CN104300151A - Preparation method of porous carbon ball-loaded M-Sn alloy nano particle composite material - Google Patents

Preparation method of porous carbon ball-loaded M-Sn alloy nano particle composite material Download PDF

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Publication number
CN104300151A
CN104300151A CN201410535826.8A CN201410535826A CN104300151A CN 104300151 A CN104300151 A CN 104300151A CN 201410535826 A CN201410535826 A CN 201410535826A CN 104300151 A CN104300151 A CN 104300151A
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porous carbon
carbon ball
preparation
composite material
nano particle
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CN201410535826.8A
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CN104300151B (en
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温鸣
陈世培
邢柯
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Tongji University
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Tongji University
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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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • 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 invention relates to a preparation method of a porous carbon ball-loaded M-Sn alloy nano particle composite material. The preparation method comprises the following steps: weighing porous carbon balls, and adding the porous carbon balls into a solvent for ultrasonic dispersion, adding tin salt for ultrasonic uniform mixing, stirring and heating for reaction; after reacting to reach a certain temperature, adding another salt (iron salt or cobalt salt or nickel salt) dissolved in advance and a reducing agent, and carrying out high-temperature returning reaction; and after the reaction is finished, carrying out centrifugal washing to collect a product so as to obtain the porous carbon ball-loaded M-Sn (M=Fe, Co and Ni) alloy nano particle composite material. The preparation method has the advantages of being simple, and universal in preparation conditions, the product is stable in shape and high in purity, the product treatment is convenient and easy, and the preparation method is suitable for industrial production with the medium scale.

Description

A kind of preparation method of porous carbon ball load M-Sn alloy nano particle composite material
Technical field
The invention belongs to field of material technology, particularly relate to a kind of preparation method of porous carbon ball load M-Sn (M=Fe, Co, Ni) alloy nano particle composite material.
Background technology
Along with to the research and development of new forms of energy, new material and the progress of utilization, sight is transferred in the research of the lithium ion battery electrode material having wide application by researchers gradually.Lithium ion battery is as an effective sustainable stored energy system, there is the advantages such as volume is little, quality is light, capacitance is large, voltage is high, safe, pollution-free, become the current internationally recognized desirable chemical energy, be widely used in the product such as mobile communications tool, electric motor car, be expected to future realize large-scale application in more wide field.Wherein, kamash alloy is that lithium ion battery negative material has high theoretical specific capacity, and rich reserves, environmentally safe, but easily reunite due to nano particle, cause in the discharge and recharge journey of battery, capacity sharply declines, and cycle performance is unstable, thus limits to its further development and application.
Namely the present invention is starting point from overcoming this quagmire, the hole wall of porous carbon ball is utilized to provide carrier for nano particle, metal nanoparticle is carried on porous carbon ball wall, not only can overcome the reunion between metal oxide nanoparticles, the frame structure of porous carbon ball also can be utilized to provide the structural stability of composite material, utilize advantage common between them, greatly widen the range of application of alloy nano particle and porous carbon ball, in chemical power source, catalyst and pharmaceutical carrier and gas sensor etc., there is important using value.So explore the control synthetic method of simple, the effective metal oxide-loaded nano particle composite material of porous carbon ball, the investigation and application for this type of composite material has important theory and realistic meaning.
Summary of the invention
The object of this invention is to provide a kind of porous carbon ball load M-Sn (M=Fe, Co, Ni) preparation method of alloy nano particle composite material, technique is simple, prepared composite material effectively can suppress reunion and the volumetric expansion of alloy nano particle, the lithium ion battery negative material prepared thus has excellent electric conductivity, and corresponding lithium ion battery specific capacity is high, good cycle.
To achieve these goals, technical scheme of the present invention is as follows:
The invention provides a kind of preparation method of porous carbon ball load M-Sn (M=Fe, Co, Ni) alloy nano particle composite material, concrete steps are as follows:
Taking porous carbon ball to join in solvent after ultrasonic disperse, add the ultrasonic mixing of pink salt again, agitating heating is reacted, after reaching 200 ~ 300 DEG C, add the another kind of salt (molysite or cobalt salt or nickel salt) and reducing agent that dissolve in advance, high temperature reflux reaction 0.5 ~ 3h, carry out centrifuge washing after terminating and collect product and obtain porous carbon ball load M-Sn (M=Fe, Co, Ni) alloy nano particle composite material; Wherein:
The concentration of described porous carbon ball is 0.2 ~ 1.0mg/mL;
Described pink salt is SnCl 22H 2o, concentration is 0.005 ~ 0.05mol/L;
Described molysite is FeCl 3, concentration is 0.005 ~ 0.05mol/L;
Described cobalt salt is CoCl 26H 2o, concentration is 0.005 ~ 0.05mol/L;
Described nickel salt is NiCl 26H 2o, concentration is 0.005 ~ 0.05mol/L;
Described reducing agent is NaBH 4, concentration is 0.01 ~ 0.2mol/L.
In the present invention, the preparation method of described porous carbon ball, concrete steps are as follows:
(1) after deionized water dissolving sodium chloroacetate, add in humidifier, produce droplet by atomization, and introduce inert gas;
(2) import in the tube furnace quartz ampoule of 500 ~ 800 DEG C of work by controlling inert gas flow velocity by droplet, by the process of body of heater, droplet fast dewatering shrinks the porous carbon ball being converted into solid;
(3) collect the solid particle of discharging from quartz ampoule with absolute ethyl alcohol, centrifugation, drying obtain porous carbon ball, wherein:
The concentration range of described sodium chloroacetate is 0.5 ~ 2mol/L;
Described inert gas is argon gas 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, is SnFe;
As M=Co, be SnCo;
As M=Ni, be SnNi.
In the present invention, described washing is by deionized water and absolute ethyl alcohol washed product successively.
Owing to adopting such scheme, the present invention has following beneficial effect:
1, present invention achieves and utilize common inorganic salts and the porous carbon ball prepared by high-temperature spray pyrolysismethod to be the presoma of reaction, 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 material.
2, the particle size of method of the present invention to the oxide nano particles of load in product has very high control.
3, the present invention adopts high temperature reflux method, has very strong versatility.
4, the product that 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 comparatively vast potential for future development and application space.
5, technique of the present invention is simple, and preparation condition is general, and product morphology is stable, purity is high, and product process is convenient succinct, is suitable for medium-scale industrial production.
6, method of the present invention have mild condition, homogeneous heating, productive rate efficient, be easy to the features such as control.
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 material in embodiment 1, and scale is 500nm;
Fig. 3 is the TEM photo of composite material in embodiment 1, and scale is 50nm;
Fig. 4 is the XRD collection of illustrative plates of composite material in embodiment 1;
Fig. 5 is the SEM photo of composite material in embodiment 2, and scale is 500nm;
Fig. 6 is the XRD collection of illustrative plates of composite material in embodiment 2;
Fig. 7 is the SEM photo of composite material in embodiment 3, and scale is 100nm.
Embodiment
Below in conjunction with accompanying drawing illustrated embodiment, the present invention is further detailed explanation.
Embodiment 1
1) high-temperature spray pyrolysismethod prepares porous carbon ball
The first step, takes 17.4g sodium chloroacetate dissolved in 100mL deionized water, adds in humidifier, produces droplet;
Second step, continues to pass into 1.2L/min argon gas in humidifier, is imported by droplet in the tube furnace quartz ampoule of 700 DEG C of work;
3rd step, utilizes absolute ethyl alcohol to collect the gas of discharging from quartz ampoule;
4th step, centrifugal product under 5000rpm collecting precipitation, in 60 DEG C of vacuum drying chambers, dry 5h, products therefrom is porous carbon ball.
2) synthesis of porous carbon ball load SnFe alloy nano particle composite material
The first step, accurately takes the triethylene glycol that 0.025g porous carbon ball is scattered in 50mL, then adds 0.0564g SnCl 22H 2after the ultrasonic mixing of O, proceed in the three-neck flask of 100mL, mechanical splash bar is also heated to 250 DEG C;
Second step, accurately takes 0.0406g FeCl 3be dissolved in 5mL triethylene glycol, in above-mentioned three-neck flask, dropwise add this solution, at 250 DEG C after back flow reaction 15min;
3rd step, dropwise adds the 0.25g NaBH be dissolved in advance in 5mL triethylene glycol 4, continue back flow reaction 1h at 250 DEG C, be cooled to after room temperature until solution after terminating, under the rotating speed of 8000rpm, centrifugal product, and by deionized water and absolute ethyl alcohol washed product successively, last 60 DEG C of desciccates, products therefrom is porous carbon ball load SnFe alloy nano particle composite material.
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 large, and specific area is large; Fig. 2 is the TEM photo of composite material in embodiment 1, and scale is 500nm, and comparison diagram 1 observable goes out porous carbon ball surface loaded particle, and is uniformly dispersed; Fig. 3 is the TEM photo of composite material in embodiment 1, and scale is 50nm, and this figure is the effect of Fig. 2 multiplication factor, can be observed loaded particle size homogeneous, and is 2 ~ 5nm nano-scale, and this is beneficial to electrical conductivity in lithium ion battery work more; Fig. 4 is the XRD collection of illustrative plates of composite material in embodiment 1, is consistent with compound S nFe standard card (JCPDS NO.25-0415), illustrates that in compound, load particle is SnFe alloy nanoparticle.
Embodiment 2
1) high-temperature spray pyrolysismethod prepares porous carbon ball
The first step, takes 11.6g sodium chloroacetate dissolved in 100mL deionized water, adds in humidifier, produces droplet;
Second step, continues to pass into 1.0L/min argon gas in humidifier, is imported by droplet in the tube furnace quartz ampoule of 700 DEG C of work;
3rd step, utilizes absolute ethyl alcohol to collect the gas of discharging from quartz ampoule;
4th step, centrifugal product under 5000rpm collecting precipitation, in 60 DEG C of vacuum drying chambers, dry 10h, products therefrom is porous carbon ball.
2) synthesis of porous carbon ball load SnCo nano composition
The first step, accurately takes the triethylene glycol that 0.030g porous carbon ball is scattered in 50mL, then adds 0.0564g SnCl 22H 2after the ultrasonic mixing of O, proceed in the three-neck flask of 100mL, mechanical splash bar is also heated to 230 DEG C;
Second step, accurately takes 0.0595g FeCl 3be dissolved in 5mL triethylene glycol, in above-mentioned three-neck flask, dropwise add this solution, at 230 DEG C after back flow reaction 15min;
3rd step, dropwise adds the 0.25g NaBH be dissolved in advance in 5mL triethylene glycol 4, continue back flow reaction 2h at 230 DEG C, be cooled to after room temperature until solution after terminating, under the rotating speed of 8000rpm, centrifugal product, and by deionized water and absolute ethyl alcohol washed product successively, last 60 DEG C of desciccates, products therefrom is porous carbon ball load SnFe alloy nano particle composite material.
Fig. 5 is the SEM photo of composite material in embodiment 2, and scale is 500nm, can find out particulate load equally and be uniformly dispersed, and after strengthening return time, particle size becomes large; Fig. 6 is the XRD collection of illustrative plates of composite material in embodiment 2, is consistent with compound S nCo standard card (JCPDS NO.02-1038), illustrates that in compound, load particle is SnCo particle.
Embodiment 3
1) high-temperature spray pyrolysismethod prepares porous carbon ball
The first step, takes 11.6g sodium chloroacetate dissolved in 100mL deionized water, adds in humidifier, produces droplet;
Second step, continues to pass into 1.0L/min argon gas in humidifier, is imported by droplet in the tube furnace quartz ampoule of 650 DEG C of work;
3rd step, utilizes absolute ethyl alcohol to collect the gas of discharging from quartz ampoule;
4th step, centrifugal product under 5000rpm collecting precipitation, in 60 DEG C of vacuum drying chambers, dry 5h, products therefrom is porous carbon ball.
2) synthesis of porous carbon ball load SnNi nano composition
The first step, accurately takes the triethylene glycol that 0.025g porous carbon ball is scattered in 50mL, then adds 0.0564g SnCl 22H 2after the ultrasonic mixing of O, proceed in the three-neck flask of 100mL, mechanical splash bar is also heated to 240 DEG C;
Second step, accurately takes 0.0594g FeCl 3be dissolved in 5mL triethylene glycol, in above-mentioned three-neck flask, dropwise add this solution, at 240 DEG C after back flow reaction 15min;
3rd step, dropwise adds the 0.25g NaBH be dissolved in advance in 5mL triethylene glycol 4continue back flow reaction 0.5h at 240 DEG C, be cooled to after room temperature until solution after end, under the rotating speed of 8000rpm, centrifugal product, and by deionized water and absolute ethyl alcohol washed product successively, last 60 DEG C of desciccates, products therefrom is porous carbon ball load SnNi alloy nano particle composite material.
Fig. 7 is the SEM photo of composite material in embodiment 3, and scale is 100nm, can be observed load capacity few, is that loaded particle is grown up ripe not enough, Gu particle size is less because the time of high temperature reflux reaction is shorter.
Above-mentioned is can understand and apply the invention for ease of those skilled in the art to the description of embodiment.Person skilled in the art obviously easily can make various amendment to these embodiments, and General Principle described herein is applied in other embodiments and need not through performing creative labour.Therefore, the invention is not restricted to embodiment here, those skilled in the art, according to announcement of the present invention, do not depart from improvement that scope makes and amendment all should within protection scope of the present invention.

Claims (5)

1. a preparation method for porous carbon ball load M-Sn alloy nano particle composite material, is characterized in that concrete steps are as follows:
Taking porous carbon ball to join in solvent after ultrasonic disperse, add the ultrasonic mixing of pink salt again, agitating heating is reacted, after reaching 200 ~ 300 DEG C, add the another kind of salt and reducing agent that dissolve 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 material, wherein: M is any one in Fe, Co or Ni; Described another kind of salt is any one in molysite, cobalt salt or nickel salt, wherein:
The concentration of described porous carbon ball is 0.2 ~ 1.0mg/mL;
Described pink salt is SnCl 22H 2o, concentration is 0.005 ~ 0.05mol/L;
Described molysite is FeCl 3, concentration is 0.005 ~ 0.05mol/L;
Described cobalt salt is CoCl 26H 2o, concentration is 0.005 ~ 0.05mol/L;
Described nickel salt is NiCl 26H 2o, concentration is 0.005 ~ 0.05mol/L;
Described reducing agent is NaBH 4, concentration is 0.01 ~ 0.2mol/L.
2. the preparation method of a kind of porous carbon ball load M-Sn alloy nano particle composite material according to claim 1, it is characterized in that the preparation method of described porous carbon ball, concrete steps are as follows:
(1) after deionized water dissolving sodium chloroacetate, add in humidifier, produce droplet by atomization, and introduce inert gas;
(2) import in the tube furnace quartz ampoule of 500 ~ 800 DEG C of work by controlling inert gas flow velocity by droplet, by the process of body of heater, droplet fast dewatering shrinks the porous carbon ball being converted into solid;
(3) collect the solid particle of discharging from quartz ampoule with absolute ethyl alcohol, centrifugation, drying obtain porous carbon ball, wherein:
The concentration range of described sodium chloroacetate is 0.5 ~ 2mol/L;
Described inert gas is argon gas or nitrogen;
Described gas flow rate is 0.5 ~ 2.5L/min.
3. the preparation method of a kind of porous carbon ball load M-Sn alloy nano particle composite material according to claim 1, is characterized in that: described solvent is triethylene glycol or TEG.
4. the preparation method of a kind of porous carbon ball load M-Sn alloy nano particle composite material according to claim 1, is characterized in that:
Described M-Sn (M=Fe, Co, Ni) alloy, as M=Fe, is SnFe;
As M=Co, be SnCo;
As M=Ni, be SnNi.
5. the preparation method of a kind of porous carbon ball load M-Sn alloy nano particle composite material according to claim 1, is characterized in that: described washing is by deionized water and absolute ethyl alcohol washed product successively.
CN201410535826.8A 2014-10-13 2014-10-13 A kind of preparation method of porous carbon ball load M-Sn alloy nano particle composite Expired - Fee Related CN104300151B (en)

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CN105789591A (en) * 2016-04-13 2016-07-20 同济大学 Method for synthesizing graphene/FeSn-nanorod array/graphene composite material of tent type frame structure
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
CN110459756A (en) * 2019-08-15 2019-11-15 深圳电丰电子有限公司 Lithium ion battery supports the preparation of high density nanocomposite with three-dimensional porous carbon

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105789591A (en) * 2016-04-13 2016-07-20 同济大学 Method for synthesizing graphene/FeSn-nanorod array/graphene composite material of tent type frame structure
CN105789591B (en) * 2016-04-13 2018-08-24 同济大学 The synthetic method of the graphene of tent type frame structure/FeSn- nanometer stick arrays/graphene composite material
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
CN110459756A (en) * 2019-08-15 2019-11-15 深圳电丰电子有限公司 Lithium ion battery supports the preparation of high density nanocomposite with three-dimensional porous carbon

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