CN106299306B - A kind of tin/carbon composite of nanostructure and its preparation method and application - Google Patents

A kind of tin/carbon composite of nanostructure and its preparation method and application Download PDF

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CN106299306B
CN106299306B CN201610866020.6A CN201610866020A CN106299306B CN 106299306 B CN106299306 B CN 106299306B CN 201610866020 A CN201610866020 A CN 201610866020A CN 106299306 B CN106299306 B CN 106299306B
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carbon
tin
nanostructure
carbon composite
stannic oxide
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CN106299306A (en
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黄建国
王昆
张先林
沈鸣
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Zhejiang University ZJU
HSC Corp
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Zhejiang University ZJU
HSC Corp
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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
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/387—Tin or alloys based on tin
    • 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
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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

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Abstract

The invention discloses a kind of tin/carbon composite preparation methods of nanostructure, using the carbon fibre material of stannic oxide package as raw material, it is dipped in the aqueous solution of carbon source, the carbon fibre material for the stannic oxide package for obtaining being surrounded by carbon film through hydro-thermal reaction and post-processing, then the tin/carbon composite with nanostructure is obtained through reduction treatment.The present invention is by the carbon fibre material surface wrapped up in nano-stannic oxide first packet carbon, rear reduction, so that obtaining partial size is respectively less than 100nm and the uniform tin/carbon composite of particle diameter distribution.The lithium ion battery assembled using tin/carbon composite of the nanostructure as negative electrode material has specific capacity high, and cyclicity is good and the advantages such as have extended cycle life.

Description

A kind of tin/carbon composite of nanostructure and its preparation method and application
Technical field
The present invention relates to the preparation fields of composite material, and in particular to a kind of tin/carbon composite of nanostructure and its Preparation method and application.
Background technique
With the fast development of modern science and technology, the application of each class of electronic devices and electric vehicle is also increasingly wider General, therefore, the requirement to electrochmical power source is also higher and higher.Lithium ion battery is since its is small in size, and energy density is high, service life Long and small pollution of the environment, therefore the extensive concern of people is received, and have become a strong electric power resource and answer Used in all trades and professions.
Currently, the negative electrode material of the lithium ion battery of commercialization is mostly carbon material, such as graphite, but the theoretical ratio of graphite Capacity (372mAh/g) is lower, and in practical applications due in SEI film forming process loss of charge be seriously also extremely difficult to Its theoretical specific capacity, therefore the requirement it is impossible to meet people to high-energy density electrode material.It has been investigated that silicon, tin (Sn) etc. the reversible lithium storage capacity of semiconductor materials is much larger than graphite, but these materials can not be kept away during lithium ion deintercalation The generation bulk effect exempted from, therefore cause its cyclical stability poor, and then influence its commercialization.So how to reduce these materials The bulk effect of material becomes the hot issue of current Study on Li-ion batteries.
In recent years, tin material due to its higher theoretical specific capacity and operating voltage and stability height and safety it is good Etc. advantages and have received widespread attention.But as previously mentioned, tin material electrode can be sent out during lithium ion deintercalation Raw serious volume expansion and contraction, therefore the crushing that will lead to material falls off, and declines its specific capacity rapidly, influences Its cyclical stability.Many methods, which have been suggested, solves the problems, such as this, and wherein complex carbon material can effectively improve tin material Expect the cycle performance of electrode.
As the Chinese patent literature of 101202340 A of Publication No. CN disclose a kind of tin carbon nanometer compound material and its Preparation method, the composite material contain nanometer tin particles and carbon, the preparation method comprises the following steps: by soluble stannate or soluble pink salt with Starch mixes, and under inert atmosphere, is first to heat to 300~400 DEG C of heat preservations, then be warming up to 500~1000 DEG C and keep the temperature, and obtains after cooling To tin carbon nanometer compound material.It as tin source, with starch is carbon skeleton and the reduction for dispersing tin that this method, which is using stannate or pink salt, Carbon source obtains tin nanoparticles by the method for carbon thermal reduction.
For another example (Wu Feng, Li Yanhong, Wuchuan, Mu Daobin, Bai Yun, Wu Sheng elder generation lithium ion battery are compound with Sn/C by Wu Feng et al. The carbon thermal reduction of material prepares the inorganization journal of, the 1st phase of volume 25, in January, 20009) it with carbon dust is directly then reducing agent, benefit Sn/C composite material is prepared for the method for carbon thermal reduction.
Therefore, preparing Sn/C composite material using the method for carbon thermal reduction is preparation process more conventional at present, but by It is lower in the fusing point of Sn, only 231.89 DEG C, it will appear reunion when using carbo-thermal process preparation, to form big Sn Particle, therefore the partial size of the tin particles of carbothermic method preparation is mostly even up to micron level in 100nm or more.Using it as electricity Pole material is easy to happen bulk effect in charge and discharge process and leads to material disintegrating, declines its chemical property sharply and shadow Ring its commercialization.
Summary of the invention
The invention proposes a kind of tin/carbon composite preparation methods of nanostructure, by nano-stannic oxide The carbon fibre material surface of package first packet carbon, rear reduction, thus obtain partial size be respectively less than 100nm and the uniform tin of particle diameter distribution/ Carbon composite.The lithium ion battery assembled using tin/carbon composite of the nanostructure as negative electrode material has specific capacity Height, cyclicity is good and the advantages such as have extended cycle life.
The invention discloses a kind of tin/carbon composite preparation method of nanostructure, the carbon that stannic oxide is wrapped up Fibrous material immerses in the aqueous solution of carbon source, the carbon fiber for the stannic oxide package for obtaining being surrounded by carbon film through hydro-thermal reaction and post-processing Material is tieed up, then obtains tin/carbon composite of the nanostructure through reduction treatment.
The present invention is directed to the serious bulk effect that generates in deintercalation of tin, using the support and buffer function of carbon material, The height ratio capacity characteristic of tin is maintained, and increases its cyclical stability.
The carbon fibre material of stannic oxide package is immersed in the aqueous solution of carbon source in the present invention, after hydro-thermal reaction, meeting One layer of carbon-coating is first coated on the carbon fibre material surface of stannic oxide package, which can prevent in reduction process, liquid Tin be agglomerated into biggish tin particles and be detached from carbon fiber.Therefore, the carbon source of selection can be carbon containing organic matter, such as carbohydrate.
Preferably, the carbon source is glucose.The molecular weight of glucose itself is smaller, there is gas phase in carbonisation Small molecule escapes simultaneously, forms lesser stomata, thus can the carbon fibre material surface that stannic oxide wraps up formed one layer compared with For fine and close carbon film, and then in reduction process, stannic oxide can either be made to come into full contact with reducing gas, and can effective ground resistance Hinder liquid tin is agglomerated into biggish particle.
Preferably, the concentration of glucose solution is 0.1~2mol/L when using glucose as carbon source.Carbon source concentration mistake Low, the carbon film coated is too thin, cannot reach covered effect well；Concentration is too high, and the carbon film of cladding is too thick, will lead to subsequent Reduction be not thorough.Therefore, the concentration of glucose solution is further defined to 0.1~0.4mol/L.
Discovery is further tested, when the concentration of glucose solution is 0.1~0.4mol/L, stannic oxide package The variation of carbon fibre material surface coated carbon film thickness less, be each about 4nm, but with the increasing of glucose solution concentration Add, in final product, the partial size for the tin particles being attached on carbon nano-fiber but has the tendency that being gradually increased.Therefore, most preferably Glucose solution concentration be 0.1mol/L.
Preferably, the temperature of the hydro-thermal reaction is 180~200 DEG C, the time is 4~5h.
Preferably, the post-processing includes washing, dry, calcining and grinding.
It is washed respectively with deionized water and ethyl alcohol in post-processing.
The calcining carries out under an inert atmosphere, and the inert gas is nitrogen or helium.
Further preferably, the calcination condition are as follows: 400~500 DEG C of calcination temperature, 5~10h of calcination time, heating speed 1~5 DEG C/min of rate.It is found through experiment that the carbon film containing O-H of hydro-thermal reaction formation can be made under the preferred calcination condition It is more thoroughly carbonized, and then forms comparatively dense carbon film on the carbon fibre material surface of stannic oxide package.
The temperature of reduction treatment is too low, makes reaction that cannot occur or restore to be not thorough；And temperature is excessively high, can occur simultaneously Carbon thermal reduction generates biggish tin particles.Preferably, the condition of the reduction treatment are as follows: 400~500 DEG C of reduction temperature, also Former 5~10h of time, heating rate 5~10 DEG C/min, reducing gas H2/N2Gaseous mixture.
Further preferably, in the gaseous mixture, H2/N2Volume ratio be 1:9.Optimal reduction can be obtained under the atmosphere Effect.
Most preferably:
The concentration of the glucose solution is 0.1mol/L, and hydrothermal temperature is 180 DEG C, time 4h.Above-mentioned Under the conditions of most preferred, the surface coated carbon film thickness of carbon fibre material of stannic oxide package is about 4nm, which is Effective cladding to stannic oxide can be achieved, and convenient for subsequent reduction treatment to remove the carbon film.
It is 500 DEG C with the adaptable optimum calcinating temperature of the carbon film of the thickness, heating rate is 1 DEG C/min；Reduction temperature It is 500 DEG C, heating rate is 5 DEG C/min.In the tin/carbon composite finally obtained the diameter of tin nanoparticles be about 20~ 50nm, and be evenly distributed.
The carbon fibre material of the stannic oxide package used in the present invention, can refer in Publication No. CN103746099A Preparation method can also be obtained by other preparation methods or other approach.Herein, with reference to the method in CN103746099A, tool Body are as follows:
(1) stannic acid tetra-isopropyl is mixed with the mixed liquor of methanol/isopropanol, configuration obtains the tin that concentration is 5~20mM Sour tetra-isopropyl solution, and it is heated to 40~60 DEG C for use；
(2) pretreated native cellulose is immersed in stannic acid tetra-isopropyl solution, keeps liquid level to be higher than natural fine The upper surface of element is tieed up, deposition is stood；
(3) post-depositional native cellulose first through the washing of the mixed liquor of 40~60 DEG C of methanol/isopropanol at least three times after, It keeps liquid level to be higher than the upper surface of native cellulose, stands deposition；Again through 40~60 DEG C of deionized water washing washing at least three After secondary, hydrolysis is stood, most the mixed liquor afterwards through 40~60 DEG C of methanol/isopropanol is drained；
(4) it after repeating the processes of step (2)~(3) several times, then filtered, be dried；
(5) post-depositional native cellulose obtains the carbon fibre material of stannic oxide package through calcining.
Preferably, repeating process at least ten times of step (2)~(3).
The invention also discloses tin/carbon composite of the nanostructure prepared according to the above method and its in lithium-ion electric Application in pond.
Compared with prior art, the invention has the following advantages that
1, the present invention is by first packet carbon, rear H2Stannic oxide is reduced to tin nanoparticles, avoids carbon by the method for reduction Thermal reduction generates biggish tin particles because reaction temperature is excessively high, liquid tin is sharply reunited, and then largely reduces material Expect the bulk effect in charge and discharge process, effectively improves the specific capacity of material.
2, preparation process of the invention is simple, but significant effect, multiple with tin/carbon of the nanostructure of the invention being prepared The lithium ion battery that condensation material is assembled as negative electrode material has specific capacity big, and cyclical stability is high, has extended cycle life etc. excellent Point.
Detailed description of the invention
Fig. 1 is the transmission electron microscope picture of the carbon fibre material of the stannic oxide package for being surrounded by carbon film prepared by embodiment 1；
Fig. 2 is scanning electron microscope of the tin/carbon composite of nanostructure prepared by embodiment 1 under different amplification Figure；
Fig. 3 is tin/carbon composite transmission electron microscope picture of nanostructure prepared by embodiment 1；
Fig. 4 is tin/carbon composite high-resolution-ration transmission electric-lens figure of nanostructure prepared by embodiment 1；
Tin/carbon composite the transmission electron microscope picture for the nanostructure that Fig. 5 is comparative example 1, comparative example 2 is prepared respectively；
Fig. 6 is tin/carbon composite scanning nuclear microprobe figure prepared by comparative example 3；
Fig. 7 is the transmission electron microscope picture of the carbon fibre material of the stannic oxide package for being surrounded by carbon film prepared by embodiment 2；
Fig. 8 is tin/carbon composite transmission electron microscope picture of nanostructure prepared by embodiment 2；
Fig. 9 is the tin/carbon composite transmission electron microscope and high-resolution transmission plot of nanostructure prepared by embodiment 3；
Figure 10 is the tin/carbon composite transmission electron microscope and high-resolution transmission plot of nanostructure prepared by embodiment 4；
Figure 11 is the transmission electron microscope picture and X-ray diffractogram of final product prepared by embodiment 5；
Figure 12 is the constant current charge-discharge cycle performance of battery 1,2,3 and the coulombic efficiency curve of battery 1；
Figure 13 is charge-discharge performance curve of the battery 1,2,3 under different multiplying.
Specific embodiment
Embodiment 1
(1) using volume ratio for 1:1 methanol and isopropanol as solvent, configuration concentration be 10mM stannic acid tetra-isopropyl it is molten Liquid, and be stirred at room temperature 1 hour, it is heated to 50 DEG C.
(2) laboratory is often placed in Suction filtration device with quantitative filter paper, is cleaned filter paper 3 times with ethyl alcohol, vacuum is drained.
(3) Suction filtration device is wrapped in heating tape, holding meanss temperature is at 50 DEG C.
(4) the stannic acid tetra-isopropyl solution of 20mL step (1) configuration is added into the Suction filtration device of step (3), filters one Half solution makes solution impregnation quantitative filter paper, and remains that liquid level is higher than the surface of quantitative filter paper, stands 3 minutes, this is Deposition process.
(5) low vacuum filters stannic acid tetra-isopropyl solution to liquid level higher than quantitative filter paper surface, and being rapidly added temperature is 50 DEG C, the methanol/isopropanol mixed solvent that volume ratio is 1:1, stand 3 minutes rinse for 6 times, and the mixed solvent of 20mL is added, Low vacuum filters, add temperature be 50 DEG C pure water rinse 4 times, and 50 DEG C of the pure water of 20mL is added, stands 3 minutes, this is Hydrolytic process.It is filtered by vacuum in air after hydrolysis 15 minutes, until quantitative filter paper is dry.
(6) liquid level in step (4) and (5) is consistently higher than quantitative filter paper surface.This deposition is hydrolyzed to cyclic process, sinks One layer of tin dioxide thin film of product with a thickness of 1.3nm, recycle 15 times, obtain the tin dioxide thin film of thickness about 20nm.
(7) quantitative filter paper that deposited tin dioxide thin film in step (6) is placed in a vacuum drying oven and is dried overnight；So Calcine 6h at 500 DEG C in argon gas afterwards, heating rate is 1 DEG C/min, obtains the carbon fibre material of nano-stannic oxide package.
(8) carbon fibre material for the nano-stannic oxide package that calcining obtains in step (7) is immersed to the Portugal of 0.1mol/L In grape sugar aqueous solution, hydro-thermal reaction 4h obtains the carbon fibre material for the stannic oxide package for being coated with carbon film at 180 DEG C.
(9) successively use pure water and ethyl alcohol clear the carbon fibre material that the stannic oxide for being coated with carbon film in step (8) wraps up It washes for several times, postposition is dried overnight in a vacuum drying oven；6h is calcined at 500 DEG C in argon gas, heating rate is 1 DEG C/min.
(10) calcined material in step (9) is ground to it is powdered, in H2/N2(v/v=1:9) 500 in gaseous mixture 6h is restored at DEG C, heating rate is 5 DEG C/min, obtains tin/carbon composite of nanostructure.
Transmission electron microscope picture such as Fig. 1 institute of the carbon fibre material of the stannic oxide package manufactured in the present embodiment for being coated with carbon film Show, is the carbon fiber of the single stannic oxide package for being coated with carbon film in figure.The carbon fiber surface of stannic oxide package is coated with The carbon film of one layer of about 4nm.
Tin/carbon composite scanning electron microscope (SEM) photograph of nanostructure manufactured in the present embodiment is as shown in Fig. 2, Fig. 2A, Fig. 2 B Respectively amplify the scanning electron microscope (SEM) photograph of 22K and 40K.Observation Fig. 2 can see, and tin nanoparticles are more uniform to be supported on carbon nanometer On fiber.
Tin/carbon composite transmission electron microscope picture of nanostructure manufactured in the present embodiment is as shown in figure 3, Fig. 3 is single Load tin nanoparticles carbon fiber.The more uniform load of tin nanoparticles is partly embedded on carbon nano-fiber, thin nanometer The diameter of particle is about within the scope of 20~50nm.
Tin/carbon composite high-resolution-ration transmission electric-lens figure of nanostructure manufactured in the present embodiment is as shown in figure 4, lattice Fringe spacing d=0.278nm corresponds to the crystal face of (101) of tetragonal phase tin, it was demonstrated that the particle of carbon fiber surface is sijna really Rice grain.
Comparative example 1
Cycle-index in (6) the step of embodiment 1 is replaced with 5 times, remaining is same as Example 1, obtains Theil indices Tin/carbon composite of different nanostructures.
Tin/carbon composite transmission electron microscope picture such as Fig. 5 A institute of the different nanostructure of the Theil indices of this comparative example preparation Show, the sijna compared with tin/carbon composite of nanostructure prepared by embodiment 1, in tin/carbon composite of nanostructure Rice grain significantly reduces, and within the scope of 20~60nm of partial size, but distribution of particles is not uniform enough.
Comparative example 2
Cycle-index in (6) the step of embodiment 1 is replaced with 10 times, remaining is same as Example 1, obtains Theil indices Tin/carbon composite of different nanostructures.
Tin/carbon composite transmission electron microscope picture such as Fig. 5 B institute of the different nanostructure of the Theil indices of this comparative example preparation Show, the sijna compared with tin/carbon composite of nanostructure prepared by embodiment 1, in tin/carbon composite of nanostructure Rice grain significantly reduces, and within the scope of 20~60nm of partial size, but distribution of particles is not uniform enough.
Comparative example 3
Step (8) in embodiment 1, (9) are omitted, remaining step is same as Example 1, obtains tin/carbon composite wood Material.
Tin/carbon composite scanning nuclear microprobe figure of this comparative example preparation is as shown in Fig. 6 A, 6B and Fig. 6 C, with reality Tin/the carbon composite for applying the nanostructure of the preparation of example 1 is compared, the sijna rice in tin/carbon composite of this comparative example preparation Grain diameter significantly increases, and about within the scope of 200~300nm, and distribution of particles is extremely uneven, simultaneously because the partial size of tin particles It is larger, it is difficult to be attached on carbon fiber, so apparent obscission can occur.
Embodiment 2
Glucose solution concentration in (8) the step of embodiment 1 is limited to 0.4M, remaining step and 1 phase of embodiment Together.
Transmission electron microscope picture such as Fig. 7 institute of the carbon fibre material of the stannic oxide package manufactured in the present embodiment for being coated with carbon film Show, is the carbon fiber of the single stannic oxide package for being coated with carbon film in figure, the carbon film thickness of cladding is about 4nm.
Tin/carbon composite transmission electron microscope picture of nanostructure manufactured in the present embodiment is as shown in figure 8, Fig. 8 is single Fiber, it can be seen that tin particles are scattered to be attached on carbon nano-fiber, and has the tendency that being detached from carbon fiber, the partial size of particle About within the scope of 50~100nm.
Embodiment 3
Glucose solution concentration in (8) the step of embodiment 1 is limited to 0.8M, remaining step and 1 phase of embodiment Together.
The transmission electron microscope picture and Fig. 7 phase of the carbon fibre material of the stannic oxide package manufactured in the present embodiment for being coated with carbon film Seemingly, the carbon film thickness of cladding is about 8nm.
Tin/carbon composite transmission of nanostructure manufactured in the present embodiment and high-resolution-ration transmission electric-lens figure are respectively as schemed Shown in 9A and 9B.Fig. 9 A is single fiber, has particle to be unevenly supported on carbon nano-fiber, the partial size of particle about 30~ Within the scope of 80nm, there are also some irregular distribution of particles in the carbon fibers.Fig. 9 B is high-resolution-ration transmission electric-lens figure, lattice fringe Spacing d=0.281nm, d=0.298nm and d=0.345nm respectively correspond the crystal faces of (101) of tin, stannous oxide (101) crystal face of (110) of crystal face and stannic oxide, shows that thorough reduction cannot be reached with this condition.
Embodiment 4
Glucose solution concentration in (8) the step of embodiment 1 is limited to 2M, remaining step is same as Example 1.
The transmission electron microscope picture and Fig. 7 phase of the carbon fibre material of the stannic oxide package manufactured in the present embodiment for being coated with carbon film Seemingly, the carbon film thickness of cladding is about 12nm.
Tin/carbon composite transmission of nanostructure manufactured in the present embodiment and high-resolution-ration transmission electric-lens figure such as Figure 10 A With shown in 10B.Figure 10 A is single fiber, has particle more equably to load or be partly embedded on carbon nano-fiber, the grain of particle Diameter is about within the scope of 20~50nm, and there are also irregular distribution of particles in the carbon fibers.Figure 10 B is high-resolution-ration transmission electric-lens Figure, lattice fringe spacing d=0.194nm, d=0.247nm and d=0.343nm respectively correspond crystal face, the oxygen of (211) of tin The crystal face for changing the crystal face of (002) of stannous and (110) of stannic oxide, shows to restore with this condition and is also not thorough.
Embodiment 5
Reduction temperature in (10) the step of embodiment 1 is reduced to 300 DEG C by 500 DEG C, remaining step and 1 phase of embodiment Together.
The transmission electron microscope picture of final product manufactured in the present embodiment is as shown in 11A, and Figure 11 A is single fiber, with reduction Before compare, what variation, the still carbon film with the presence of one layer of about 4nm do not occur for fiber.
X-ray diffraction (XRD) figure of final product manufactured in the present embodiment is as shown in Figure 11 B, the crystal face diffraction in Figure 11 B Peak all corresponds to the crystal face of cubic phase rutile type stannic oxide, and showing that this experiment restores under the conditions of temperature is lower can not Stannic oxide is reduced into tin.
Application examples
Materials A is ground into 1h in the agate mortar, weigh 40mg and with mass ratio 80:10:10 and conductive agent acetylene black and Binder PVDF is mixed, and is dried in vacuum overnight at 80 DEG C；After be tuned into pasty slurry, ultrasonic 1h is added magneton and is stirred overnight, rear to apply In in nickel foam, it is dried in vacuo 12 hours, tabletting.
When materials A is tin/carbon composite of the nanostructure that is prepared of embodiment, the lithium ion battery that is prepared into Negative electrode tab is denoted as 1；
When materials A is the tin/carbon composite for the nanostructure that comparative example 1 and comparative example 2 are prepared respectively, preparation At anode plate for lithium ionic cell be denoted as 2,3 respectively；
Anode plate for lithium ionic cell is assembled in the glove box full of argon gas with positive plate-lithium piece respectively respectively, is obtained CR2025 type button cell.The electrolyte used is with LiPF6It is the ethylene carbonate (EC) and carbon of 1:1 with volume ratio for solute Diethyl phthalate (DEC) is solvent, and the diaphragm used is Celgard 2300.
The button cell of assembling is tested, tests battery respectively using battery system under constant current and different multiplying Charge-discharge performance, charge and discharge voltage range be 0.01~3.0V.
Battery 1 charge-discharge performance and coulombic efficiency under the constant current of 100mA/g is as shown in figure 12, first lap charge and discharge Electric specific capacity is respectively 539mAh/g and 1241mAh/g, coulombic efficiency 43%.After 150 circle of circulation, specific discharge capacity still has 468mAh/g, the coulombic efficiency after stablizing are maintained at 98% or more.Illustrate tin/carbon composite wood of the nanostructure of embodiment preparation The lithium battery of material assembling has biggish specific capacity and preferable cyclical stability.
The comparison of the constant current charge-discharge cycle performance of battery 2,3 is as shown in figure 12.It can be seen from the figure that circulation 100 After circle, the specific capacity of battery 1 still has 468mAh/g, and the specific capacity of battery 2 has fallen to 318mAh/g, 3 specific capacity of battery Only 231mAh/g.
Charge-discharge performance of the battery 1 under different multiplying is as shown in figure 13, in 100mA/g, 200mA/g, 500mA/ Ten circles are circuited sequentially under the current density of g, 1A/g, 2A/g, 3A/g, finally return 100mA/g.Specific capacity is still when 3000mA/g There is about 60mAh/g, after returning to 100mA/g, specific capacity is returned to 345mAh/g or more.
The comparison of charge-discharge performance of the battery 2,3 under different multiplying is as shown in figure 13.Since precursor is in filter paper Upper frequency of depositing is different, and Theil indices are different in material 1,2,3.Tin nanoparticles in material 1 will be significantly more than material 2,3, and It is respectively 15.9%, 9.9% and 7.9% by the Theil indices that thermogravimetric tests to obtain in material 1,2,3.Tin in material 1 simultaneously The distribution of nano particle wants more more uniform compared with material 2,3.So the high rate performance of battery 1 will be significantly better than battery 2、3。

Claims (8)

1. a kind of tin/carbon composite preparation method of nanostructure, which is characterized in that the carbon fiber for wrapping up stannic oxide Material immerses in the aqueous solution of carbon source, the carbon fiber material for the stannic oxide package for obtaining being surrounded by carbon film through hydro-thermal reaction and post-processing Material, then tin/carbon composite of the nanostructure is obtained through reduction treatment；
The carbon source is selected from carbohydrate, and the concentration of carbon source aqueous solution is 0.1 ~ 2mol/L；
The condition of the reduction treatment are as follows: 400 ~ 500 oC of reduction temperature, 5 ~ 10 h of recovery time, 5 ~ 10 oC/ of heating rate Min, reducing gas H2/N2Gaseous mixture；
In tin/carbon composite of the nanostructure, tin nanoparticles equably load or are partly embedded in carbon nano-fiber On.
2. tin/carbon composite preparation method of nanostructure according to claim 1, which is characterized in that described Carbon source is glucose.
3. tin/carbon composite preparation method of nanostructure according to claim 1, which is characterized in that described The concentration of carbon source aqueous solution is 0.1 ~ 0.4mol/L.
4. tin/carbon composite preparation method of nanostructure according to claim 1, which is characterized in that the water The temperature of thermal response is 180 ~ 200 oC, and the time is 4 ~ 5h.
5. tin/carbon composite preparation method of nanostructure according to claim 1, which is characterized in that described Post-processing includes washing, dry, calcining and grinding.
6. tin/carbon composite preparation method of nanostructure according to claim 5, which is characterized in that described Calcination condition are as follows: 400 ~ 500 oC of calcination temperature, 5 ~ 10 h of calcination time, 1 ~ 5 oC/min of heating rate.
7. tin/carbon composite of the nanostructure of method preparation described in a kind of any claim according to claim 1 ~ 6.
8. a kind of application of tin/carbon composite of nanostructure according to claim 7 in lithium ion battery.
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CN108321376B (en) * 2018-02-08 2020-05-22 合肥工业大学 N-doped porous carbon nanofiber @ tin dioxide lithium ion battery cathode material and preparation method thereof
CN108417780A (en) * 2018-02-08 2018-08-17 陕西科技大学 A kind of preparation and its application of anode material of lithium-ion battery stainless (steel) wire load carbon covered stannum rice structure
CN111540897B (en) * 2020-05-11 2021-08-06 中国科学院重庆绿色智能技术研究院 Preparation method of high-performance hollow three-dimensional tin-carbon lithium battery cathode material
CN111682184B (en) * 2020-06-23 2023-07-14 欣旺达电动汽车电池有限公司 Tin-based composite material, preparation method thereof, negative plate and lithium ion battery
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CN114597369B (en) * 2022-03-16 2023-08-01 四川轻化工大学 Carbon tin nanocomposite and preparation method and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102683654A (en) * 2011-03-10 2012-09-19 丰田自动车株式会社 Tin carbon composite, preparation method thereof, battery anode part comprising tin carbon composite, and battery with anode part
CN102983315A (en) * 2012-12-20 2013-03-20 福州大学 Method for preparing one-dimensional C/ Sn@C/ C composite nano tubes by using CuO nano wires as template
CN103746099A (en) * 2014-01-17 2014-04-23 江苏华盛精化工股份有限公司 Preparation method of tin-dioxide-coated carbon fiber material, and product and application thereof
CN105206815A (en) * 2015-09-28 2015-12-30 清华大学 Carbon-coated Li4Ti5O12-TiO2/Sn nanocomposite and preparation and application thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10003075B2 (en) * 2014-06-12 2018-06-19 Council Of Scientific And Industrial Research Carbon nanotube-metal nanocomposites as flexible, free standing, binder free high performance anode for Li-ion battery

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102683654A (en) * 2011-03-10 2012-09-19 丰田自动车株式会社 Tin carbon composite, preparation method thereof, battery anode part comprising tin carbon composite, and battery with anode part
CN102983315A (en) * 2012-12-20 2013-03-20 福州大学 Method for preparing one-dimensional C/ Sn@C/ C composite nano tubes by using CuO nano wires as template
CN103746099A (en) * 2014-01-17 2014-04-23 江苏华盛精化工股份有限公司 Preparation method of tin-dioxide-coated carbon fiber material, and product and application thereof
CN105206815A (en) * 2015-09-28 2015-12-30 清华大学 Carbon-coated Li4Ti5O12-TiO2/Sn nanocomposite and preparation and application thereof

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