CN106299306A - A kind of stannum/carbon composite of nanostructured and its preparation method and application - Google Patents
A kind of stannum/carbon composite of nanostructured and its preparation method and application Download PDFInfo
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
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Abstract
The invention discloses the preparation method of the stannum/carbon composite of a kind of nanostructured, with tin ash parcel carbon fibre material as raw material, it is dipped in the aqueous solution of carbon source, obtain being surrounded by the carbon fibre material of the tin ash parcel of carbon film through hydro-thermal reaction and post processing, then obtain the stannum/carbon composite with nanostructured through reduction treatment.The present invention, by the carbon fibre material surface first bag carbon of nano-stannic oxide parcel, reduce afterwards, thus obtains particle diameter and is respectively less than the stannum/carbon composite of 100nm and even particle size distribution.The lithium ion battery assembled as negative material using the stannum/carbon composite of this nanostructured, has specific capacity high, the advantages such as cyclicity is good and has extended cycle life.
Description
Technical field
The present invention relates to the preparation field of composite, be specifically related to a kind of nanostructured stannum/carbon composite and
Preparation method and application.
Background technology
Along with the fast development of modern science and technology, the application of each class of electronic devices and electric vehicle is more and more wider
General, therefore, the requirement to electrochmical power source is more and more higher.Lithium ion battery is little due to its volume, and energy density is high, service life
Long and to environment pollution is little, has therefore suffered from the extensive concern of people, and become a strong electric power resource should
It is used in all trades and professions.
At present, the negative material of the lithium ion battery of commercialization mostly is material with carbon element, such as graphite, but the theory of graphite ratio
Capacity (372mAh/g) is relatively low, and in actual applications due in SEI film forming process loss of charge also seriously be difficult to reach
Its theoretical specific capacity, is unable to the requirement meeting people to high-energy-density electrode material.It has been investigated that, silicon, stannum
Etc. (Sn) the reversible lithium storage capacity of semi-conducting material is much larger than graphite, but these materials can not be kept away during lithium ion deintercalation
The generation bulk effect exempted from, therefore causes its cyclical stability poor, and then affects its commercialization.So how reduce these materials
The bulk effect of material becomes the hot issue of current Study on Li-ion batteries.
In recent years, tin material is due to its higher theoretical specific capacity and running voltage, and stability is high and safety is good
Of great interest etc. advantage.But as previously mentioned, tin material electrode can be sent out during lithium ion deintercalation
Raw serious volumetric expansion and contraction, therefore can cause the pulverizing of material to come off, make its specific capacity decline rapidly further, impact
Its cyclical stability.Many methods have been suggested this problem of solution, and wherein complex carbon material can improve stannum material effectively
The cycle performance of material electrode.
As the Chinese patent literature of Publication No. CN 101202340 A disclose a kind of tin carbon nanometer compound material and
Preparation method, this composite contains nanometer tin granule and carbon, and preparation method is: by solubility stannate or solubility pink salt with
Starch mixes, and under inert atmosphere, is first to heat to 300～400 DEG C of insulations, then is warmed up to 500～1000 DEG C and is incubated, after cooling
To tin carbon nanometer compound material.The method is to be carbon skeleton and the reduction of dispersion stannum with stannate or pink salt as Xi Yuan, with starch
Carbon source, obtains tin nanoparticles by the method for carbon thermal reduction.
And for example Wu Feng et al. (Wu Feng, Li Yanhong, Wuchuan, Mu Daobin, Bai Yun, Wu Shengxian. lithium ion battery with Sn/C be combined
Prepared by the carbon thermal reduction of material. inorganization journal, the 1st phase of volume 25, in January, 20009) the most direct carbon dust is reducing agent, profit
It is prepared for Sn/C composite by the method for carbon thermal reduction.
Therefore, using the method for carbon thermal reduction to prepare Sn/C composite is the most conventional preparation technology, but by
Relatively low in the fusing point of Sn, only 231.89 DEG C, there will be reunion when using carbo-thermal process to prepare, thus form big Sn
Granule, therefore the particle diameter of tin particles prepared by carbothermic method is many is even up to micron level at more than 100nm.Using it as electricity
Pole material is susceptible to bulk effect in charge and discharge process and causes material disintegrating so that it is chemical property drastically declines and shadow
Ring its commercialization.
Summary of the invention
The present invention proposes the preparation method of the stannum/carbon composite of a kind of nanostructured, by nano-stannic oxide
The carbon fibre material surface first bag carbon of parcel, reduce afterwards, thus obtain particle diameter be respectively less than the stannum of 100nm and even particle size distribution/
Carbon composite.The lithium ion battery assembled as negative material using the stannum/carbon composite of this nanostructured, has specific capacity
Height, the advantages such as cyclicity is good and has extended cycle life.
The invention discloses the preparation method of the stannum/carbon composite of a kind of nanostructured, the carbon wrapped up by tin ash
Fibrous material immerses in the aqueous solution of carbon source, and the carbon obtaining being surrounded by the tin ash parcel of carbon film through hydro-thermal reaction and post processing is fine
Dimension material, then the stannum/carbon composite of described nanostructured is obtained through reduction treatment.
The present invention is directed to the serious bulk effect that stannum produces when deintercalation, utilize support and the cushioning effect of material with carbon element,
Maintain the height ratio capacity characteristic of stannum, and add its cyclical stability.
The carbon fibre material that tin ash wraps up is immersed by the present invention in the aqueous solution of carbon source, after hydro-thermal reaction, meeting
First being coated with one layer of carbon-coating on the carbon fibre material surface of tin ash parcel, this carbon-coating is possible to prevent in reduction process, liquid
Stannum be agglomerated into bigger tin particles and depart from carbon fiber.Therefore, the carbon source of selection can be the Organic substance of carbon containing, such as saccharide.
As preferably, described carbon source is glucose.The molecular weight of glucose itself, has gas phase in carbonisation
Little molecule escapes simultaneously, forms less pore, therefore can form one layer relatively on the carbon fibre material surface of tin ash parcel
For fine and close carbon film, and then in reduction process, tin ash can either be made to be fully contacted with reducing gas, again can effective ground resistance
Hinder liquid tin is agglomerated into bigger granule.
As preferably, during with glucose for carbon source, the concentration of D/W is 0.1～2mol/L.Carbon source concentration mistake
Low, the carbon film being coated with is the thinnest, it is impossible to reach covered effect well；Concentration is the highest, and the carbon film of cladding is the thickest, can cause follow-up
Reduction the most thorough.Therefore, the concentration of D/W is further defined to 0.1～0.4mol/L.
Through testing discovery further, when the concentration of D/W is 0.1～0.4mol/L, tin ash wraps up
The change of carbon fibre material surface coated carbon film thickness little, be each about 4nm, but along with the increasing of D/W concentration
Adding, in end product, the particle diameter of the tin particles being attached on carbon nano-fiber but has the trend being gradually increased.Therefore, most preferably
The concentration of D/W be 0.1mol/L.
As preferably, the temperature of described hydro-thermal reaction is 180～200 DEG C, and the time is 4～5h.
As preferably, described post processing includes washing, be dried, calcine and grinding.
Post processing is washed with deionized water and ethanol respectively.
Described calcining is carried out under an inert atmosphere, and described noble gas is nitrogen or helium.
Further preferably, described calcination condition is: calcining heat 400～500 DEG C, calcination time 5～10h, and heat up speed
Rate 1～5 DEG C/min.Find through test, under this preferred calcination condition, it is possible to make the carbon film containing O-H that hydro-thermal reaction is formed
Carbonization the most up hill and dale, and then form comparatively dense carbon film on the carbon fibre material surface of tin ash parcel.
The temperature of reduction treatment is too low, makes reaction can not occur or reduce the most thorough；Temperature is too high, can occur simultaneously
Carbon thermal reduction produces bigger tin particles.As preferably, the condition of described reduction treatment is: reduction temperature 400～500 DEG C, also
The former time 5～10h, heating rate 5～10 DEG C/min, reducing gas is H2/N2Gaseous mixture.
Further preferably, in described gaseous mixture, H2/N2Volume ratio be 1:9.Optimal reduction can be obtained under this atmosphere
Effect.
Most preferably:
The concentration of described D/W is 0.1mol/L, and hydrothermal temperature is 180 DEG C, and the time is 4h.Above-mentioned
Under the conditions of You Xuan, the surface coated carbon film thickness of carbon fibre material of tin ash parcel is about 4nm, and this carbon film thickness is i.e.
The effective cladding to tin ash can be realized, be easy to again follow-up reduction treatment to remove this carbon film.
The optimum calcinating temperature adapted with the carbon film of this thickness is 500 DEG C, and heating rate is 1 DEG C/min；Reduction temperature
Being 500 DEG C, heating rate is 5 DEG C/min.In the final stannum/carbon composite obtained the diameter of tin nanoparticles be about 20～
50nm, and be evenly distributed.
The carbon fibre material of the tin ash parcel used in the present invention, refers in Publication No. CN103746099A
Preparation method, it is possible to obtained by other preparation method or other approach.Herein, with reference to the method in CN103746099A, tool
Body is:
(1) being mixed with the mixed liquor of methanol/isopropanol by stannic acid four isopropyl ester, configuration obtains the stannum that concentration is 5～20mM
Acid four isopropyl ester solution, and be heated to 40～60 DEG C stand-by；
(2) pretreated native cellulose is immersed in stannic acid four isopropyl ester solution, keeps liquid level higher than natural fibre
The upper surface of dimension element, stands deposition；
(3) after the first mixed liquor through the methanol/isopropanol of 40～60 DEG C of post-depositional native cellulose washs at least three times,
Keep the liquid level upper surface higher than native cellulose, stand deposition；Deionized water wash through 40～60 DEG C washs at least three again
After secondary, stand hydrolysis, after drain through the mixed liquor of the methanol/isopropanol of 40～60 DEG C；
(4) repeat the process of step (2)～(3) several times after, then carry out sucking filtration, dried；
(5) post-depositional native cellulose obtains the carbon fibre material of tin ash parcel through calcining.
As preferably, repeat the process at least ten times of step (2)～(3).
The invention also discloses the stannum/carbon composite of the nanostructured prepared according to said method and at lithium-ion electric
Application in pond.
Compared with prior art, the invention have the advantages that
1, the present invention is through first bag carbon, rear H2The method of reduction, is reduced to tin nanoparticles by tin ash, it is to avoid carbon
Thermal reduction produces bigger tin particles because reaction temperature is too high, liquid tin is drastically reunited, and then largely reduces material
Material bulk effect in charge and discharge process, is effectively improved the specific capacity of material.
2, the preparation technology of the present invention is simple, but effect is notable, and the stannum/carbon of the nanostructured prepared with the present invention is multiple
The lithium ion battery that condensation material assembles as negative material, has specific capacity big, and cyclical stability is high, has extended cycle life etc. excellent
Point.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope picture of the carbon fibre material of the tin ash parcel being surrounded by carbon film of embodiment 1 preparation；
Fig. 2 is the stannum/carbon composite of the nanostructured of embodiment 1 preparation scanning electron microscope under different amplification
Figure；
Fig. 3 is the transmission electron microscope picture of the stannum/carbon composite of the nanostructured of embodiment 1 preparation；
Fig. 4 is the high-resolution-ration transmission electric-lens figure of the stannum/carbon composite of the nanostructured of embodiment 1 preparation；
Fig. 5 is the transmission electron microscope picture of the stannum/carbon composite of the nanostructured that comparative example 1, comparative example 2 are prepared respectively；
Fig. 6 is the scanning nuclear microprobe figure of the stannum/carbon composite of comparative example 3 preparation；
Fig. 7 is the transmission electron microscope picture of the carbon fibre material of the tin ash parcel being surrounded by carbon film of embodiment 2 preparation；
Fig. 8 is the transmission electron microscope picture of the stannum/carbon composite of the nanostructured of embodiment 2 preparation；
Fig. 9 is transmission electron microscope and the high-resolution transmission plot of the stannum/carbon composite of the nanostructured of embodiment 3 preparation；
Figure 10 is transmission electron microscope and the high-resolution transmission plot of the stannum/carbon composite of the nanostructured of embodiment 4 preparation；
Figure 11 is transmission electron microscope picture and the X-ray diffractogram of the end product of embodiment 5 preparation；
Figure 12 is constant current charge-discharge cycle performance and the coulombic efficiency curve of battery 1 of battery 1,2,3；
Figure 13 is the battery 1,2,3 charge-discharge performance curve under different multiplying.
Detailed description of the invention
Embodiment 1
(1) methanol with volume ratio as 1:1 and isopropanol are as solvent, and configuration concentration is that stannic acid four isopropyl ester of 10mM is molten
Liquid, and be stirred at room temperature 1 hour, it is heated to 50 DEG C.
(2) laboratory being commonly used quantitative filter paper to be placed in Suction filtration device, with ethanol purge filter paper 3 times, vacuum is drained.
(3) Suction filtration device being wrapped in heating tape, holding means temperature is at 50 DEG C.
(4) in the Suction filtration device of step (3), the stannic acid four isopropyl ester solution that 20mL step (1) configures, sucking filtration one are added
Half solution, makes solution impregnation quantitative filter paper, and remains that liquid level is higher than the surface of quantitative filter paper, stand 3 minutes, and this is
Deposition process.
(5) coarse vacuum sucking filtration stannic acid four isopropyl ester solution is to liquid level higher than quantitative filter paper surface, and being rapidly added temperature is 50
DEG C, volume ratio be the methanol/isopropanol mixed solvent of 1:1, rinse 6 times, and add this mixed solvent of 20mL, stand 3 minutes,
Coarse vacuum sucking filtration, adding temperature is 50 DEG C of pure water rinses 4 times, and adds the pure water of 50 DEG C of 20mL, stands 3 minutes, and this is
Hydrolytic process.Vacuum filtration 15 minutes in atmosphere after hydrolysis, are dried to quantitative filter paper.
(6) liquid level in step (4) and (5) is consistently higher than quantitative filter paper surface.This deposits, is hydrolyzed to cyclic process, heavy
The thickness of long-pending one layer of tin dioxide thin film is 1.3nm, circulates 15 times, obtains 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 vacuum drying oven it is dried overnight；So
After in argon at 500 DEG C calcine 6h, heating rate is 1 DEG C/min, obtain nano-stannic oxide parcel carbon fibre material.
(8) carbon fibre material of nano-stannic oxide parcel calcining in step (7) obtained immerses the Portugal of 0.1mol/L
In grape sugar aqueous solution, at 180 DEG C, hydro-thermal reaction 4h obtains being coated with the carbon fibre material of the tin ash parcel of carbon film.
(9) the carbon fibre material priority pure water and the ethanol that are wrapped up by the tin ash being coated with carbon film in step (8) are clear
Wash for several times, be placed in vacuum drying oven and be dried overnight；Calcining 6h in argon at 500 DEG C, heating rate is 1 DEG C/min.
(10) material after calcining in step (9) is ground to powder, at H2/N2(v/v=1:9) in gaseous mixture 500
Reduction 6h at DEG C, heating rate is 5 DEG C/min, obtains the stannum/carbon composite of nanostructured.
Transmission electron microscope picture such as Fig. 1 institute of the carbon fibre material of the tin ash parcel of prepared by the present embodiment be coated with carbon film
Show, for the carbon fiber of the single tin ash parcel being coated with carbon film in figure.The carbon fiber surface of tin ash parcel is coated with
The carbon film of one layer of about 4nm.
The scanning electron microscope (SEM) photograph of the stannum/carbon composite of nanostructured prepared by the present embodiment is as in figure 2 it is shown, Fig. 2 A, Fig. 2 B
It is respectively the scanning electron microscope (SEM) photograph amplifying 22K and 40K.Observe Fig. 2 and be supported on carbon nanometer it will be seen that tin nanoparticles is more uniform
On fiber.
The transmission electron microscope picture of the stannum/carbon composite of nanostructured prepared by the present embodiment is as it is shown on figure 3, Fig. 3 is single
The carbon fiber of tin supported nano-particle.The more uniform load of tin nanoparticles or be partly embedded on carbon nano-fiber, thin nanometer
The diameter of granule is about in the range of 20～50nm.
The high-resolution-ration transmission electric-lens figure of the stannum/carbon composite of nanostructured prepared by the present embodiment as shown in Figure 4, lattice
Fringe spacing d=0.278nm correspond to the crystal face of (101) of Tetragonal stannum, it was demonstrated that the granule of carbon fiber surface is sijna really
Rice grain.
Comparative example 1
Cycle-index in the step (6) of embodiment 1 being replaced with 5 times, remaining is the most same as in Example 1, obtains Theil indices
Stannum/the carbon composite of different nanostructureds.
The transmission electron microscope picture such as Fig. 5 A institute of the stannum/carbon composite of the nanostructured that Theil indices prepared by this comparative example is different
Show, compared with the stannum/carbon composite of the nanostructured of embodiment 1 preparation, the sijna in the stannum/carbon composite of nanostructured
Rice grain significantly reduces, and in the range of particle diameter 20～60nm, but distribution of particles is the most uniform.
Comparative example 2
Cycle-index in the step (6) of embodiment 1 being replaced with 10 times, remaining is the most same as in Example 1, obtains Theil indices
Stannum/the carbon composite of different nanostructureds.
The transmission electron microscope picture such as Fig. 5 B institute of the stannum/carbon composite of the nanostructured that Theil indices prepared by this comparative example is different
Show, compared with the stannum/carbon composite of the nanostructured of embodiment 1 preparation, the sijna in the stannum/carbon composite of nanostructured
Rice grain significantly reduces, and in the range of particle diameter 20～60nm, but distribution of particles is the most uniform.
Comparative example 3
All being omitted in step (8) in embodiment 1, (9), remaining step is same as in Example 1, obtains stannum/carbon composite wood
Material.
The scanning nuclear microprobe figure of stannum/carbon composite prepared by this comparative example is as shown in Fig. 6 A, 6B and Fig. 6 C, with reality
Stannum/the carbon composite of the nanostructured executing example 1 preparation is compared, the sijna rice in stannum/carbon composite prepared by this comparative example
Grain diameter significantly increases, and about in the range of 200～300nm, and distribution of particles is the most uneven, simultaneously because the particle diameter of tin particles
Relatively big, it is difficult to be attached on carbon fiber, so obvious obscission can occur.
Embodiment 2
D/W concentration in the step (8) of embodiment 1 is defined to 0.4M, remaining step and embodiment 1 phase
With.
Transmission electron microscope picture such as Fig. 7 institute of the carbon fibre material of the tin ash parcel of prepared by the present embodiment be coated with carbon film
Showing, for the carbon fiber of the single tin ash parcel being coated with carbon film in figure, the carbon film thickness of cladding is about 4nm.
As shown in Figure 8, Fig. 8 is single to the transmission electron microscope picture of the stannum/carbon composite of nanostructured prepared by the present embodiment
Fiber, it can be seen that scattered being attached on carbon nano-fiber of tin particles, and have the trend departing from carbon fiber, the particle diameter of granule
About in the range of 50～100nm.
Embodiment 3
D/W concentration in the step (8) of embodiment 1 is defined to 0.8M, remaining step and embodiment 1 phase
With.
Prepared by the present embodiment is coated with transmission electron microscope picture and Fig. 7 phase of the carbon fibre material of the tin ash parcel of carbon film
Seemingly, the carbon film thickness of cladding is about 8nm.
The transmission of the stannum/carbon composite of nanostructured prepared by the present embodiment and high-resolution-ration transmission electric-lens figure are respectively such as figure
Shown in 9A and 9B.Fig. 9 A is single fiber, has granule to be supported on unevenly on carbon nano-fiber, the particle diameter of granule about 30～
In the range of 80nm, also have 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 correspond to the crystal face of (101) of stannum, Tin monoxide respectively
(101) crystal face and the crystal face of (110) of tin ash, show can not reach with this understanding to reduce thoroughly.
Embodiment 4
D/W concentration in the step (8) of embodiment 1 is defined to 2M, and remaining step is same as in Example 1.
Prepared by the present embodiment is coated with transmission electron microscope picture and Fig. 7 phase of the carbon fibre material of the tin ash parcel of carbon film
Seemingly, the carbon film thickness of cladding is about 12nm.
The transmission of the stannum/carbon composite of nanostructured prepared by the present embodiment and high-resolution-ration transmission electric-lens figure such as Figure 10 A
Shown in 10B.Figure 10 A is single fiber, has granule load the most equably or be partly embedded on carbon nano-fiber, the grain of granule
, about in the range of 20～50nm, also there are some irregular distribution of particles in footpath 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 correspond to the crystal face of (211) of stannum, oxygen respectively
Change the crystal face of (002) of stannous and the crystal face of (110) of tin ash, show to reduce with this understanding the most thorough.
Embodiment 5
Reduction temperature in the step (10) of embodiment 1 is reduced to 300 DEG C by 500 DEG C, remaining step and embodiment 1 phase
With.
The transmission electron microscope picture of end product prepared by the present embodiment is as shown in 11A, and Figure 11 A is single fiber, with reduction
Before compare, fiber does not occur anything to change, still with the presence of the carbon film of one layer of about 4nm.
X-ray diffraction (XRD) figure of end product prepared by the present embodiment as shown in Figure 11 B, the crystal face diffraction in Figure 11 B
Peak all correspond to the crystal face of Tetragonal rutile-type tin ash, and showing that this experiment is reduced under conditions of temperature is relatively low can not
Tin ash is reduced into stannum.
Application examples
Materials A is ground in agate mortar 1h, weigh 40mg and with mass ratio 80:10:10 and conductive agent acetylene black and
Binding agent PVDF mixes, dried in vacuum overnight at 80 DEG C；Rear furnishing pasty slurry, ultrasonic 1h, add magneton and be stirred overnight, be coated with afterwards
In nickel foam, it is vacuum dried 12 hours, tabletting.
When stannum/carbon composite that materials A is the nanostructured that embodiment prepares, the lithium ion battery being prepared as
Negative plate is designated as 1；
When the stannum/carbon composite of the nanostructured that materials A is comparative example 1 and comparative example 2 prepares respectively, preparation
The anode plate for lithium ionic cell become is designated as 2,3 respectively；
Anode plate for lithium ionic cell is assembled respectively with positive plate-lithium sheet respectively in the glove box of full argon, obtains
CR2025 type button cell.The electrolyte used is with LiPF6For solute, the ethylene carbonate (EC) with volume ratio as 1:1 and carbon
Diethyl phthalate (DEC) is solvent, and the barrier film of use is Celgard 2300.
The button cell assembled is tested, uses battery system to test battery respectively under constant current and different multiplying
Charge-discharge performance, charge and discharge voltage range is 0.01～3.0V.
Battery 1 under the constant current of 100mA/g charge-discharge performance and coulombic efficiency as shown in figure 12, first lap charge and discharge
Electricity specific capacity is respectively 539mAh/g and 1241mAh/g, coulombic efficiency 43%.After circulation 150 circle, specific discharge capacity still has
468mAh/g, the coulombic efficiency after stablizing is maintained at more than 98%.Stannum/carbon the composite wood of nanostructured prepared by embodiment is described
The lithium battery that material assembles has bigger specific capacity and preferable cyclical stability.
The contrast of the constant current charge-discharge cycle performance of battery 2,3 is as shown in figure 12.It can be seen 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, battery 3 specific capacity
Only 231mAh/g.
The battery 1 charge-discharge performance under different multiplying as shown in figure 13, at 100mA/g, 200mA/g, 500mA/
Circulate ten circles under the electric current density of g, 1A/g, 2A/g, 3A/g successively, finally return 100mA/g.During 3000mA/g, specific capacity is still
Having about 60mAh/g, after returning to 100mA/g, specific capacity is returned to more than 345mAh/g.
The contrast of the battery 2,3 charge-discharge performance under different multiplying is as shown in figure 13.Owing to precursor is at filter paper
Upper frequency of depositing is different, and in material 1,2,3, Theil indices is different.Tin nanoparticles material to be significantly more than 2,3 in material 1, and
The Theil indices obtained in material 1,2,3 by thermogravimetric test is respectively 15.9%, 9.9% and 7.9%.Stannum in material 1 simultaneously
The distribution of nano-particle is more uniform compared with material 2,3.So, the high rate performance battery to be significantly better than of battery 1
2、3。
Claims (10)
1. the preparation method of the stannum/carbon composite of a nanostructured, it is characterised in that the carbon fiber that tin ash is wrapped up
Material immerses in the aqueous solution of carbon source, obtains being surrounded by the carbon fiber material of the tin ash parcel of carbon film through hydro-thermal reaction and post processing
Material, then the stannum/carbon composite of described nanostructured is obtained through reduction treatment.
The preparation method of the stannum/carbon composite of nanostructured the most according to claim 1, it is characterised in that described
Carbon source is glucose.
The preparation method of the stannum/carbon composite of nanostructured the most according to claim 2, it is characterised in that described
The concentration of carbon source aqueous solution is 0.1～2mol/L.
The preparation method of the stannum/carbon composite of nanostructured the most according to claim 3, it is characterised in that described
The concentration of carbon source aqueous solution is 0.1～0.4mol/L.
The preparation method of the stannum/carbon composite of nanostructured the most according to claim 1, it is characterised in that described water
The temperature of thermal response is 180～200 DEG C, and the time is 4～5h.
The preparation method of the stannum/carbon composite of nanostructured the most according to claim 1, it is characterised in that described
Post processing includes washing, be dried, calcine and grinding.
The preparation method of the stannum/carbon composite of nanostructured the most according to claim 6, it is characterised in that described
Calcination condition is: calcining heat 400～500 DEG C, calcination time 5～10h, heating rate 1～5 DEG C/min.
The preparation method of the stannum/carbon composite of nanostructured the most according to claim 1, it is characterised in that described also
The condition of original place reason is: reduction temperature 400～500 DEG C, recovery time 5～10h, heating rate 5～10 DEG C/min, reducing gas
For H2/N2Gaseous mixture.
9. stannum/carbon the composite wood of the nanostructured prepared according to the method described in claim 1～8 any claim
Material.
10. stannum/the carbon composite of a nanostructured according to claim 9 application in lithium ion battery.
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| CN111682184A (en) * | 2020-06-23 | 2020-09-18 | 欣旺达电动汽车电池有限公司 | Tin-based composite material and preparation method thereof, negative plate and lithium ion battery |
| CN114433835A (en) * | 2021-12-20 | 2022-05-06 | 中山大学 | Preparation method and application of tin/carbon composite nano material |
| CN114597369A (en) * | 2022-03-16 | 2022-06-07 | 四川轻化工大学 | Carbon-tin nano composite material and preparation method and application thereof |
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| 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 |
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| CN114433835B (en) * | 2021-12-20 | 2022-12-20 | 中山大学 | Preparation method and application of tin/carbon composite nano material |
| CN114597369A (en) * | 2022-03-16 | 2022-06-07 | 四川轻化工大学 | Carbon-tin nano composite material and preparation method and application thereof |
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Address after: 215635 No.10, Qinghai Road, Yangzi River International Chemical Industry Park, Zhangjiagang, Suzhou, Jiangsu Province Co-patentee after: Zhejiang University Patentee after: Jiangsu Huasheng lithium battery materials Co., Ltd Address before: 215635, Qinghai Road, Zhangjiagang International Chemical Industrial Park, Yangzi River, Suzhou, Jiangsu 28, China Co-patentee before: Zhejiang University Patentee before: HSC Corporation |