CN104300151B - A kind of preparation method of porous carbon ball load M-Sn alloy nano particle composite - Google Patents
A kind of preparation method of porous carbon ball load M-Sn alloy nano particle composite Download PDFInfo
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- CN104300151B CN104300151B CN201410535826.8A CN201410535826A CN104300151B CN 104300151 B CN104300151 B CN 104300151B CN 201410535826 A CN201410535826 A CN 201410535826A CN 104300151 B CN104300151 B CN 104300151B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to the preparation method of a kind of porous carbon ball load M Sn alloy nano particle composite, comprise the following steps: weigh porous carbon ball and join in solvent after ultrasonic disperse, add the ultrasonic mixing of pink salt, agitating heating is reacted, after reaching uniform temperature, add the another kind of salt (iron salt or cobalt salt or nickel salt) and reducing agent dissolved in advance, high temperature reflux reacts, carry out centrifuge washing collection product after end and obtain porous carbon ball load M Sn (M=Fe, Co, Ni) alloy nano particle composite.The technique of the present invention is simple, and preparation condition is general, and product morphology is stable, purity is high, and product processes convenient succinct, is suitable for medium-scale commercial production.
Description
Technical field
The invention belongs to field of material technology, particularly relate to the preparation method of a kind of porous carbon ball load M-Sn (M=Fe, Co, Ni) alloy nano particle composite.
Background technology
Along with researching and developing new forms of energy, new material and the progress utilized, sight is gradually transferred to have in the research of the lithium ion battery electrode material of wide application by researchers.Lithium ion battery is as an effective sustainable energy-storage bank system, there is the advantages such as volume is little, light weight, capacitance are big, voltage is high, safe and pollution-free, have become as the current internationally recognized desirable chemical energy, it is widely used in the product such as mobile communications tool, electric motor car, will be expected to future realize large-scale application in broader field.Wherein, kamash alloy is that lithium ion battery negative material has high theoretical specific capacity, and rich reserves, environmentally safe, but owing to nanoparticle is easily reunited, cause in the discharge and recharge journey of battery, capacity drastically declines, and cycle performance is unstable, thus limits to its further development and application.
The present invention is i.e. starting point from overcoming this quagmire, the hole wall utilizing porous carbon ball provides carrier for nanoparticle, metal nanoparticle is carried on porous carbon ball wall, it is possible not only to the reunion overcome between metal oxide nanoparticles, it is also with the frame structure of porous carbon ball to provide the structural stability of composite, utilize advantage common between them, significantly widen alloy nano particle and the range of application of porous carbon ball, at electrochmical power source, catalyst and the aspect such as pharmaceutical carrier and gas sensor, there is important using value.So exploring the control synthetic method of the metal oxide-loaded nano particle composite material of porous carbon ball simple, effective, research and application for this type of composite have important theory and realistic meaning.
Summary of the invention
It is an object of the invention to provide a kind of porous carbon ball load M-Sn (M=Fe, Co, Ni) preparation method of alloy nano particle composite, technique is simple, prepared composite can effectively suppress reunion and the volumetric expansion of alloy nano particle, the lithium ion battery negative material thus prepared has the electric conductivity of excellence, and corresponding lithium ion battery specific capacity is high, good cycle.
To achieve these goals, technical scheme is as follows:
The invention provides the preparation method of a kind of porous carbon ball load M-Sn (M=Fe, Co, Ni) alloy nano particle composite, specifically comprise the following steps that
Weigh porous carbon ball and join in solvent after ultrasonic disperse, add the ultrasonic mixing of pink salt, agitating heating is reacted, after reaching 200 ~ 300 DEG C, add the another kind of salt (iron salt or cobalt salt or nickel salt) and reducing agent dissolved in advance, high temperature reflux reaction 0.5 ~ 3h, carry out centrifuge washing collection product after terminating and obtain porous carbon ball load M-Sn (M=Fe, Co, Ni) alloy nano particle composite;Wherein:
The concentration of described porous carbon ball is 0.2 ~ 1.0mg/mL;
Described pink salt is SnCl2·2H2O, concentration is 0.005 ~ 0.05mol/L;
Described iron salt is FeCl3, concentration is 0.005 ~ 0.05mol/L;
Described cobalt salt is CoCl2·6H2O, concentration is 0.005 ~ 0.05mol/L;
Described nickel salt is NiCl2·6H2O, concentration is 0.005 ~ 0.05mol/L;
Described reducing agent is NaBH4, concentration is 0.01 ~ 0.2mol/L.
In the present invention, the preparation method of described porous carbon ball, specifically comprise the following steps that
(1), after deionized water dissolving sodium chloroacetate, add in humidifier, produce droplet by atomization, and introduce noble gas;
(2) being imported by droplet by controlling noble gas flow velocity in the tube furnace quartz ampoule of 500 ~ 800 DEG C of work, during body of heater, droplet fast dewatering shrinks the porous carbon ball being converted into solid;
(3) collect the solid particle discharged from quartz ampoule with dehydrated alcohol, centrifugation, be dried to obtain porous carbon ball, wherein:
The concentration range of described sodium chloroacetate is 0.5 ~ 2mol/L;
Described noble gas is argon or nitrogen;
Described gas flow rate range is 0.5 ~ 2.5L/min.
In the present invention, described solvent is triethylene glycol or TEG.
In the present invention, described M-Sn (M=Fe, Co, Ni) alloy, as M=Fe, for SnFe;
As M=Co, for SnCo;
As M=Ni, for SnNi.
In the present invention, described washing is by deionized water and dehydrated alcohol washed product successively.
Owing to using such scheme, the method have the advantages that
1, present invention achieves the presoma that porous carbon ball is reaction utilizing common inorganic salt and having been prepared by high-temperature spray pyrolysismethod, porous carbon ball load M-Sn (M=Fe has been synthesized first by simple and easy method one-step method, Co, Ni) alloy nano particle composite.
2, the method for the present invention has the highest control to the size of the oxide nano particles of load in product.
3, the present invention uses high temperature reflux method, has the strongest versatility.
4, product prepared by the present invention is loose structure, and load nano particle is uniformly dispersed and is nano-scale, as lithium ion battery negative material, has height ratio capacity and high service life cycle, has more vast potential for future development and application space.
5, the technique of the present invention is simple, and preparation condition is general, and product morphology is stable, purity is high, and product processes convenient succinct, is suitable for medium-scale commercial production.
6, the method for the present invention has the features such as mild condition, homogeneous heating, productivity be efficient, easily controllable.
Accompanying drawing explanation
Fig. 1 is the TEM photo of porous carbon ball in embodiment 1, and scale is 200nm;
Fig. 2 is the TEM photo of composite in embodiment 1, and scale is 500nm;
Fig. 3 is the TEM photo of composite in embodiment 1, and scale is 50nm;
Fig. 4 is the XRD figure spectrum of composite in embodiment 1;
Fig. 5 is the SEM photograph of composite in embodiment 2, and scale is 500nm;
Fig. 6 is the XRD figure spectrum of composite in embodiment 2;
Fig. 7 is the SEM photograph of composite in embodiment 3, and scale is 100nm.
Detailed description of the invention
The present invention is further detailed explanation for illustrated embodiment below in conjunction with the accompanying drawings.
Embodiment 1
1) high-temperature spray pyrolysismethod prepares porous carbon ball
The first step, weighs 17.4g sodium chloroacetate dissolved in 100mL deionized water, adds in humidifier, produces droplet;
Second step, is continually fed into 1.2L/min argon in humidifier, is imported by droplet in the tube furnace quartz ampoule of 700 DEG C of work;
3rd step, utilizes dehydrated alcohol to collect expellant gas from quartz ampoule;
4th step, is centrifuged product and collects precipitation under 5000rpm, dry 5h in 60 DEG C of vacuum drying ovens, and products therefrom is porous carbon ball.
2) synthesis of porous carbon ball load SnFe alloy nano particle composite
The first step, accurately weighs 0.025g porous carbon ball and is scattered in the triethylene glycol of 50mL, add 0.0564g SnCl2·2H2After the ultrasonic mixing of O, proceeding in the three-neck flask of 100mL, machinery splash bar is also heated to 250 DEG C;
Second step, accurately weighs 0.0406g FeCl3It is dissolved in 5mL triethylene glycol, in above-mentioned three-neck flask, is added dropwise over this solution, at 250 DEG C after back flow reaction 15min;
3rd step, is added dropwise over the 0.25g NaBH being dissolved in advance in 5mL triethylene glycol4, continue back flow reaction 1h at 250 DEG C, after terminating after solution is cooled to room temperature, under the rotating speed of 8000rpm, centrifugal product, and by deionized water and dehydrated alcohol washed product successively, last 60 DEG C of desciccates, products therefrom is porous carbon ball load SnFe alloy nano particle composite.
Fig. 1 is the TEM photo of porous carbon ball in embodiment 1, and scale is 200nm, can see that carbon ball is loose structure from picture, and duct is abundant and capacity is big, and specific surface area is big;Fig. 2 is the TEM photo of composite in embodiment 1, and scale is 500nm, and comparison diagram 1 observable goes out porous carbon ball surface load granule, and is uniformly dispersed;Fig. 3 is the TEM photo of composite in embodiment 1, and scale is 50nm, and this figure is the effect of Fig. 2 amplification, can be observed to load granular size homogeneous, and is 2 ~ 5nm nano-scale, and this is more favorable for electronics conduction in lithium ion battery work;Fig. 4 is the XRD figure spectrum of composite in embodiment 1, is consistent with compound SnFe standard card (JCPDS NO.25-0415), illustrates that loading particle in complex is SnFe alloy nanoparticle.
Embodiment 2
1) high-temperature spray pyrolysismethod prepares porous carbon ball
The first step, weighs 11.6g sodium chloroacetate dissolved in 100mL deionized water, adds in humidifier, produces droplet;
Second step, is continually fed into 1.0L/min argon in humidifier, is imported by droplet in the tube furnace quartz ampoule of 700 DEG C of work;
3rd step, utilizes dehydrated alcohol to collect expellant gas from quartz ampoule;
4th step, is centrifuged product and collects precipitation under 5000rpm, dry 10h in 60 DEG C of vacuum drying ovens, and products therefrom is porous carbon ball.
2) synthesis of porous carbon ball load SnCo nano composition
The first step, accurately weighs 0.030g porous carbon ball and is scattered in the triethylene glycol of 50mL, add 0.0564g SnCl2·2H2After the ultrasonic mixing of O, proceeding in the three-neck flask of 100mL, machinery splash bar is also heated to 230 DEG C;
Second step, accurately weighs 0.0595g FeCl3It is dissolved in 5mL triethylene glycol, in above-mentioned three-neck flask, is added dropwise over this solution, at 230 DEG C after back flow reaction 15min;
3rd step, is added dropwise over the 0.25g NaBH being dissolved in advance in 5mL triethylene glycol4, continue back flow reaction 2h at 230 DEG C, after terminating after solution is cooled to room temperature, under the rotating speed of 8000rpm, centrifugal product, and by deionized water and dehydrated alcohol washed product successively, last 60 DEG C of desciccates, products therefrom is porous carbon ball load SnFe alloy nano particle composite.
Fig. 5 is the SEM photograph of composite in embodiment 2, and scale is 500nm, can be seen that particulate load equally and is uniformly dispersed, and after strengthening return time, particle size becomes big;Fig. 6 is the XRD figure spectrum of composite in embodiment 2, is consistent with compound SnCo standard card (JCPDS NO.02-1038), illustrates that loading particle in complex is SnCo granule.
Embodiment 3
1) high-temperature spray pyrolysismethod prepares porous carbon ball
The first step, weighs 11.6g sodium chloroacetate dissolved in 100mL deionized water, adds in humidifier, produces droplet;
Second step, is continually fed into 1.0L/min argon in humidifier, is imported by droplet in the tube furnace quartz ampoule of 650 DEG C of work;
3rd step, utilizes dehydrated alcohol to collect expellant gas from quartz ampoule;
4th step, is centrifuged product and collects precipitation under 5000rpm, dry 5h in 60 DEG C of vacuum drying ovens, and products therefrom is porous carbon ball.
2) synthesis of porous carbon ball load SnNi nano composition
The first step, accurately weighs 0.025g porous carbon ball and is scattered in the triethylene glycol of 50mL, add 0.0564g SnCl2·2H2After the ultrasonic mixing of O, proceeding in the three-neck flask of 100mL, machinery splash bar is also heated to 240 DEG C;
Second step, accurately weighs 0.0594g FeCl3It is dissolved in 5mL triethylene glycol, in above-mentioned three-neck flask, is added dropwise over this solution, at 240 DEG C after back flow reaction 15min;
3rd step, is added dropwise over the 0.25g NaBH being dissolved in advance in 5mL triethylene glycol4, continue back flow reaction 0.5h at 240 DEG C, after terminating after solution is cooled to room temperature, under the rotating speed of 8000rpm, centrifugal product, and by deionized water and dehydrated alcohol washed product successively, last 60 DEG C of desciccates, products therefrom is porous carbon ball load SnNi alloy nano particle composite.
Fig. 7 is the SEM photograph of composite in embodiment 3, and scale is 100nm, load capacity be can be observed few, is that load Grain growth is the most ripe, Gu particle size is less owing to the time of high temperature reflux reaction is shorter.
The above-mentioned description to embodiment is to be understood that for ease of those skilled in the art and apply the present invention.These embodiments obviously easily can be made various amendment by person skilled in the art, and General Principle described herein is applied in other embodiments without through performing creative labour.Therefore, the invention is not restricted to embodiment here, those skilled in the art should be within protection scope of the present invention according to the announcement of the present invention, the improvement made without departing from scope and amendment.
Claims (4)
1. the preparation method of a porous carbon ball load M-Sn alloy nano particle composite, it is characterised in that specifically comprise the following steps that
Weigh porous carbon ball and join in solvent after ultrasonic disperse, add the ultrasonic mixing of pink salt, agitating heating is reacted, after reaching 200 ~ 300 DEG C, add the another kind of salt and reducing agent dissolved in advance, high temperature reflux reaction 0.5 ~ 3h, carry out centrifuge washing collection product after terminating and obtain porous carbon ball load M-Sn alloy nano particle composite, wherein: M is any one in Fe, Co or Ni;Described another kind of salt is any one in iron salt, cobalt salt or nickel salt, wherein:
The concentration of described porous carbon ball is 0.2 ~ 1.0mg/mL;
Described pink salt is SnCl2·2H2O, concentration is 0.005 ~ 0.05mol/L;
Described iron salt is FeCl3, concentration is 0.005 ~ 0.05mol/L;
Described cobalt salt is CoCl2·6H2O, concentration is 0.005 ~ 0.05mol/L;
Described nickel salt is NiCl2·6H2O, concentration is 0.005 ~ 0.05mol/L;
Described reducing agent is NaBH4, concentration is 0.01 ~ 0.2mol/L;
The preparation method of described porous carbon ball, specifically comprises the following steps that
(1), after deionized water dissolving sodium chloroacetate, add in humidifier, produce droplet by atomization, and introduce noble gas;
(2) being imported by droplet by controlling noble gas flow velocity in the tube furnace quartz ampoule of 500 ~ 800 DEG C of work, during body of heater, droplet fast dewatering shrinks the porous carbon ball being converted into solid;
(3) collect the solid particle discharged from quartz ampoule with dehydrated alcohol, centrifugation, be dried to obtain porous carbon ball, wherein:
The concentration range of described sodium chloroacetate is 0.5 ~ 2mol/L;
Described noble gas is argon or nitrogen;
Described gas flow rate is 0.5 ~ 2.5L/min.
The preparation method of a kind of porous carbon ball the most according to claim 1 load M-Sn alloy nano particle composite, it is characterised in that: described solvent is triethylene glycol or TEG.
The preparation method of a kind of porous carbon ball the most according to claim 1 load M-Sn alloy nano particle composite, it is characterised in that:
Described M-Sn alloy, as M=Fe, for SnFe;
As M=Co, for SnCo;
As M=Ni, for SnNi.
The preparation method of a kind of porous carbon ball the most according to claim 1 load M-Sn alloy nano particle composite, it is characterised in that: described washing is by deionized water and dehydrated alcohol washed product successively.
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CN108199029A (en) * | 2018-01-11 | 2018-06-22 | 电子科技大学 | A kind of silkworm excrement mixes tin iron cell negative material and preparation method thereof |
CN110459756B (en) * | 2019-08-15 | 2020-07-07 | 深圳电丰电子有限公司 | Preparation of three-dimensional porous carbon supported high-density nano composite material for lithium ion battery |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101877406A (en) * | 2009-04-28 | 2010-11-03 | 株式会社电装 | Battery with nonaqueous electrolyte is with negative pole and the battery with nonaqueous electrolyte that uses this negative pole to make |
CN103022522A (en) * | 2012-12-07 | 2013-04-03 | 太原理工大学 | Ternary carbon loaded palladium tin platinum nanoparticle catalyst and preparation method thereof |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101877406A (en) * | 2009-04-28 | 2010-11-03 | 株式会社电装 | Battery with nonaqueous electrolyte is with negative pole and the battery with nonaqueous electrolyte that uses this negative pole to make |
CN103022522A (en) * | 2012-12-07 | 2013-04-03 | 太原理工大学 | Ternary carbon loaded palladium tin platinum nanoparticle catalyst and preparation method thereof |
Non-Patent Citations (3)
Title |
---|
Facile Synthesis of grapheme supported FeSn2 nanocrystals with enhanced Li-stroage capacity;Ye Ya;《RSC Adv》;20140430;第4卷;实验部分,结果讨论部分 * |
Porous Carbon Powers Prepared by Ultrasonic Spray Pyrolysis;SaraE.Skrabalak;《J.Am.Chem.SOc》;20060913;第128卷;第12642页第2-5段 * |
Single-Crystal Intermetallic M-Sn(M=Fe,Cu,Co,Ni)Nanospheres as Negative Electrodes for Lithium-ion Batteries;Xiao-Liang Wang;《Applied Materials&Interfaces》;20100430;第2卷(第5期);实验部分以及结果讨论部分 * |
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