CN100366532C - Silicon/oxidative silicon nuclear-shell structured nano-composite material, its preparation and use - Google Patents
Silicon/oxidative silicon nuclear-shell structured nano-composite material, its preparation and use Download PDFInfo
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- CN100366532C CN100366532C CNB2006100274399A CN200610027439A CN100366532C CN 100366532 C CN100366532 C CN 100366532C CN B2006100274399 A CNB2006100274399 A CN B2006100274399A CN 200610027439 A CN200610027439 A CN 200610027439A CN 100366532 C CN100366532 C CN 100366532C
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Abstract
A silicon/monox core-shell structured nanometer-composite material, its production and use are disclosed. The process is carried out by building in and removing lithium ion by sol-gel method. Its advantages include stable crystal structure, better reversible capacity and circulation performance, better operability, repeatability and quality. It can be used in production of lithium-ion battery.
Description
Technical field
The invention belongs to technical field of electrochemistry, be specifically related to a kind of method for preparing silicon/oxidative silicon nuclear-shell structured nano-composite material, more particularly, the present invention relates to a kind of is nuclear with the nano-silicon by Prepared by Sol Gel Method, and silicon oxide is the method for the nano composite material of shell.The invention still further relates to the silicon/oxidative silicon nuclear-shell structured nano-composite material that obtains by aforesaid method.Simultaneously, the invention still further relates to the application of this nano composite material, 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 PowerSources.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.
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 finishing field of nano-silicon, found that and adopt sol-gel method can coat one deck poly silicic acid gel on the nano-silicon surface, processing can change the poly silicic acid gel into silicon oxide (SiOx:x≤2) crystal under proper temperature (0-1200 ℃), it is good to form Stability Analysis of Structures, even particle distribution, security, capacity height, embedding lithium and the silicon/oxidative silicon nuclear-shell structured nano-composite material that takes off the embedding good reversibility.And adopt the silicon/oxidative silicon matrix material as lithium ion battery negative material, be assembled into lithium ion battery.
Therefore, an object of the present invention is to provide a kind of method for preparing silicon/oxidative silicon nuclear-shell structured nano-composite material, this method makes the nano-silicon that coated embed and take off in the embedding process at lithium, can not reunite, and has improved cyclical stability.
Another object of the present invention provides a kind of silicon/oxidative silicon nuclear-shell structured nano-composite material of being produced by the inventive method.
A further object of the present invention provides a kind of application of the silicon/oxidative silicon nuclear-shell structured nano-composite material 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 silicon/oxidative silicon nuclear-shell structured nano-composite material, and this method comprises following step:
(1) obtain solution: organic positive silicon ester, organic solvent and deionized water are matched well than mixing according to certain volume, and stir (general 1 minute-5 hours) make as clear as crystal solution.
(2) ultra-sonic dispersion: nano-silicon is added in step (1) the gained solution, stir, continuous ultrasound disperses (general 1 minute-5 hours) again, and nano-silicon is uniformly dispersed.
(3) collosol and gel: step (2) gained mixing liquid is warming up to 50-100 ℃, magnetic force or mechanical stirring 10 minutes-24 hours.Add proper catalyst then, continue to stir 10 minutes-24 hours, hydrolytic polymerization forms the poly silicic acid gel.
(4) ageing drying: the ageing 1 minute-14 days in air of step (3) products therefrom is dry under 30 to 100 ℃ of temperature then, obtain xerogel, grind to form the gel powder.
(5) thermal treatment: the gel powder of step 4) gained in inert atmosphere, 200-1000 ℃ of temperature lower calcination for some time, is finally obtained silicon/oxidative silicon nuclear-shell structured nano composite material.
The present invention provides a kind of silicon/oxidative silicon nuclear-shell structured nano-composite material on the other hand, and the particle diameter of its one-level particle is 0.1 ~ 1000 nanometer.
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 silicon/oxidative silicon nuclear-shell structured nano-composite material preparation method of the present invention, step 1) relates to the process for preparation of solution.Used organic positive silicon ester and organic solvent can be technical grades in this step, also can be that reagent is pure.From the cost angle, preferred technical grade.Organic positive silicon ester comprises tetraethoxy, positive silicic acid propyl ester, the positive positive butyl ester of silicic acid and other positive silicon ester, is preferably tetraethoxy.The consumption of organic positive silicon ester is every gram nano-silicon 0.8ml-8ml in the step (2), preferred 1.6-4ml.Organic solvent can be alcohols such as ethanol, propyl alcohol, also can be other volatile organic solvent; As the organic solvent of organic positive silicon ester, with the volume ratio proportioning of organic positive silicon ester be 10: 1-1: 1, preferred 5: 1-1: 1, more preferably 2: 1; The volume ratio proportioning of deionized water and organic positive silicon ester is 5: 1-1: 1, preferred 3: 1-1: 1, and more preferably 2: 1.Churning time 1 minute-5 hours preferably was controlled at it 20 minutes-2 hours.
In silicon/oxidative silicon nuclear-shell structured nano-composite material preparation method of the present invention, step (2) 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.Ultrasonic time 1 minute-5 hours preferably was controlled at it 20 minutes-1 hour.
In silicon/oxidative silicon nuclear-shell structured nano-composite material preparation method of the present invention, step (3) relates to sol-gel process.Particularly, at 50-100 ℃, preferred 60-80 ℃ of lower magnetic force or mechanical stirring 10 minutes to 10 hours form uniform reaction soln with the resulting mixing solutions of step (2).Keep stirring, at 50-100 ℃, add proper catalyst under preferred 60-80 ℃ the temperature, hydrolytie polycondensation 10 minutes-24 hours forms the poly silicic acid gel.The catalyzer that is used for this step comprises that ammoniacal liquor, hydrochloric acid, carbonic acid gas, oxalic acid, citric acid or acetic acid etc. can be used for regulating the reagent or the material of pH value.Catalyst consumption has influence on the pH value of solution, thereby has influence on the particle diameter of gel time and the final silicon oxide particle that forms.Under alkaline environment (when for example catalyzer is ammoniacal liquor), can regulate the pH value and be 7-12, preferred 9-10.Under sour environment (when being hydrochloric acid), can regulate the pH value and be 4-7, preferred 5-6 as catalyzer.In alkaline environment, gel time reduces with the increase of pH value, and in sour environment, and gel time reduces and reduces with the pH value.Reason is that the micelle electro kinetic potential reduces to be accelerated when alkalescence or acid when strong, and pedesis is quickened, and causes that effective collision increases between micelle, loses gel speed and increases, and colloid diameter increases.
In silicon/oxidative silicon nuclear-shell structured nano-composite material preparation method of the present invention, step (4) relates to the ageing and the drying of gained wet gel behind step (3) collosol and gel.Aged purpose is to make the poly silicic acid with three-dimensional space network shape structure that forms in the gelation process full cross-linked, improves the stability of gel.Ageing is carried out in air, digestion time 1 minute-14 days, preferred 1 hour-7 days.Gel after the ageing is at 30 ℃-100 ℃, dry under the preferred 50-80 ℃ of temperature, obtain xerogel, grind and obtain the gel powder.
In silicon/oxidative silicon nuclear-shell structured nano-composite material preparation method of the present invention, step (5) relates to the thermal treatment of the resultant gel powder of step (4).This step temperature is preferably at 250-600 ℃, and more preferably 300-500 ℃, most preferably 400-450 ℃.Calcining is at inert atmosphere (for example Ar, Ne, He, Xe, N
2) under carry out.Calcination time can be 1 minute～96 hours, preferred 1 hour-24 hours.
The present invention's used wording " nucleocapsid structure " in term " silicon/oxidative silicon nuclear-shell structured nano-composite material " is meant in sol-gel process of the present invention, the poly silicic acid micelle that the nano-silicon particle is formed in the sol-gel process coats fully, after sol-gel process is finished, with resulting nano-silicon/poly silicic acid presoma ageing drying, form stable crosslinked clad structure, through Overheating Treatment, poly silicic acid is converted into the silica crystal particulate material, is coated on the nano-silicon surface and forms stable matrix material.When lithium ion took place to embed and takes off embedding, the shell material with stable crystal structure can be protected inner nanoparticle, avoids the reunion effect between the nanoparticle, and stable simultaneously shell material will prevent the efflorescence and the reunion of nanoparticle.The matrix material of this kind structure has high reversible capacity and excellent cycle performance.
In the inventive method owing to use sol-gel method, make nano-silicon coated with uniform one deck polymer at short notice, ageing drying then, obtain stablizing the nano-silicon/poly silicic acid presoma of crosslinked coating, and by thermal treatment, make polymer be converted into stable silica crystal, obtain the finished product, the silicon/oxidative silicon nuclear-shell structured nano-composite material Stability Analysis of Structures of gained thus, be uniformly dispersed, when finishing the silicon oxide coating, still kept final resulting matrix material particle diameter below micron order.
Silicon/oxidative silicon nuclear-shell structured nano-composite material by the present invention's preparation has stable nucleocapsid structure, shell material with stable crystal structure can be avoided the lithium ion embedding and take off the reunion between the nanoparticle in the embedding process, 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 of the present invention and embodiment 1.
Fig. 2 (a) is transmission electron microscope (TEM) photo of the embodiment of the invention 1 gained silicon/oxidative silicon nuclear-shell structured nano-composite material; Fig. 2 (b) is that the part of Fig. 2 (a) is amplified.
Embodiment
The present invention below will be described in more detail by reference Comparative Examples and embodiment, but protection scope of the present invention is not limited to these embodiment.
Comparative Examples
Nano-silicon with not coating is a working electrode, 1mol/L LiPF
6, EC-DEC (volume ratio 1: 1) is an electrolyte solution, metallic lithium is that counter electrode is formed two electrode simulated batteries, and nano-silicon in the working electrode, carbon black, PVDF weight percent are 40: 40: 20, charging and discharging currents density is 0.2mA/cm
2The initial charge capacity is 1831.4mAh/g, and 20 times circulation back capacity remains on 6.5% of initial capacity, and capacity is shown in Fig. 1 with the round-robin result of variations.
Embodiment 1
10mL (about 0.045mol) tetraethoxy, 20mL ethanol, 20mL deionized water are mixed stirring 30 minutes, obtain as clear as crystal solution.Add 1.26g nano-silicon (about 0.045mol), continue to stir after 1 hour, continuous ultrasound disperseed 2 hours again, and nano-silicon is uniformly dispersed.Mixing liquid is warming up to 70 ℃, and magnetic agitation 2 hours adds 3 strong aquas then, and keeping temperature is 70 ℃, continues stir about and forms gel after 2 hours.With gel ageing 24 hours in air, dry under 70 ℃ of temperature then, obtain xerogel, grind to form the gel powder.Should brown gel powder 500 ℃ of calcinings 6 hours under inert atmosphere protection, obtain brown silicon/oxidative silicon nuclear-shell structured nano-composite material, its transmission electron microscope is illustrated in Fig. 2.
The silicon/oxidative silicon nuclear-shell structured electrochemical property test that obtains is as follows.With the silicon/oxidative silicon nuclear-shell structured nano-composite material is working electrode, 1mol/L LiPF
6, EC-DEC (volume ratio 1: 1) is an electrolyte solution, metallic lithium is a counter electrode, form two electrode simulated batteries, silicon/oxidative silicon nuclear-shell structured nano-composite material in the working electrode, carbon black, the PVDF weight percent is 40: 40: 20, and charging and discharging currents density is 0.2mA/cm
2Recording the initial charge capacity is 827.3mAh/g, and 20 times circulation back capacity remains on 65.1% of initial capacity, and capacity is shown in Fig. 1 with the round-robin result of variations.
Embodiment 2
The positive silicic acid propyl ester of 10mL (about 0.045mol), 40mL propyl alcohol, 20mL deionized water are mixed stirring 30 minutes, obtain as clear as crystal solution.Add 1.26g nano-silicon (about 0.045mol), continue to stir after 1 hour, continuous ultrasound disperseed 2 hours again, and nano-silicon is uniformly dispersed.Mixing liquid is warming up to 70 ℃, and magnetic agitation 2 hours adds 3 strong aquas then, and keeping temperature is 70 ℃, continues stir about and forms gel after 2 hours.With gel ageing 24 hours in air, dry under 70 ℃ of temperature then, obtain xerogel, grind to form the gel powder.Should brown gel powder 700 ℃ of calcinings 2 hours under inert atmosphere protection, obtain brown silicon/oxidative silicon nuclear-shell structured nano-composite material.Silicon/oxidative silicon nuclear-shell structured electrochemical property test is identical with embodiment 1.Recording the initial charge capacity is 916.8mAh/g, and 20 times circulation back capacity remains on 59.2% of initial capacity.
Embodiment 3
10mL (about 0.045mol) butyl silicate, 20mL methyl alcohol, 40mL deionized water are mixed stirring 30 minutes, obtain as clear as crystal solution.Add 1.26g nano-silicon (about 0.045mol), continue to stir after 1 hour, continuous ultrasound disperseed 2 hours again, and nano-silicon is uniformly dispersed.Mixing liquid is warming up to 70 ℃, and magnetic agitation 2 hours adds 3 strong aquas then, and keeping temperature is 70 ℃, continues stir about and forms gel after 2 hours.With gel ageing 24 hours in air, dry under 70 ℃ of temperature then, obtain xerogel, grind to form the gel powder.Should brown gel powder 800 ℃ of calcinings 1 hour under inert atmosphere protection, obtain brown silicon/oxidative silicon nuclear-shell structured nano-composite material.Silicon/oxidative silicon nuclear-shell structured electrochemical property test is identical with embodiment 1.Recording the initial charge capacity is 785.8mAh/g, and 20 times circulation back capacity remains on 69.2% of initial capacity.
Embodiment 4
10mL (about 0.045mol) tetraethoxy, 20mL dimethyl formamide, 20mL deionized water are mixed stirring 30 minutes, obtain as clear as crystal solution.Add 2.52g nano-silicon (about 0.090mol), continue to stir after 1 hour, continuous ultrasound disperseed 2 hours again, and nano-silicon is uniformly dispersed.Mixing liquid is warming up to 70 ℃, and magnetic agitation 2 hours adds 3 strong aquas then, and keeping temperature is 70 ℃, continues stir about and forms gel after 2 hours.With gel ageing 24 hours in air, dry under 70 ℃ of temperature then, obtain xerogel, grind to form the gel powder.Should brown gel powder 500 ℃ of calcinings 6 hours under inert atmosphere protection, obtain brown silicon/oxidative silicon nuclear-shell structured nano-composite material.Silicon/oxidative silicon nuclear-shell structured electrochemical property test is identical with embodiment 1.Recording the initial charge capacity is 1036.2mAh/g, and 20 times circulation back capacity remains on 57.3% of initial capacity.
Claims (5)
1. method for preparing silicon/oxidative silicon nuclear-shell structured nano-composite material is characterized in that concrete steps are as follows:
(1) obtain solution: organic positive silicon ester, organic solvent and deionized water are mixed, stir, make as clear as crystal solution, wherein, organic positive silicon ester and volume of organic solvent ratio are 10: 1-1: 1, and organic positive silicon ester and deionized water volume ratio are 5: 1-1: 1;
(2) ultra-sonic dispersion: nano-silicon is added in step (1) the gained solution, and continuous ultrasound disperseed 1 minute-5 hours, and nano-silicon is uniformly dispersed; Used nano-silicon is the technical grade nano-silicon, and its particle diameter is at 1nm-500nm,
(3) collosol and gel: step (2) gained mixing liquid is warming up to 50-100 ℃, and magnetic force or mechanical stirring 10 minutes-24 hours add catalyzer then, continue to stir 10 minutes-24 hours, and hydrolytic polymerization forms the poly silicic acid gel; Catalyst system therefor is ammoniacal liquor, hydrochloric acid, carbonic acid gas, oxalic acid, citric acid or acetic acid, is used to regulate the pH value;
(4) ageing drying: the ageing 1 minute-14 days in air of step (3) products therefrom is dry under 30 to 100 ℃ of temperature then, obtain xerogel, grind to form the gel powder;
(5) thermal treatment: the gel powder of step (4) gained in inert atmosphere, at 200-1000 ℃ of temperature lower calcination, is finally obtained silicon/oxidative silicon nuclear-shell structured nano-composite material.
2. method according to claim 1 is characterized in that used organic positive silicon ester and organic solvent are that technical grade or reagent are pure in the step (1).
3. method according to claim 1, when it is characterized in that step (3) is carried out under alkaline environment, regulating the pH value is 7-12; When carrying out under sour environment, regulating the pH value is 5-6.
4. method according to claim 1 is characterized in that in the step (4), digestion time 2 days-7 days, and drying temperature is at 50 ℃-80 ℃.
5. method according to claim 1 is characterized in that the calcining temperature in the step (5) is 250-600 ℃, and calcination time is 1 hour-24 hours.
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| JP5298609B2 (en) * | 2008-04-08 | 2013-09-25 | ソニー株式会社 | Negative electrode for secondary battery and secondary battery |
| US20090317726A1 (en) | 2008-04-08 | 2009-12-24 | Sony Corporation | Anode and secondary battery |
| CN101570314B (en) * | 2008-05-04 | 2011-07-13 | 比亚迪股份有限公司 | Preparation method of hydrogen storage material |
| CN101777651B (en) * | 2009-01-12 | 2012-06-20 | 比亚迪股份有限公司 | Silicon anode material and preparation method thereof and lithium battery using silicon anode material |
| JPWO2012098639A1 (en) * | 2011-01-18 | 2014-06-09 | Ｎｅｃエナジーデバイス株式会社 | Non-aqueous electrolyte secondary battery |
| CN102593426A (en) * | 2011-05-07 | 2012-07-18 | 天津锦美碳材科技发展有限公司 | Method for preparing silicon oxide (SiOx) / carbon (C) composite materials and prepared silicon carbon cathode materials for lithium ion battery |
| CN102709563B (en) * | 2012-04-06 | 2015-09-09 | 中国科学院苏州纳米技术与纳米仿生研究所 | Lithium ion battery silicon cathode material and preparation method thereof |
| CN103474636B (en) * | 2013-09-18 | 2015-11-25 | 上海交通大学 | Silica-based lithium ion battery cathode material and its preparation method |
| CN103904306B (en) * | 2014-02-19 | 2017-02-08 | 上海璞泰来新能源科技股份有限公司 | Silicon negative electrode composite material and preparation method thereof |
| CN105742587B (en) * | 2016-02-25 | 2018-10-23 | 南京师范大学 | A kind of preparation method of lithium-sulphur cell positive electrode sulphur/silica dioxide gel three-dimensional composite material |
| CN109713242B (en) * | 2017-10-26 | 2022-02-18 | 银隆新能源股份有限公司 | Titanium silicon carbon negative electrode material with core-shell pomegranate structure and preparation method thereof |
| KR20200073350A (en) * | 2018-12-13 | 2020-06-24 | 삼성전자주식회사 | Negative active material, lithium secondary battery including the material, and method for manufacturing the material |
| WO2021031201A1 (en) * | 2019-08-22 | 2021-02-25 | 于志远 | Microchannel reactor and method for preparing precursor micro-nano particles of positive electrode materials and negative electrode materials of lithium battery |
| CN115117315A (en) * | 2022-07-07 | 2022-09-27 | 兰州大学 | Silica negative electrode material, negative electrode piece, lithium battery and preparation method thereof |
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