CN100422076C - Silicon/charcoal core-shell structure nanometer composite material and its preparation method and uses - Google Patents
Silicon/charcoal core-shell structure nanometer composite material and its preparation method and uses Download PDFInfo
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Abstract
The present invention relates to a method for preparing a silicon / carbon core-shell structure nanometer composite material with an emulsion polymerization method and a silicon / carbon core-shell structure nanometer composite material obtained with the method. The silicon / carbon core-shell structure nanometer composite material prepared with the method of the present invention has a stable core-shell structure, the diameter of particles the silicon / carbon core-shell structure nanometer composite material is hundreds of nanometers, or the particles are small. In the process of the insertion and the separation of lithium ions, a shell material with a hard structure can avoid the agglomeration of the nanometer particles so as to make a lithium ion battery have high reversible capability and a favorable cycle performance. In addition, the method of the present invention has the advantages of strong operability, good reproducibility and stable obtained product quality.
Description
Technical field
The invention belongs to technical field of nano material, be specifically related to a kind of silicon/silicon/charcoal core-shell structure nanometer composite material and its production and use, more particularly, the present invention relates to a kind of is nuclear with the nano-silicon by emulsion polymerization prepared, and the polymer cracking charcoal is the method for the nano composite material of shell.The invention still further relates to the purposes of the silicon/silicon/charcoal core-shell structure nanometer composite material 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, JPower 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.
Summary of the invention
What the objective of the invention is to Stability Analysis of Structures, embedding lithium and take off the embedding good reversibility can be used as nano composite material of lithium ion battery negative and preparation method thereof.
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 emulsion polymerisation process to coat one layer of polymeric on the nano-silicon surface, thermal treatment can be hard charcoal with polymer transition under low temperature (＜1200 ℃), it is good to form Stability Analysis of Structures, even particle distribution, security, capacity height, embedding lithium and the silicon/silicon/charcoal core-shell structure nanometer composite material that takes off the embedding good reversibility.And to adopt silicon/carbon composite be lithium ion battery negative material, is assembled into lithium ion battery.
Therefore, the nano composite material that the present invention proposes, be a kind of be nuclear with the nano-silicon, at nano-silicon surface coated polymer layer, again through low-temperature heat treatment, the carbon charcoal that is transformed into by polymer layer is the silicon/silicon/charcoal core-shell structure material of shell with emulsion polymerisation process.Wherein, the particle diameter of nuclear is the 1-500 nanometer, and the thickness of shell is the 2-50 nanometer.
Above-mentioned silicon/silicon/charcoal core-shell structure nanometer composite material, the polymer layer that becomes hard charcoal is a kind of or wherein several mixture of resol, Resins, epoxy, polyacrylonitrile, polystyrene or polyacrylic acid etc.
Above-mentioned silicon/silicon/charcoal core-shell structure nanometer composite material provided by the invention can be used as lithium ion battery negative material, is assembled into lithium ion battery.
The preparation method of above-mentioned silicon/silicon/charcoal core-shell structure nanometer composite material provided by the invention comprises following step:
(1) ultra-sonic dispersion: nano-silicon and dispersion agent are added in the entry, and continuous ultrasound disperseed 1 minute-5 hours, and nano-silicon is uniformly dispersed.
(2) sound emulsification: emulsifying agent is added in step (1) the gained mixing liquid continuous ultrasound emulsification 1 minute-5 hours.
(3) letex polymerization: add polymer precursor and initiator in step (2) gained mixing liquid, logical rare gas element emptying is 1 minute-10 hours under magnetic force or the mechanical stirring.Then stir and inert atmosphere under 50-120 ℃ of letex polymerization 30 minutes-48 hours.
(4) drying:, obtain nano-silicon/polymer precursor with dry under-30 ℃ to 100 ℃ temperature after step (3) the products therefrom centrifugation.
(5) high-temperature calcination: the presoma of step (4) gained was calcined 1 minute～96 hours under 600～1200 ℃ in inert atmosphere.
Aforesaid method of the present invention makes the nano-silicon that coated embed and take off in the embedding process at lithium, can not reunite, and has improved reversible capacity.
Above-mentioned kind of silicon/silicon/charcoal core-shell structure nanometer composite material provided by the invention, the particle diameter of its one-level particle is 100 nanometers or littler.
In silicon of the present invention/silicon/charcoal core-shell structure nanometer composite material preparation method, 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.The dispersion agent that is used for this step comprises a kind of of organic polymers such as polyvinylpyrrolidone, polyvinyl alcohol, polyacrylic acid and poly-methyl acrylate or wherein several, dispersant dosage is the 0.1-5 gram based on every gram nano-silicon, preferred 0.2-2.5 gram, more preferably 0.5-1 gram.Ultrasonic time 1 minute-5 hours preferably was controlled at it 20 minutes-1 hour.
In silicon of the present invention/silicon/charcoal core-shell structure nanometer composite material preparation method, step (2) relates to the ultrasonic emulsification of step (1) gained mixing liquid.The emulsifying agent that is used for this step comprises OP
9Emulsifying agents such as (a kind of commodity emulsifying agent or tensio-active agent that contains ethylene oxide unit), sodium lauryl sulphate, sodium laurylsulfonate a kind of or wherein several.The preferred 0.01wt.%-10wt.% of the concentration of emulsifying agent, preferred 0.05wt.%-5wt.%, more preferably 1wt.%-wt.3%.Ultrasonic time 1 minute-5 hours preferably was controlled at it 20 minutes-1 hour.
In silicon of the present invention/silicon/charcoal core-shell structure nanometer composite material preparation method, step (3) relates to emulsion polymerization process.Particularly, polymer precursor and initiator are added in the resulting mixing liquid of step (2), logical rare gas element emptying is 1 minute-24 hours under magnetic force or the mechanical stirring, forms uniform reaction soln.Keep then stirring and inert atmosphere, the emulsion polyase 13 is 0 minute-48 hours under 50-120 ℃, preferred 70-90 ℃ temperature, preferred 4 hours-12 hours.The polymer precursor that is used for this step comprises resol, Resins, epoxy, polyacrylonitrile, polystyrene, polyacrylic presoma, or several mixture in these presomas.The raw material of used polymer precursor can be a technical grade in this step, also can be that reagent is pure.From the cost angle, preferred technical grade.The concentration of polymer precursor depends on the consumption of nano-silicon, and for example its consumption can restrain for 0.5-5 based on every gram nano-silicon, preferred 1-2.5 gram.Equally, the initiator that is used for this step comprises Potassium Persulphate, Diisopropyl azodicarboxylate (AIBN), dibenzoyl peroxide (BPO) or ammonium persulphate etc.Initiator concentration depends on the concentration of polymer precursor, and for example when polymer precursor was vinyl cyanide, the consumption of Potassium Persulphate was the 0.1wt. ‰-10wt. ‰ of vinyl cyanide consumption, preferred 0.5wt.%-5wt. ‰.In this step, the letex polymerization temperature is 50-120 ℃, preferred 70-90 ℃, and the preferred 4-12 of polymerization time hour.
In silicon of the present invention/silicon/charcoal core-shell structure nanometer composite material preparation method, step (4) relates to the centrifugation and the drying of gained mixing solutions after step (3) letex polymerization.The purpose of centrifugation is to remove dispersion agent, emulsifying agent and other impurity in the mixing solutions after the letex polymerization, purified product.Centrifugation should be carried out repeatedly, do not have bubble in the mixing solutions after separating till.The product of centrifugation is at-30 ℃-100 ℃, dry under the preferred 50-80 ℃ of temperature, obtain nano-silicon/polymer precursor.
In silicon of the present invention/silicon/charcoal core-shell structure nanometer composite material preparation method, step (5) relates to the high-temperature calcination of the resultant nano-silicon/polymer precursor of step (4).This step temperature is preferably at 600-1200 ℃, and more preferably 700-1000 ℃, most preferably 750-850 ℃.(thermal treatment below＜1200 ℃ can change " hard charcoal " into, so calcining temperature must be controlled at below 1200 ℃ because polymkeric substance is only at low temperature.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.
The present invention's used wording " nucleocapsid structure " in term " silicon/silicon/charcoal core-shell structure nanometer composite material " is meant in emulsion polymerization process of the present invention, the nano-silicon surface is aggregated thing (polyacrylonitrile) and coats fully, after letex polymerization is finished, resulting nano-silicon/polymer precursor is at high temperature calcined, making polymer transition is " hard charcoal ", 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 rigid structure can be protected inner nanoparticle, avoids the reunion effect between the nanoparticle, and hard shell material will prevent the efflorescence and the reunion of nanoparticle simultaneously.The matrix material of this kind structure has high reversible capacity and excellent cycle performance.
The contriver thinks in the inventive method owing to use emulsion polymerisation process, make nano-silicon coated with uniform one layer of polymeric at short notice, centrifugation then, drying obtains nano-silicon/polymer precursor, and make polymer cracking become " hard charcoal " by high-temperature calcination (＜1200 ℃), obtain the finished product, the silicon of gained/silicon/charcoal core-shell structure nanometer composite material Stability Analysis of Structures thus, be uniformly dispersed, still having kept final resulting matrix material when finishing hard charcoal coating is nanometer particle size.
Silicon/silicon/charcoal core-shell structure nanometer composite material by the present invention's preparation has stable nucleocapsid structure, shell material with rigid 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 chemical property contrast of Comparative Examples and embodiment 2: (a) charging and discharging curve for the first time; (b) cycle performance;
Transmission electron microscope (TEM) photo of Fig. 2 (a) embodiment of the invention 2 gained silicon/silicon/charcoal core-shell structure nanometer composite materials; (b) be the electronic energy spectrum that is coated on the charcoal shell zone on the nano-silicon of circle markings in (a).
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.Its first charge-discharge curve and cycle performance are shown in Fig. 1.
0.5g nano-silicon and 0.5g polyvinylpyrrolidone are added in the 200ml water, and continuous ultrasound disperseed 30 minutes, and nano-silicon is uniformly dispersed.Add the 1g sodium lauryl sulphate again, continuous ultrasound emulsification 30 minutes.Add 0.5g vinyl cyanide (AN) and 0.005g Potassium Persulphate then, logical rare gas element emptying is 30 minutes under the magnetic agitation.Continue to stir, oil bath is warming up to 70 ℃ of letex polymerizations 12 hours under inert atmosphere.After letex polymerization was finished, with the mixing liquid centrifugation, product was dry under 60 ℃ of temperature, obtains brown micro mist, i.e. nano-silicon/polyacrylonitrile presoma.Should brown micro mist 700 ℃ of calcinings 24 hours under inert atmosphere protection, obtain black silicon/silicon/charcoal core-shell structure nanometer composite material.
The electrochemical property test of the silicon/silicon/charcoal core-shell structure that obtains is as follows.With silicon/silicon/charcoal core-shell structure nanometer 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, forms two electrode simulated batteries, and silicon/silicon/charcoal core-shell structure nanometer composite material in the working electrode, carbon black, PVDF weight percent are 40: 40: 20, charging and discharging currents density is 0.2mA/cm
2Recording the initial charge capacity is 1364.8mAh/g, and 20 times circulation back capacity remains on 26.8% of initial capacity.
Embodiment 2
0.5g nano-silicon and 0.5g polyvinylpyrrolidone (polyvinylpyrrolidone) are added in the 200ml water, and continuous ultrasound disperseed 30 minutes, and nano-silicon is uniformly dispersed.Add 1gOP again
9, continuous ultrasound emulsification 30 minutes.Add 1g vinyl cyanide (AN) and 0.005g Potassium Persulphate then, logical rare gas element emptying is 1 hour under the magnetic agitation.Continue to stir, oil bath is warming up to 70 ℃ of letex polymerizations 12 hours under inert atmosphere.After letex polymerization was finished, with the mixing liquid centrifugation, product was dry under 60 ℃ of temperature, obtains brown micro mist, i.e. nano-silicon/polyacrylonitrile presoma.Should brown micro mist 750 ℃ of calcinings 24 hours under inert atmosphere protection, obtain black silicon/silicon/charcoal core-shell structure nanometer composite material.The transmission electron microscope picture and the electronic energy spectrum of the nano composite material that obtains are seen Fig. 2, and this figure shows that matrix material is a core/shell structure.The electrochemical property test of silicon/silicon/charcoal core-shell structure is identical with embodiment 1.Recording the initial charge capacity is 1137.4mAh/g, and 20 times circulation back capacity remains on 52.5% of initial capacity.Its first charge-discharge curve and cycle performance are shown in Fig. 1.
Embodiment 3
0.5g nano-silicon and 0.5g polyvinylpyrrolidone are added in the 200ml water, and continuous ultrasound disperseed 30 minutes, and nano-silicon is uniformly dispersed.Add the 1g sodium laurylsulfonate again, continuous ultrasound emulsification 1 hour.Add 1.5g vinylbenzene and 0.01g Diisopropyl azodicarboxylate (AIBN) then, logical rare gas element emptying is 2 hours under the magnetic agitation.Continue to stir, oil bath is warming up to 70 ℃ of letex polymerizations 8 hours under inert atmosphere.After letex polymerization was finished, with the mixing liquid centrifugation, product was dry under 60 ℃ of temperature, obtains brown micro mist, i.e. nano-silicon/polystyrene presoma.Should brown micro mist 800 ℃ of calcinings 16 hours under inert atmosphere protection, obtain black silicon/silicon/charcoal core-shell structure nanometer composite material.The electrochemical property test of silicon/silicon/charcoal core-shell structure is identical with embodiment 1.Recording the initial charge capacity is 1020.6mAh/g, and 20 times circulation back capacity remains on 39.2% of initial capacity.
0.5g nano-silicon and 0.5g polyvinylpyrrolidone (polyvinylpyrrolidone) are added in the 200ml water, and continuous ultrasound disperseed 30 minutes, and nano-silicon is uniformly dispersed.Add 1gOP again
10, continuous ultrasound emulsification 1 hour.Add 2g vinylbenzene and 0.01g Diisopropyl azodicarboxylate (AIBN) then, logical rare gas element emptying is 3 hours under the magnetic agitation.Continue to stir, oil bath is warming up to 70 ℃ of letex polymerizations 10 hours under inert atmosphere.After letex polymerization was finished, with the mixing liquid centrifugation, product was dry under 60 ℃ of temperature, obtains brown micro mist, i.e. nano-silicon/polyacrylonitrile presoma.Should brown micro mist 750 ℃ of calcinings 24 hours under inert atmosphere protection, obtain black silicon/silicon/charcoal core-shell structure nanometer composite material.The electrochemical property test of silicon/silicon/charcoal core-shell structure is identical with embodiment 1.Recording the initial charge capacity is 885.3mAh/g, and 20 times circulation back capacity remains on 36.9% of initial capacity.
Claims (9)
1. a method for preparing silicon/silicon/charcoal core-shell structure nanometer composite material is characterized in that comprising the steps:
(1) ultra-sonic dispersion: nano-silicon and dispersion agent are added in the entry, 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 controlled at 1nm-500nm;
(2) ultrasonic emulsification: emulsifying agent is added in step (1) the gained mixing liquid continuous ultrasound emulsification 1 minute-5 hours;
(3) letex polymerization: add polymer precursor and initiator in step (2) gained mixing liquid, logical rare gas element emptying is 1 minute-24 hours under magnetic force or the mechanical stirring; Then stir and inert atmosphere under 50-120 ℃ of letex polymerization 30 minutes-48 hours;
(4) drying:, obtain nano-silicon/polymer precursor with dry under-30 ℃ to 100 ℃ temperature after step (3) the products therefrom centrifugation;
(5) high-temperature calcination: the presoma of step (4) gained was calcined 1 minute～96 hours under 600～1200 ℃ in inert atmosphere.
2. method according to claim 1 is characterized in that used dispersion agent is polyvinylpyrrolidone, polyvinyl alcohol, polyacrylic acid or poly-methyl acrylate in the step (1), and dispersant dosage is the 0.1-5 gram based on every gram nano-silicon.
3. according to the described method of claim 1, it is characterized in that used emulsifying agent is OP9, sodium lauryl sulphate or sodium laurylsulfonate in the step (2), the concentration of emulsifying agent is 0.01wt%-10wt%.
4. method according to claim 1, it is characterized in that used polymer precursor is the presoma of resol, Resins, epoxy, polyacrylic acid, polyacrylonitrile, polystyrene in the step (3), or several mixture in these presomas, its consumption is the 0.5-5 gram based on every gram nano-silicon; Used initiator is Potassium Persulphate, Diisopropyl azodicarboxylate, dibenzoyl peroxide or ammonium persulphate.
5. method according to claim 1 is characterized in that in the step (3), 70-90 ℃ of letex polymerization temperature, 4-12 hour letex polymerization time.
6. method according to claim 1 is characterized in that drying temperature is 50-80 ℃ in the step (4).
7. method according to claim 1 is characterized in that calcining temperature is 700-1000 ℃ in the step (5), and calcination time is 1 hour-24 hours.
8. one kind by any silicon/silicon/charcoal core-shell structure nanometer composite material that described method obtains among the claim 1-7, it is characterized in that with the nano-silicon being nuclear, with emulsion polymerisation process at nano-silicon surface coated polymer layer, again through low-temperature heat treatment, the hard charcoal that is transformed into by polymer layer is the nuclear-shell structured nano-composite material of shell, wherein, the particle diameter of nuclear is the 1-500 nanometer, and the thickness of shell is the 2-50 nanometer.
9. the described silicon/silicon/charcoal core-shell structure nanometer composite material of claim 8 is as the application of lithium ion battery negative material.
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| FR2980191B1 (en) | 2011-09-20 | 2014-10-24 | Commissariat Energie Atomique | PROCESS FOR PRODUCING A SILICON / CARBON COMPOSITE MATERIAL AND THE USE OF SUCH A MATERIAL |
| CN103682286B (en) * | 2013-12-18 | 2015-09-02 | 南京毕汉特威高分子材料有限公司 | Silicon/high molecular composite microsphere and silicon-carbon composite anode material for lithium ion battery and preparation method thereof |
| KR101615439B1 (en) | 2014-07-17 | 2016-05-13 | 오씨아이 주식회사 | Manufacturing mehtod of carbon-silicon composite |
| US10199643B2 (en) * | 2014-12-16 | 2019-02-05 | GM Global Technology Operations LLC | Negative electrode for lithium-based batteries |
| CN105140477B (en) * | 2015-07-30 | 2018-02-02 | 湖北大学 | Si-C composite material and preparation method thereof |
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| CN108987727A (en) * | 2018-08-23 | 2018-12-11 | 宝鸡文理学院 | A kind of anode material for lithium-ion batteries and preparation method thereof with clad |
| CN110854368B (en) * | 2019-11-21 | 2021-09-28 | 陕西煤业化工技术研究院有限责任公司 | High-capacity silicon-carbon negative electrode precursor material and preparation method thereof |
| CN112919448A (en) * | 2021-01-26 | 2021-06-08 | 常德速碳新能源科技有限公司 | Carbon negative electrode material for lithium ion battery and preparation method thereof |
| CN113422009B (en) * | 2021-06-01 | 2022-03-18 | 广东工业大学 | Lithium ion battery cathode material and preparation method and application thereof |
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