and nano silicon composite materials " is meant that nano-silicon is dispersed in carbon material surface in ultra-sonic dispersion process of the present invention, forms clad structure.After fully disperseing,, resulting carbon material/nano-silicon dry powder is at high temperature calcined, improved nano-silicon and the carrier-bound stability of carbon material, obtain stable matrix material through drying process.This matrix material can be used as the negative material of lithium ion battery, when lithium ion takes place to embed and takes off embedding, because nanoparticle is dispersed in carbon material surface, and has stronger reactive force with the surface, avoided the reunion effect between a large amount of nanoparticles, because carbon material has stable structure, the matrix material of this kind structure has high reversible capacity and excellent cycle performance simultaneously.
In the inventive method owing to use ultra-sonic dispersion method, make nano-silicon be dispersed in the carbon material carrier surface at short notice, after the organic solvent volatilization, improve nano-silicon and the carrier-bound stability of carbon material by high-temperature calcination, obtain the finished product, the carbon material and nano silicon composite materials Stability Analysis of Structures of gained is uniformly dispersed thus, under the situation of the cycle performance that has kept carrier carbon material excellence, improved the reversible capacity of matrix material.
Carbon material and nano silicon composite materials by the present invention's preparation has stable structure, and nanoparticle is dispersed in carbon material surface, has avoided the reunion effect between a large amount of nanoparticles, makes lithium ion battery have high reversible capacity and excellent cycle performance.Grain graininess is even in addition, favorable dispersity.At last, the inventive method is workable, favorable reproducibility, and the prepared constant product quality that gets.
Description of drawings
Fig. 1 is the cycle performance contrast of Comparative Examples 1 and embodiment 1.
Fig. 2 is scanning electron microscope (SEM) photo of the embodiment of the invention 1 gained carbon material and nano silicon composite materials.
Embodiment
The present invention is described in more detail below by reference Comparative Examples and embodiment, but protection scope of the present invention is not limited to these embodiment.
Comparative Examples 1
With the SSG of dopen Nano silicon (modified natural graphite, Loudi, Hunan brightness space Science and Technology Ltd. product) not is working electrode, 1mol/L LiPF
6EC-DEC (volume ratio 1: 1) be electrolyte solution, metallic lithium is that counter electrode is formed two electrode simulated batteries, SSG, carbon black, PVDF weight percent are 70: 20: 10 in the working electrode, charging and discharging currents density is 0.24mA/cm
2The initial charge capacity is 299.8mAh/g, and 20 circulation backs are because electrode fully activates, and capacity is 120% of an initial capacity, near the theoretical capacity of graphite material.
Embodiment 1
3.0gSSG and 0.3g nano-silicon are added in the 50mL anhydrous methanol, stirred 12 hours under the room temperature, and then continuous ultrasound disperseed 12 hours, nano-silicon is dispersed in the carbon material carrier.Slowly be warming up to 30 ℃ then, about 24 hours of continuously stirring makes the anhydrous methanol volatilization clean, obtains carbon material/nano-silicon dried powder.Powder was calcined 6 hours under 600 ℃ in inert atmosphere, obtained the carbon material and nano silicon composite materials of black.
The electrochemical property test of the carbon material and nano silicon composite materials that obtains is as follows.With the carbon material and nano silicon composite materials is working electrode, 1mol/L LiPF
6EC-DEC (volume ratio 1: 1) be electrolyte solution, metallic lithium is a counter electrode, forms two electrode simulated batteries, carbon material and nano silicon composite materials, carbon black, PVDF weight percent are 70: 20: 10 in the working electrode, charging and discharging currents density is 0.24mA/cm
2Recording the initial charge capacity is 562.1mAh/g, and 20 times circulation back capacity remains on 100% of initial capacity.
Comparative Examples 2
With the CMS of dopen Nano silicon (synthetic graphite, Shanghai Shanshan Science and Technology Co., Ltd's product) not is working electrode, 1mol/L LiPF
6EC-DEC (volume ratio 1: 1) be electrolyte solution, metallic lithium is that counter electrode is formed two electrode simulated batteries, CMS, carbon black, PVDF weight percent are 70: 20: 10 in the working electrode, charging and discharging currents density is 0.24mA/cm
2The initial charge capacity is 280mAh/g, and 20 times circulation back capacity is 99% of an initial capacity.
Embodiment 2
The above-mentioned CMS of 3.0g and 0.25g nano-silicon are added in the 50mL anhydrous methanol, stirred 12 hours under the room temperature, and then continuous ultrasound disperseed 12 hours, nano-silicon is dispersed in the carbon material carrier.Slowly be warming up to 30 ℃ then, about 24 hours of continuously stirring makes the anhydrous methanol volatilization clean, obtains carbon material/nano-silicon dried powder.Powder was calcined 2 hours under 800 ℃ in inert atmosphere, obtained the carbon material and nano silicon composite materials of black.The electrochemical property test of carbon material and nano silicon composite materials is identical with embodiment 1.Recording the initial charge capacity is 525.7mAh/g, and 20 times circulation back capacity remains on 100% of initial capacity.
Comparative Examples 3
With the MCMB of dopen Nano silicon (synthetic graphite, Osaka, Japan coal gas company limited product) not is working electrode, 1mol/L LiPF
6EC-DEC (volume ratio 1: 1) be electrolyte solution, metallic lithium is that counter electrode is formed two electrode simulated batteries, CMS, carbon black, PVDF weight percent are 70: 20: 10 in the working electrode, charging and discharging currents density is 0.24mA/cm
2The initial charge capacity is 286mAh/g, and 20 times circulation back capacity is 99% of an initial capacity.
Embodiment 3
The above-mentioned MCMB of 3.0g and 0.6g nano-silicon are added in the 50mL anhydrous methanol, stirred 12 hours under the room temperature, and then continuous ultrasound disperseed 12 hours, nano-silicon is dispersed in the carbon material carrier.Slowly be warming up to 30 ℃ then, about 24 hours of continuously stirring makes the anhydrous methanol volatilization clean, obtains carbon material/nano-silicon dried powder.Powder was calcined 12 hours under 400 ℃ in inert atmosphere, obtained the carbon material and nano silicon composite materials of black.The electrochemical property test of carbon material and nano silicon composite materials is identical with embodiment 1.Recording the initial charge capacity is 634.6mAh/g, and 20 times circulation back capacity remains on 100% of initial capacity.
Claims (8)
1. method for preparing carbon material and nano silicon composite materials is characterized in that concrete steps are as follows:
(1) ultra-sonic dispersion: carbon material and nano-silicon are added in the organic solvent, stir, and then continuous ultrasound disperseed 1 minute-24 hours, nano-silicon is dispersed in the carbon material carrier, wherein, the weight ratio of carbon material and nano-silicon is 1-100: 1, and consumption of organic solvent is carbon material and nano-sized carbon gross weight 0.01-100 a times;
(2) drying: will be warming up to 20-100 ℃ in step (1) the gained mixing liquid, continuously stirring 5 minutes-96 hours makes the organic solvent volatilization clean, obtains carbon material/nano-silicon dried powder;
(3) calcining: the mixed powder of step (2) gained was calcined 1 minute～96 hours under 100～1200 ℃ in inert atmosphere or reducing atmosphere.
2. method according to claim 1 is characterized in that used carbon material is synthetic graphite, natural graphite or low temperature decolorizing carbon in the step (1), and the median size of carbon material is 0.01 ~ 1000 micron.
3. method according to claim 1, the particle diameter that it is characterized in that used nano-silicon in the step (1) is 1nm-500nm.
4. according to the described method of claim 1, it is characterized in that organic solvent used in the step (1) is methyl alcohol, ethanol or ether.
5. method according to claim 1 is characterized in that ultrasonic time is 2 hours-20 hours in the step (1).
6. method according to claim 1 is characterized in that the organic solvent volatilization time was controlled at 30 minutes-48 hours in the step (2).
7. carbon material and nano silicon composite materials that obtains according to the described method of one of claim 1-6, for be dispersed in the clad structure that carbon material surface forms by nano-silicon, wherein the median size of carbon material is 0.01 ~ 1000 micron, the particle diameter of nano-silicon is 1 ~ 500 nanometer, and the particle diameter of matrix material is 0.1～1000 micron.
8. carbon material and nano silicon composite materials as claimed in claim 7 is as the application of lithium ion battery negative material.
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| CN101510602B (en) * | 2009-02-19 | 2010-11-03 | 上海交通大学 | Method for preparing silicon composite cathode material of lithium ion battery |
| CN101986447A (en) * | 2010-05-25 | 2011-03-16 | 耿世达 | High-energy composite cathode material for lithium ion battery and preparation method thereof |
| CN102651476A (en) * | 2012-05-28 | 2012-08-29 | 深圳市贝特瑞新能源材料股份有限公司 | Lithium ion battery silicon carbide composite anode material and preparation method thereof |
| CN102867944A (en) * | 2011-07-06 | 2013-01-09 | 东丽纤维研究所（中国）有限公司 | Mesoporous carbon/silicon composite anode material and preparation method thereof |
| CN103094525A (en) * | 2011-10-28 | 2013-05-08 | 清华大学 | Lithium ion battery negative electrode and preparation method thereof |
| CN105226241A (en) * | 2014-08-27 | 2016-01-06 | 深圳市国创新能源研究院 | A kind of silicon-carbon composite cathode material of lithium ion battery and preparation method thereof |
| CN105489855A (en) * | 2015-11-25 | 2016-04-13 | 天津师范大学 | Core-shell silicon carbon composite negative electrode material for high-capacity type lithium ion battery and preparation method therefor |
| CN110605385A (en) * | 2019-10-29 | 2019-12-24 | 广东银纳科技有限公司 | Preparation method of tungsten-based micro-nano composite powder and tungsten-based micro-nano composite powder |
| US10629895B2 (en) | 2014-02-06 | 2020-04-21 | Wacker Chemie Ag | Si/G/C-composites for lithium-ion-batteries |
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| WO2005090234A1 (en) * | 2004-03-17 | 2005-09-29 | Denki Kagaku Kogyo Kabushiki Kaisha | Silicon particle, silicon particle superlattice and method for production thereof |
| CN1328805C (en) * | 2004-04-05 | 2007-07-25 | 中国科学院物理研究所 | Negative electrode active material and use of secondary lithium battery |
| CN100422112C (en) * | 2005-07-08 | 2008-10-01 | 中国科学院物理研究所 | Carbon-silicon composite material with spherical nucleocapsid, and its preparing method and use |
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| CN101510602B (en) * | 2009-02-19 | 2010-11-03 | 上海交通大学 | Method for preparing silicon composite cathode material of lithium ion battery |
| CN101986447A (en) * | 2010-05-25 | 2011-03-16 | 耿世达 | High-energy composite cathode material for lithium ion battery and preparation method thereof |
| CN102867944A (en) * | 2011-07-06 | 2013-01-09 | 东丽纤维研究所（中国）有限公司 | Mesoporous carbon/silicon composite anode material and preparation method thereof |
| CN103094525A (en) * | 2011-10-28 | 2013-05-08 | 清华大学 | Lithium ion battery negative electrode and preparation method thereof |
| CN102651476A (en) * | 2012-05-28 | 2012-08-29 | 深圳市贝特瑞新能源材料股份有限公司 | Lithium ion battery silicon carbide composite anode material and preparation method thereof |
| WO2013178059A1 (en) * | 2012-05-28 | 2013-12-05 | 深圳市贝特瑞新能源材料股份有限公司 | Lithium-ion battery silicon-carbon composite negative electrode material and preparation method therefor |
| CN102651476B (en) * | 2012-05-28 | 2015-01-28 | 深圳市贝特瑞新能源材料股份有限公司 | Lithium ion battery silicon carbide composite anode material and preparation method thereof |
| US10629895B2 (en) | 2014-02-06 | 2020-04-21 | Wacker Chemie Ag | Si/G/C-composites for lithium-ion-batteries |
| CN105226241A (en) * | 2014-08-27 | 2016-01-06 | 深圳市国创新能源研究院 | A kind of silicon-carbon composite cathode material of lithium ion battery and preparation method thereof |
| CN105489855A (en) * | 2015-11-25 | 2016-04-13 | 天津师范大学 | Core-shell silicon carbon composite negative electrode material for high-capacity type lithium ion battery and preparation method therefor |
| CN105489855B (en) * | 2015-11-25 | 2017-11-14 | 天津师范大学 | High capacity type lithium ion battery nucleocapsid silicon-carbon composite cathode material and preparation method thereof |
| CN110605385A (en) * | 2019-10-29 | 2019-12-24 | 广东银纳科技有限公司 | Preparation method of tungsten-based micro-nano composite powder and tungsten-based micro-nano composite powder |
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