CN106941176B - A kind of SnO as negative electrode of lithium ion battery2/ C nano medicine ball and preparation method thereof - Google Patents

A kind of SnO as negative electrode of lithium ion battery2/ C nano medicine ball and preparation method thereof Download PDF

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CN106941176B
CN106941176B CN201710352905.9A CN201710352905A CN106941176B CN 106941176 B CN106941176 B CN 106941176B CN 201710352905 A CN201710352905 A CN 201710352905A CN 106941176 B CN106941176 B CN 106941176B
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sno
medicine ball
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CN106941176A (en
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李柳青
张海燕
李争晖
钟威豪
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Guangdong University of Technology
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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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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 present invention provides a kind of SnO as negative electrode of lithium ion battery2The preparation method of/C nano medicine ball, comprising the following steps: A) by tin source compound and crosslinking agent existing for the catalyst under the conditions of carry out cross-linking reaction, obtain cross-linked polymer nanometer medicine ball；B) the cross-linked polymer nanometer medicine ball is carbonized, obtains SnO2/ C nano medicine ball.Preparation method provided by the invention is simple, the SnO that the method is prepared2/ C nano composite material has the characteristics that high-energy density, high power density and stable cycle performance.

Description

A kind of SnO as negative electrode of lithium ion battery2/ C nano medicine ball and preparation method thereof
Technical field
The invention belongs to technical field of lithium ion, and in particular to a kind of SnO2/C as negative electrode of lithium ion battery Nanometer medicine ball and preparation method thereof.
Background technique
With the development of electronic equipment and electric car, lithium ion battery is because its energy density is high, has extended cycle life, in day Often increasingly important role is played in life.In order to meet the needs of people are growing for lithium ion battery, people It has done a large amount of work and has looked for the novel anode material with high capacity and outstanding cycle performance.Graphite is due to its special layer Structure becomes a kind of most classic negative electrode material, but because its theoretical capacity only has 372mAh g-1, this works as far from satisfaction Preceding needs.In order to solve this problem, many is for Si sill, metal alloy, metal oxide and metal chalcogenide chemical combination Object, which has been carried out, to come.Because stannic oxide has theoretical capacity height (790mAh g-1), the advantages that storage resources are abundant, so Stannic oxide sill is considered as one of most promising negative electrode material of lithium ion battery.
There are many schemes for improving SnO at present2The lithium ion battery negative material of base.For example, reducing insertion SnO2 The size of particle is to reduce its volume expansion ratio when as lithium ion battery negative material during charge and discharge removal lithium embedded Example reduces the stress due to caused by volume expansion with this to reducing SnO2Dusting of the particle in charge and discharge process； In addition there are one researchers by SnO2Particles coat protects SnO in porous carbon layer with this2Particle from charge and discharge process by It is crushed caused by volume expansion, to improve SnO2The charge-discharge performance of/C composite.But above-mentioned SnO2/ C is compound The preparation process of material complexity is always one and is difficult to the problem of breaking through.So far for simply preparing while having ultra-fine SnO2The nanocomposite that particle is embedded into two big advantages of more empty carbon structures is still a problem.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that providing a kind of SnO as negative electrode of lithium ion battery2/C Nanometer medicine ball and preparation method thereof, preparation method provided by the invention is simple, the SnO that the method is prepared2/ C nano is multiple Condensation material has the characteristics that high-energy density, high power density and stable cycle performance.
The present invention provides a kind of SnO as negative electrode of lithium ion battery2The preparation method of/C nano medicine ball, including with Lower step:
A cross-linking reaction is carried out under the conditions of) by tin source compound and crosslinking agent existing for the catalyst, obtains cross-linked polymer Nanometer medicine ball；
B) the cross-linked polymer nanometer medicine ball is carbonized, obtains SnO2/ C nano medicine ball.
Preferably, the molar ratio of the tin source compound and crosslinking agent is 1:(15~20).
Preferably, the tin source compound is selected from stannous phenide, triphenyltin, tetraphenyltin, diphenyl tin halides, triphen One of base tin halides and tetraphenyl tin halides are a variety of.
Preferably, the crosslinking agent be selected from dimethoxy alkane, dimethoxy alkene, dihalo alkane, dihalo alkene, One of alkane diacid, alkene diacid, dihalo alkanone and dihalo ketenes are a variety of.
Preferably, the crosslinking agent be selected from dimethoxymethane, dimethoxy-ethane, dimethoxy propane, methylene chloride, Dichloroethanes, dichloropropane, ethanedioic acid, malonic acid, succinic acid, dichloroacetone, dichloro butanone or dichloro pentanone.
Preferably, the catalyst is selected from aluminium chloride, iron chloride, sulfuric acid, stannic chloride, zinc chloride or hydrofluoric acid.
Preferably, it is described carry out cross-linking reaction solvent be dichloroethanes, methylene chloride, carbon tetrachloride, hexamethylene, benzene, One of nitrobenzene, acetic acid, ethylene glycol, dimethylformamide, ethyl acetate and ethyl alcohol are a variety of.
Preferably, the temperature of the cross-linking reaction is 50~100 DEG C, and the time of cross-linking reaction is the h of 7min~12.
Preferably, the carbonization are as follows:
600~900 DEG C are warming up to the heating rate of 0.5~20 DEG C/min, keeps the temperature 30min to 10h.
The present invention also provides a kind of SnO as negative electrode of lithium ion battery that above-mentioned preparation method is prepared2/ C receives Rice medicine ball, which is characterized in that including amorphous carbon and the nano SnO being filled in inside the amorphous carbon2Particle, it is described SnO2The partial size of/C nano medicine ball is 300~600nm, the nano SnO2The partial size of particle is 3~10nm, the nanometer SnO2Particle accounts for the SnO2The mass percent of/C nano medicine ball is 10%~30%.
Compared with prior art, the present invention provides a kind of SnO as negative electrode of lithium ion battery2/ C nano medicine ball Preparation method, comprising the following steps: A) by tin source compound and crosslinking agent existing for the catalyst under the conditions of carry out cross-linking reaction, Obtain cross-linked polymer nanometer medicine ball；B) the cross-linked polymer nanometer medicine ball is carbonized, obtains SnO2/ C nano is solid Ball.Preparation method provided by the invention is simple, the SnO that the method is prepared2/ C nano composite material have high-energy density, The characteristics of high power density and stable cycle performance.
The result shows that SnO prepared by the present invention2/ C nano composite material is in 200mAg-1Electric current under first put and first fill Capacity respectively reaches 1453.0mAh g-1With 718.8mAh g-1Capacity still keeps 628.5mAh g after circulation 120 is enclosed-1Its Capacity retention ratio (C100th/C2nd) reach 87.4%.High current 2A g in high rate performance-1Its lower capacity is 381mAh g-1, Even in 5A g-1Electric current under its capacity still keep 280mAh g-1.And the electric current Jing Guo multiple and different size of current When electric current comes back to 200mA g after test-1When its capacity still preferably remain 705mAh g-1。
Detailed description of the invention
Fig. 1 is the infrared spectrogram of triphenyl tin chloride and obtained nanometer medicine ball；
Fig. 2 is that the SEM of cross-linked polymer nanometer medicine ball schemes；
Fig. 3 is cross-linked polymer nanometer medicine ball, SnO2/ C nano medicine ball, carbon and business SnO2XRD diagram；
Fig. 4 is SnO2The TEM of/C nano medicine ball schemes；
Fig. 5 is SnO2The thermogravimetric curve of/C nano medicine ball；
Fig. 6 is SnO2The cyclic voltammetry curve figure of/C nano medicine ball；
Fig. 7 is carbon, nano-stannic oxide and SnO prepared by the present invention2The chemical property of/C nano medicine ball compares；
Fig. 8 is SnO2The TEM of/C nano medicine ball schemes；
Fig. 9 is SnO2The TEM of/C nano medicine ball schemes；
Figure 10 is SnO2The TEM of/C nano medicine ball schemes；
Figure 11 is the SnO obtained under the conditions of different carburizing temperatures2The XRD diagram of/C nano medicine ball；
Figure 12 is the SnO obtained under the conditions of different carbonization times2The XRD diagram of/C nano medicine ball；
Figure 13 is the SnO obtained under different carbonization ramp rate conditions2The XRD of/C nano medicine ball schemes.
Specific embodiment
The present invention provides a kind of SnO as negative electrode of lithium ion battery2The preparation method of/C nano medicine ball, including with Lower step:
A cross-linking reaction is carried out under the conditions of) by tin source compound and crosslinking agent existing for the catalyst, obtains cross-linked polymer Nanometer medicine ball；
B) the cross-linked polymer nanometer medicine ball is carbonized, obtains SnO2/ C nano medicine ball.
Cross-linking reaction is carried out under the conditions of the present invention is first by tin source compound and crosslinking agent existing for the catalyst, is handed over Linked polymer nanometer medicine ball.
In the present invention, the tin source compound be selected from stannous phenide, triphenyltin, tetraphenyltin, diphenyl tin halides, One of triphenyl phosphonium halides tin and tetraphenyl tin halides are a variety of, preferably stannous phenide, triphenyltin, tetraphenyltin, two Phenyltin chloride, triphenyl tin chloride or tetraphenylphosphonichloride chloride tin.
The crosslinking agent is selected from dimethoxy alkane, dimethoxy alkene, dihalo alkane, dihalo alkene, alkane two One of acid, alkene diacid, dihalo alkanone and dihalo ketenes are a variety of, preferably dimethoxymethane, dimethoxy Ethane, dimethoxy propane, methylene chloride, dichloroethanes, dichloropropane, ethanedioic acid, malonic acid, succinic acid, dichloroacetone, two Neoprene ketone or dichloro pentanone.
The molar ratio of the tin source compound and crosslinking agent is preferably 1:(15~20), more preferably 1:20.
The catalyst is selected from aluminium chloride, iron chloride, sulfuric acid, stannic chloride, zinc chloride or hydrofluoric acid.
Tin source compound is dissolved in solvent (carrying out the solvent of cross-linking reaction) by the present invention, and catalyst and friendship is being added Join agent, carries out cross-linking reaction, obtain cross-linked polymer nanometer medicine ball.
Wherein, the solvent for carrying out cross-linking reaction is dichloroethanes, methylene chloride, carbon tetrachloride, hexamethylene, benzene, nitre One of base benzene, acetic acid, ethylene glycol, dimethylformamide, ethyl acetate and ethyl alcohol are a variety of.
In the present invention, the cross-linking reaction is Friedel-Crafts reaction.The temperature of the cross-linking reaction is 50~100 DEG C, preferably It is 70~90 DEG C, the time of the cross-linking reaction is 7min~12h.
Then, the cross-linked polymer nanometer medicine ball is carbonized, obtains SnO2/ C nano medicine ball.
In the present invention, the process of the carbonization specifically:
600~900 DEG C are warming up to the heating rate of 0.5~20 DEG C/min, keeps the temperature 30min to 10h.
Wherein, the heating rate of the carbonization is preferably 1~15 DEG C/min, and more preferably 5~10 DEG C；The temperature of the carbonization Preferably 650~850 DEG C, more preferably 700~800 DEG C of degree；The time of the heat preservation is preferably 1~8h, more preferably 3~ 5h。
Finally, superfine nano SnO is obtained2Particle is uniformly embedded into the SnO in unsetting carbon2/ C nano medicine ball.
The present invention also provides a kind of SnO as negative electrode of lithium ion battery being prepared using above-mentioned preparation method2/ C nano medicine ball, including amorphous carbon and the nano SnO being filled in inside the amorphous carbon2Particle, the SnO2/ C receives The partial size of rice medicine ball is 300~600nm, the nano SnO2The partial size of particle is 3~10nm, the nano SnO2Particle accounts for The SnO2The mass percent of/C nano medicine ball is 10~30%.
Preferably, the SnO2The specific surface area size of/C nano medicine ball is 300~800m2g-1, in 200mA g-1's 120 circle capacity of circulation remains 628.5mAh g under electric current-1。
Preparation method provided by the invention is simple, and method provided by the invention is prepared for a kind of as negative electrode of lithium ion battery SnO2/ C nano medicine ball.SnO is embodied when the material is applied to lithium ion battery negative material2High energy density Feature, and due to the protective effect of unsetting carbon, which shows preferable cycle performance simultaneously.
The result shows that SnO prepared by the present invention2/ C nano composite material is in 200mA g-1Electric current under first put and first fill Capacity respectively reaches 1453.0mAh g-1With 718.8mAh g-1, capacity still keeps 628.5mAh g after circulation 120 is enclosed-1, Its capacity retention ratio (C100th/C2nd) reach 87.4%.High current 2A g in high rate performance-1Its lower capacity is 381mAh g-1Even in 5A g-1Electric current under its capacity still keep 280mAh g-1.And the electricity Jing Guo multiple and different size of current When electric current comes back to 200mA g after current test-1When its capacity still preferably remain 705mAh g-1。
For a further understanding of the present invention, below with reference to embodiment to provided by the invention as negative electrode of lithium ion battery SnO2/C nanometers of medicine balls and preparation method thereof are illustrated, and protection scope of the present invention is not limited by the following examples.
Embodiment 1
(1) 80mL 1 is taken, 2- dichloroethanes is incorporated in 250mL three-neck flask as solvent, and flask is placed in 60 DEG C water-bath in.
(2) it weighs 2g triphenyl tin chloride to be added in flask, weighs the anhydrous chlorination of 4g catalyst again after it is completely dissolved Aluminium.
(3) 4mL is pipetted with syringe and is added in flask as the crosslinking agent of the reaction using dimethoxymethane.Allow three Phenyltin chloride and dimethoxymethane obtain crosslinking after 60 DEG C of cross-linking reaction 15min and obtain triphenyl tin chloride and dimethoxy The cross-linked polymer nanometer medicine ball of methylmethane.
(4) reaction solution that step (3) obtains is filtered into cleaning with deionized water and alcohol respectively and obtains yellow powder afterwards three times End.Yellow powder is dried into 12h in 80 DEG C of drying box, obtains dry cross-linked polymer nanometer medicine ball.
Infrared spectroscopy detection is carried out to triphenyl tin chloride and obtained cross-linked polymer nanometer medicine ball, as a result sees figure 1, Fig. 1 is the infrared spectrogram of triphenyl tin chloride and obtained nanometer medicine ball.
Electronic Speculum observation is scanned to obtained cross-linked polymer nanometer medicine ball, as a result sees that Fig. 2, Fig. 2 are crosslinking high score The SEM of sub- nanometer medicine ball schemes.
(5) cross-linked polymer nanometer medicine ball prepared by step (4) is warming up to the heating rate of 2 DEG C/min from 50 DEG C 1h is kept the temperature after 600 DEG C to be carbonized to obtain ultra-fine SnO2Metallic particles is uniformly embedded into the SnO in unsetting carbon2/ C nano medicine ball.
Measure the SnO2The partial size of/C nano medicine ball is 500nm, the nano SnO being embedded in indefinite form carbon pores gap2Particle Partial size be 4nm, the nano SnO2Particle accounts for the SnO2The mass percent of/C nano medicine ball is 20%.The SnO2/ The specific surface area of C nano medicine ball is 463.3m2g-1。
To cross-linked polymer nanometer medicine ball obtained above, SnO2/ C nano medicine ball, carbon and business SnO2Material X-ray diffraction is carried out, as a result sees that Fig. 3, Fig. 3 are cross-linked polymer nanometer medicine ball, SnO2/ C nanometers of medicine ball, carbon and quotient Industry SnO2The XRD diagram of material (Chinese Shanghai, Fengxian, the road south bridge Qi Gang, Aladdin reagent Shanghai Co., Ltd).
To SnO obtained above2/ C nano medicine ball carries out transmission electron microscope observation, as a result sees that Fig. 4, Fig. 4 are SnO2The TEM of/C nano medicine ball schemes.In Fig. 4, right figure is the partial enlarged view of left figure.As shown in Figure 4, side provided by the invention Method has been successfully prepared SnO2/ C nano medicine ball.
To the above-mentioned SnO being prepared2/ C nano medicine ball carries out thermogravimetric analysis, as a result sees Fig. 5, Fig. 5 SnO2/ C receives The thermogravimetric curve of rice medicine ball.
By the above-mentioned SnO being prepared2/ C nano medicine ball is prepared into negative electrode of lithium ion battery using lithium piece as to electricity Pole, Celgard 2400 are diaphragm, and the assembling of 2302 electrode shells is lower at room temperature to measure SnO2The cyclicity of/C nanometers of medicine ball Can, as a result see Fig. 6, Fig. 6 SnO2The cyclic voltammetry curve figure of/C nano medicine ball.
To the SnO of carbon, nano-stannic oxide and above-mentioned preparation2/ C nano medicine ball carries out electrical performance testing, as a result See that Fig. 7, Fig. 7 are carbon, nano-stannic oxide and SnO prepared by the present invention2The chemical property of/C nano medicine ball compares.
By above-mentioned SnO2The assembled battery of/C nano composite material is in blue electric battery test system (CT2001A, Wuhan LAND Corporation, China) under carry out electrochemical property test.When current density is 200mA g-1When, the battery Head is put and the first capacity filled respectively reaches 1453.0mAh g-1With 718.8mAh g-1.Capacity is still kept after circulation 120 is enclosed 628.5mAh g-1, capacity retention ratio (C100th/C2nd) reach 87.4%.In its high rate performance, when current density reaches 2 A g-1When its capacity be 381mAh g-1Even in 5A g-1Electric current under its capacity still keep 280mAh g-1.And After the testing current of multiple and different size of current, electric current comes back to 200mA g-1When its capacity be still preferably restored to 705mAh g-1。
Embodiment 2
(1) 80mL 1 is taken, 2- dichloroethanes is incorporated in 250mL three-neck flask as solvent, and flask is placed in 60 DEG C water-bath in.
(2) it weighs 2g triphenyl tin chloride to be added in flask, weighs the anhydrous chlorination of 4g catalyst again after it is completely dissolved Aluminium.
(3) 4mL is pipetted with syringe and is added in flask as the crosslinking agent of the reaction using dimethoxymethane.Allow three Phenyltin chloride and dimethoxymethane obtain crosslinking after 60 DEG C of cross-linking reaction 15min and obtain triphenyl tin chloride and dimethoxy The cross-linked polymer nanometer medicine ball of methylmethane.
(4) reaction solution that step (3) obtains is filtered into cleaning with deionized water and alcohol respectively and obtains yellow powder afterwards three times End.Yellow powder is dried into 12h in 80 DEG C of drying box.
(5) by step (4) preparation cross-linked polymer ball with the heating rate of 2 DEG C/min from 50 DEG C be warming up to 700 DEG C after Heat preservation 1h is carbonized to obtain ultra-fine SnO2Metallic particles is uniformly embedded into the nanometer medicine ball in unsetting carbon.
To SnO obtained above2/ C nano medicine ball carries out transmission electron microscope observation, as a result sees that Fig. 8, Fig. 8 are SnO2The TEM of/C nano medicine ball schemes.Its XRD diagram is as shown in figure 11, and Figure 11 is obtained under the conditions of different carburizing temperatures SnO2The XRD diagram of/C nano medicine ball, SnO in Figure 112/ C-2-700-1 is to be carbonized with 2 DEG C/min from room temperature to 700 DEG C Keep the temperature 1h SnO obtained2The XRD diagram of/C nano medicine ball.
Embodiment 3
(1) 80mL 1 is taken, 2- dichloroethanes is incorporated in 250mL three-neck flask as solvent, and flask is placed in 60 DEG C water-bath in.
(2) it weighs 2g triphenyl tin chloride to be added in flask, weighs the anhydrous chlorination of 4g catalyst again after it is completely dissolved Aluminium.
(3) 4mL is pipetted with syringe and is added in flask as the crosslinking agent of the reaction using dimethoxymethane.Allow three Phenyltin chloride and dimethoxymethane obtain crosslinking after 60 DEG C of cross-linking reaction 15min and obtain triphenyl tin chloride and dimethoxy The cross-linked polymer nanometer medicine ball of methylmethane.
(4) reaction solution that step (3) obtains is filtered into cleaning with deionized water and alcohol respectively and obtains yellow powder afterwards three times End.Yellow powder is dried into 12h in 80 DEG C of drying box.
(5) by step (4) preparation cross-linked polymer ball with the heating rate of 2 DEG C/min from 50 DEG C be warming up to 800 DEG C after Heat preservation 1h is carbonized to obtain ultra-fine SnO2Metallic particles is uniformly embedded into the nanometer medicine ball in unsetting carbon.
To SnO obtained above2/ C nano medicine ball carries out transmission electron microscope observation, as a result sees that Fig. 9, Fig. 9 are SnO2The TEM of/C nano medicine ball schemes.Its XRD diagram is as shown in figure 11, and Figure 11 is obtained under the conditions of different carburizing temperatures SnO2The XRD diagram of/C nano medicine ball, SnO in Figure 112/ C-2-800-1 is to be carbonized with 2 DEG C/min from room temperature to 800 DEG C Keep the temperature 1h SnO obtained2The XRD diagram of/C nano medicine ball.
Embodiment 4
(1) 80mL 1 is taken, 2- dichloroethanes is incorporated in 250mL three-neck flask as solvent, and flask is placed in 60 DEG C water-bath in.
(2) it weighs 2g triphenyl tin chloride to be added in flask, weighs the anhydrous chlorination of 4g catalyst again after it is completely dissolved Aluminium.
(3) 4mL is pipetted with syringe and is added in flask as the crosslinking agent of the reaction using dimethoxymethane.Allow three Phenyltin chloride and dimethoxymethane obtain crosslinking after 60 DEG C of cross-linking reaction 15min and obtain triphenyl tin chloride and dimethoxy The cross-linked polymer nanometer medicine ball of methylmethane.
(4) reaction solution that step (3) obtains is filtered into cleaning with deionized water and alcohol respectively and obtains yellow powder afterwards three times End.Yellow powder is dried into 12h in 80 DEG C of drying box.
(5) by step (4) preparation cross-linked polymer ball with the heating rate of 2 DEG C/min from 50 DEG C be warming up to 900 DEG C after Heat preservation 1h is carbonized to obtain ultra-fine SnO2Metallic particles is uniformly embedded into the nanometer medicine ball in unsetting carbon.
To SnO obtained above2/ C nano medicine ball carries out transmission electron microscope observation, the result is shown in Figure 10, Tu10Wei SnO2The TEM of/C nano medicine ball schemes.Its XRD diagram is as shown in figure 11, and Figure 11 is obtained under the conditions of different carburizing temperatures SnO2The XRD diagram of/C nano medicine ball, SnO in Figure 112/ C-2-900-1 is to be carbonized with 2 DEG C/min from room temperature to 900 DEG C Keep the temperature 1h SnO obtained2The XRD diagram of/C nano medicine ball.
Embodiment 5
(1) 80mL1 is taken, 2- dichloroethanes is incorporated in 250mL three-neck flask as solvent, and flask is placed in 60 DEG C Water-bath in.
(2) it weighs 2g triphenyl tin chloride to be added in flask, weighs the anhydrous chlorination of 4g catalyst again after it is completely dissolved Aluminium.
(3) 4mL is pipetted with syringe and is added in flask as the crosslinking agent of the reaction using dimethoxymethane.Allow three Phenyltin chloride and dimethoxymethane obtain crosslinking after 60 DEG C of cross-linking reaction 15min and obtain triphenyl tin chloride and dimethoxy The cross-linked polymer nanometer medicine ball of methylmethane.
(4) reaction solution that step (3) obtains is filtered into cleaning with deionized water and alcohol respectively and obtains yellow powder afterwards three times End.Yellow powder is dried into 12h in 80 DEG C of drying box.
(5) by step (4) preparation cross-linked polymer ball with the heating rate of 2 DEG C/min from 50 DEG C be warming up to 600 DEG C after Heat preservation 2h is carbonized to obtain ultra-fine SnO2Metallic particles is uniformly embedded into the nanometer medicine ball in unsetting carbon.Its XRD diagram such as Figure 12 Shown, Figure 12 is the SnO obtained under the conditions of different carbonization times2The XRD diagram of/C nano medicine ball, SnO in Figure 122/C-2- 600-2 is to be warming up to 600 DEG C of heat preservations, 2 hours obtained SnO from 50 DEG C with 2 DEG C/min2The XRD diagram of/C nano medicine ball.
Embodiment 6
(1) 80mL 1 is taken, 2- dichloroethanes is incorporated in 250mL three-neck flask as solvent, and flask is placed in 60 DEG C water-bath in.
(2) it weighs 2g triphenyl tin chloride to be added in flask, weighs the anhydrous chlorination of 4g catalyst again after it is completely dissolved Aluminium.
(3) 4mL is pipetted with syringe and is added in flask as the crosslinking agent of the reaction using dimethoxymethane.Allow three Phenyltin chloride and dimethoxymethane obtain crosslinking after 60 DEG C of cross-linking reaction 15min and obtain triphenyl tin chloride and dimethoxy The cross-linked polymer nanometer medicine ball of methylmethane.
(4) reaction solution that step (3) obtains is filtered into cleaning with deionized water and alcohol respectively and obtains yellow powder afterwards three times End.Yellow powder is dried into 12h in 80 DEG C of drying box.
(5) by step (4) preparation cross-linked polymer ball with the heating rate of 2 DEG C/min from 50 DEG C be warming up to 600 DEG C after Heat preservation 4h is carbonized to obtain ultra-fine SnO2Metallic particles is uniformly embedded into the nanometer medicine ball in unsetting carbon.Its XRD diagram such as Figure 12 Shown, Figure 12 is the SnO obtained under the conditions of different carbonization times2The XRD diagram of/C nano medicine ball, SnO in Figure 122/C-2- 600-4 is to be warming up to 600 DEG C of heat preservations, 4 hours obtained SnO from 50 DEG C with 2 DEG C/min2The XRD diagram of/C nano medicine ball.
Embodiment 7
(1) 80mL 1 is taken, 2- dichloroethanes is incorporated in 250mL three-neck flask as solvent, and flask is placed in 60 DEG C water-bath in.
(2) it weighs 2g triphenyl tin chloride to be added in flask, weighs the anhydrous chlorination of 4g catalyst again after it is completely dissolved Aluminium.
(3) 4mL is pipetted with syringe and is added in flask as the crosslinking agent of the reaction using dimethoxymethane.Allow three Phenyltin chloride and dimethoxymethane obtain crosslinking after 60 DEG C of cross-linking reaction 15min and obtain triphenyl tin chloride and dimethoxy The cross-linked polymer nanometer medicine ball of methylmethane.
(4) reaction solution that step (3) obtains is filtered into cleaning with deionized water and alcohol respectively and obtains yellow powder afterwards three times End.Yellow powder is dried into 12h in 80 DEG C of drying box.
(5) by step (4) preparation cross-linked polymer ball with the heating rate of 5 DEG C/min from 50 DEG C be warming up to 600 DEG C after Heat preservation 1h is carbonized to obtain ultra-fine SnO2Metallic particles is uniformly embedded into the nanometer medicine ball in unsetting carbon.Its XRD diagram such as Figure 13 Shown, Figure 13 is the SnO obtained under different carbonization ramp rate conditions2The XRD diagram of/C nano medicine ball, SnO in Figure 132/ C-5-600-1 be with 5 DEG C of min from 50 DEG C be warming up to 600 DEG C after the obtained SnO of heat preservation 1h2The XRD diagram of/C nano medicine ball.
Embodiment 8
(1) 80mL 1 is taken, 2- dichloroethanes is incorporated in 250mL three-neck flask as solvent, and flask is placed in 60 DEG C water-bath in.
(2) it weighs 2g triphenyl tin chloride to be added in flask, weighs the anhydrous chlorination of 4g catalyst again after it is completely dissolved Aluminium.
(3) 4mL is pipetted with syringe and is added in flask as the crosslinking agent of the reaction using dimethoxymethane.Allow three Phenyltin chloride and dimethoxymethane obtain crosslinking after 60 DEG C of cross-linking reaction 15min and obtain triphenyl tin chloride and dimethoxy The cross-linked polymer nanometer medicine ball of methylmethane.
(4) reaction solution that step (3) obtains is filtered into cleaning with deionized water and alcohol respectively and obtains yellow powder afterwards three times End.Yellow powder is dried into 12h in 80 DEG C of drying box.
(5) by step (4) preparation cross-linked polymer ball with the heating rate of 10 DEG C/min from 50 DEG C be warming up to 600 DEG C after Heat preservation 1h is carbonized to obtain ultra-fine SnO2Metallic particles is uniformly embedded into the nanometer medicine ball in unsetting carbon.Its XRD diagram such as Figure 13 Shown, Figure 13 is the SnO obtained under different carbonization ramp rate conditions2The XRD diagram of/C nano medicine ball, SnO in Figure 132/ C-10-600-1 be with 10 DEG C of min from 50 DEG C be warming up to 600 DEG C after the obtained SnO of heat preservation 1h2The XRD diagram of/C nano medicine ball.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered It is considered as protection scope of the present invention.

Claims (8)

1. a kind of SnO as negative electrode of lithium ion battery2The preparation method of/C nano medicine ball, which is characterized in that including following step It is rapid:
A cross-linking reaction is carried out under the conditions of) by tin source compound and crosslinking agent existing for the catalyst, obtains cross-linked polymer nanometer Medicine ball；
The tin source compound be selected from stannous phenide, triphenyltin, tetraphenyltin, diphenyl tin halides, triphenyl phosphonium halides tin and One of tetraphenyl tin halides are a variety of；
The crosslinking agent is selected from dimethoxy alkane, dimethoxy alkene, dihalo alkane, dihalo alkene, alkane diacid, alkene One of hydrocarbon diacid, dihalo alkanone and dihalo ketenes are a variety of；
B) the cross-linked polymer nanometer medicine ball is carbonized, obtains SnO2/ C nano medicine ball.
2. preparation method according to claim 1, which is characterized in that the molar ratio of the tin source compound and crosslinking agent is 1:(15~20).
3. preparation method according to claim 1, which is characterized in that the crosslinking agent is selected from dimethoxymethane, diformazan Oxygroup ethane, dimethoxy propane, methylene chloride, dichloroethanes, dichloropropane, ethanedioic acid, malonic acid, succinic acid, dichloro third Ketone, dichloro butanone or dichloro pentanone.
4. preparation method according to claim 1, which is characterized in that the catalyst is selected from aluminium chloride, iron chloride, sulphur Acid, stannic chloride, zinc chloride or hydrofluoric acid.
5. preparation method according to claim 1, which is characterized in that the solvent for carrying out cross-linking reaction is two chloroethenes Alkane, methylene chloride, carbon tetrachloride, hexamethylene, benzene, nitrobenzene, acetic acid, ethylene glycol, dimethylformamide, ethyl acetate and ethyl alcohol One of or it is a variety of.
6. preparation method according to claim 1, which is characterized in that the temperature of the cross-linking reaction is 50~100 DEG C, is handed over The time of connection reaction is 7min-12h.
7. preparation method according to claim 1, which is characterized in that the carbonization are as follows:
600~900 DEG C are warming up to the heating rate of 0.5~20 DEG C/min, keeps the temperature 30min to 10h.
8. a kind of preparation method as described in claim 1~7 any one be prepared as negative electrode of lithium ion battery SnO2/ C nano medicine ball, which is characterized in that including amorphous carbon and the nano SnO being filled in inside the amorphous carbon2? Grain, the SnO2The partial size of/C nano medicine ball is 300~600nm, the nano SnO2The partial size of particle is 3~10nm, described Nano SnO2Particle accounts for the SnO2The mass percent of/C nano medicine ball is 10%~30%.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102255079A (en) * 2011-05-17 2011-11-23 奇瑞汽车股份有限公司 Stannum-carbon composite material used for lithium ion battery cathode, preparation method thereof and lithium ion battery
CN103346301A (en) * 2013-06-25 2013-10-09 上海交通大学 Preparation method and application of three-dimensional-structure graphene-base metal oxide composite material
CN103441246A (en) * 2013-06-25 2013-12-11 上海交通大学 Preparation method and application of three-dimensional nitrogen-doped graphene base tin dioxide composite material
CN103606662A (en) * 2013-11-12 2014-02-26 上海交通大学 Preparation method and application of three-dimensional graphene-based tin dioxide composite material
WO2016189047A1 (en) * 2015-05-27 2016-12-01 Ecole Polytechnique Federale De Lausanne (Epfl) Epfl-Tto Method for the preparation of a coating

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102255079A (en) * 2011-05-17 2011-11-23 奇瑞汽车股份有限公司 Stannum-carbon composite material used for lithium ion battery cathode, preparation method thereof and lithium ion battery
CN103346301A (en) * 2013-06-25 2013-10-09 上海交通大学 Preparation method and application of three-dimensional-structure graphene-base metal oxide composite material
CN103441246A (en) * 2013-06-25 2013-12-11 上海交通大学 Preparation method and application of three-dimensional nitrogen-doped graphene base tin dioxide composite material
CN103606662A (en) * 2013-11-12 2014-02-26 上海交通大学 Preparation method and application of three-dimensional graphene-based tin dioxide composite material
WO2016189047A1 (en) * 2015-05-27 2016-12-01 Ecole Polytechnique Federale De Lausanne (Epfl) Epfl-Tto Method for the preparation of a coating

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