CN103746099A - Preparation method of tin-dioxide-coated carbon fiber material, and product and application thereof - Google Patents
Preparation method of tin-dioxide-coated carbon fiber material, and product and application thereof Download PDFInfo
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- H01M4/02—Electrodes composed of, or comprising, active material
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Abstract
The invention discloses a preparation method of a tin-dioxide-coated carbon fiber material, and a product and application thereof. The preparation method comprises the following steps: depositing a tin dioxide film on the surface of natural cellulose by a sol-gel process by using tetraisopropyl stannate as a precursor and the natural cellulose as a template and carbon source, and calcining in an inert gas protective atmosphere to obtain the tin-dioxide-coated carbon fiber material. The raw material natural cellulose used as the template and carbon source has the advantages of wide sources and low price; the preparation method is simple and easy to implement, and has the advantages of low cost and no pollution; and when being used as a lithium ion battery negative pole material, the prepared tin-dioxide-coated carbon fiber material has the advantages of high specific capacity, high loop stability, long cycle life and the like.
Description
Technical field
The present invention relates to lithium ion battery field, be specifically related to a kind of preparation method, product and application of carbon fibre material of tin ash parcel.
Background technology
Along with scientific and technical fast development, various electronic equipments and electric automobile have had application widely, also more and more higher to the requirement of chemical power source.Lithium ion battery is because its volume is little, and specific capacity is high, and environmental protection such as can repeatedly discharge and recharge at the advantage, has been widely used in electronic equipment.The negative material of current commercial lithium ion battery mostly is graphite, but the lower theoretical specific capacity (372mAh/g) of graphite has limited further developing of high-capacity lithium ion cell.Research finds, the reversible lithium storage capacity of tinbase, silica-based and other alloy materials is much larger than graphite, but due to the bulk effect in lithium ion deintercalation process, causes the cyclical stability of these materials poor, cannot commercialization.So the bulk effect that how to reduce these materials has become the hot issue in current Study on Li-ion batteries using.
At non-graphite, be in negative material, SnO
2because the advantages such as theoretical specific capacity higher (781mAh/g), stability are high, safe, pollution-free have obtained paying close attention to widely.But in lithium ion deintercalation process, volumetric expansion is serious with contraction, can cause material disintegrating to come off, and specific capacity declines fast, and cyclical stability is poor.Complex carbon material or to SnO
2the control of material microstructure can effectively improve the cycle performance of material.
The Chinese patent literature that is CN101462045B as publication number discloses the composite material of a kind of tin ash and carbon, and this composite material contains nano-stannic oxide and carbon, and described carbon is carbon fiber, and described nano-stannic oxide is coated on described carbon fiber surface.The preparation method of described nano-stannic oxide/carbon composite comprises the carbon fiber of surface oxidation is contacted with alkaline solution, then under alkali condition, contacts with butter of tin.The people such as Du Kai (Du Kai, Wei Ronghui, Wei Shizhong, Li Liben, Yang Haibin. structure and the relevant nature of carbon fiber/tin ash composite material. Journal of Henan University, the 41st the 4th phase of volume, in July, 2011) carbon fiber surface is modified, by the low temperature liquid phase precipitation method, prepare carbon fiber/tin ash composite material.
In above-mentioned disclosed document, all directly adopting carbon fiber is raw material, and production cost is high.
Summary of the invention
The present invention proposes a kind of preparation method, product and application of carbon fibre material of tin ash parcel.Employing native cellulose is raw material, as template and carbon source, and native cellulose wide material sources, cheap, described preparation method is simple, low cost, pollution-free; The carbon fibre material of the tin ash parcel preparing, as the negative material of lithium ion battery, has specific capacity large, and cyclical stability is high, and the advantage such as have extended cycle life.
The invention discloses a kind of preparation method of carbon fibre material of tin ash parcel; take stannic acid four isopropyl esters as precursor; native cellulose is template and carbon source; first through sol-gel process at native cellulose surface deposition tin dioxide thin film, then calcining obtains the carbon fibre material of described tin ash parcel under argon shield.
The present invention is directed to the serious bulk effect that tin ash produces when lithium deintercalation, utilize support and the cushioning effect of material with carbon element, keep the characteristic of tin ash height ratio capacity, and increase its cyclical stability.The material with carbon element adopting in the present invention is obtained by native cellulose calcining charing, native cellulose is a kind of straight chain polysaccharide, carbon containing, hydrogen, three kinds of elements of oxygen, in inert gas, heat, starting stage is by the moisture evaporation in native cellulose, after arriving 275 ℃, start spontaneous charing, the in the situation that of anoxic, only there are carbon and other the composition of fraction to be burnt, when temperature reaches 400～500 ℃, charing completes, obtain carbon fiber, described carbon fiber has retained the original multi-level network structure of native cellulose on microcosmic.
As preferably, described native cellulose, before use through preliminary treatment, is specially: described native cellulose cleans after 3 times through ethanol, more stand-by after vacuum filtration.
As preferably, described native cellulose is the natural fiber materials such as quantitative filter paper, absorbent cotton, more preferably quantitative filter paper of described native cellulose.Quantitative filter paper is interwoven by many micron order fleeces, and these micron order fibers are interwoven by many nano-scale fiber bindings, have fibrous hierarchical structure, there is very large specific area, be conducive to the transmission of electronics, improve the conductivity of material, can effectively improve the specific capacity of material.
Described sol-gel process in the concrete steps of the nano level tin dioxide thin film of native cellulose surface deposition is:
(1) stannic acid four isopropyl esters are mixed with isopropyl alcohol/methyl alcohol mixed liquor, configuration stannic acid four isopropyl ester solution, be heated to 40～60 ℃ stand-by;
The concentration of described stannic acid four isopropyl ester solution is 5～20mM;
(2) pretreated native cellulose is immersed in described stannic acid four isopropyl ester solution, keeps the upper surface of liquid level higher than native cellulose, standing deposition;
(3) post-depositional native cellulose is first through isopropyl alcohol/methyl alcohol mixed liquor washing of 40～60 ℃ at least 3 times, then after the pure water rinse of 40～60 ℃ at least 3 times, standing hydrolysis;
(4) after the process 10～20 times of repeating step (2)～(3), then through suction filtration, dry processing.
As preferably, the preliminary treatment of above-mentioned native cellulose and the deposition process of tin dioxide thin film are all carried out in suction filtration device.
(1) preliminary treatment of native cellulose: native cellulose is placed in to suction filtration device, with ethanol cleaning 3 times, vacuum filtration.
(2) at the nano level tin dioxide thin film of native cellulose fibre surface deposition: add described stannic acid four isopropyl ester solution in suction filtration device, suction filtration solution is to the upper surface of liquid level higher than native cellulose, make solution impregnation native cellulose, and standing deposition; Wash away unnecessary stannic acid four isopropyl ester solution with isopropyl alcohol/methyl alcohol mixed solution of 40～60 ℃; Use again after the pure water rinse of 40～60 ℃ standing hydrolysis; Cyclic deposition, hydrolytic process several times.
Above-mentioned process is all carried out in suction filtration device, can save the transfer through each step native cellulose after treatment, avoids its structural damage.
As preferably, the volume ratio of described isopropyl alcohol/methyl alcohol mixed liquor is 1:1.
As preferably, the concentration of described stannic acid four isopropyl ester solution is 10mM.Concentration is too low, carbon fiber surface tin ash coated inhomogeneous; Excessive concentration, the tin ash in coating layer is graininess.Under described preferred concentration, deposition obtains coated even, nano level tin dioxide thin film.The thickness of individual layer tin dioxide thin film is about 1.3nm, the about 8nm of average grain diameter of tin oxide nano particles.
Described inert gas can be nitrogen or helium.
As preferably, described calcination condition is: 400～500 ℃ of calcining heats, calcining 5～10h.
As preferably, the heating rate of described calcination process is 1～5 ℃/min; More preferably 2 ℃/min.
The invention also discloses the carbon fibre material that adopts the tin ash parcel that described preparation method obtains.
The application of the carbon fibre material that the invention also discloses described tin ash parcel in lithium ion battery.The carbon fibre material of the tin ash parcel of specifically being prepared by the present invention is as the negative material of lithium ion battery, has larger specific capacity compared with graphite negative electrodes material conventional in current commercial Li-ion batteries.
Compared with prior art, the present invention has the following advantages:
1, the present invention selects natural fiber cellulosic material, wide material sources, price is low, the quantitative filter paper of selecting is interwoven by many micron order fleeces, and these micron order fibers are interwoven by many nano-scale fiber bindings, have fibrous hierarchical structure, there is very large specific area, be conducive to the transmission of electronics, improve the conductivity of material, can effectively improve the specific capacity of material.
2, simple, the low cost, pollution-free of the preparation method in the present invention.
The carbon fibre material of tin ash that 3, the present invention prepares parcel, as the lithium ion battery of negative material assembling, has specific capacity large, and cyclical stability is high, and the advantage such as have extended cycle life.
Accompanying drawing explanation
Fig. 1 is the carbon fibre material of the tin ash parcel prepared of the embodiment stereoscan photograph under different amplification;
Fig. 2 is the transmission electron microscope photo of the carbon fibre material of the tin ash parcel prepared of embodiment;
Fig. 3 is the high-resolution-ration transmission electric-lens photo of the carbon fibre material of the tin ash parcel prepared of embodiment;
Fig. 4 is the transmission electron microscope photo of the tin dioxide nanometer tube material prepared of comparative example;
Fig. 5 is constant current charge and discharge cycle performance and coulomb efficiency curve of battery 1;
Fig. 6 is the charge-discharge performance curve of battery 1 under different multiplying;
Fig. 7 is the comparison diagram of the constant current charge-discharge cycle performance curve of battery 1,2.
Embodiment
Embodiment:
(1) isopropyl alcohol take volume ratio as 1:1 and methyl alcohol are solvent, the stannic acid four isopropyl ester solution that configuration concentration is 10mM, and at room temperature stir 1 hour, be heated to 50 ℃.
(2) conventional laboratory quantitative filter paper is placed in to suction filtration device, cleans filter paper 3 times with ethanol, vacuum is drained.
(3) suction filtration device is wrapped in heating tape, holding device temperature is at 50 ℃.
(4) to the stannic acid four isopropyl ester solution that add 20mL step (1) configuration in the suction filtration device of step (3), suction filtration half solution, makes solution impregnation native cellulose, and remains the surface of liquid level higher than native cellulose, standing 3 minutes, this was deposition process.
(5) low vacuum suction filtration stannic acid isopropyl ester solution to liquid level a little more than filter paper surface, adding rapidly temperature is 50 ℃, the volume ratio isopropyl alcohol that is 1:1 and the mixed solvent of methyl alcohol, rinse 6 times, and add this solvent of 20mL, and standing 3 minutes, low vacuum suction filtration, adding temperature is 50 ℃ of pure water rinses 4 times again, and add the pure water of 20mL50 ℃, standing 3 minutes, this was hydrolytic process.After hydrolysis in air vacuum filtration 15 minutes, dry to filter paper.
(6) in step (4) and (5), liquid level should be all the time higher than filter paper surface.This deposits, is hydrolyzed to cyclic process, and the thickness of deposition one deck tin dioxide thin film is 1.3nm, circulates 15 times, obtains the tin dioxide thin film of the about 20nm of thickness.
(7) filter paper that has deposited tin dioxide thin film in step (6) is placed in to vacuum drying chamber dried overnight; In argon gas, at 500 ℃, calcine 6h, heating rate is 2 ℃/min, obtains the carbon fibre material of tin ash parcel.
As shown in Figure 1, Fig. 1 (A) is for amplifying 10k stereoscan photograph doubly, the photo that interior accompanying drawing is material for the stereoscan photograph of the carbon fibre material of tin ash parcel prepared by the present embodiment; Fig. 1 (B) is for amplifying 50k stereoscan photograph doubly.Observing Fig. 1 can see, the carbon fibre material of tin ash parcel has copied the filamentary structure of filter paper well, and the diameter of fiber is 100～200nm.
The transmission electron microscope photo of the carbon fibre material of tin ash parcel prepared by the present embodiment as shown in Figure 2, is the carbon fiber of single tin ash parcel in figure.The diameter 150nm of fiber, fiber surface is wrapped in the stannic oxide particle of diameter 8nm, and these stannic oxide particles have formed the film of the about 20nm of a layer thickness at carbon fiber surface.Fig. 3 is the high-resolution-ration transmission electric-lens photo of the carbon fibre material of tin ash parcel, interior accompanying drawing is the selected area electron diffraction figure of material, can see (110) of rutile-type tin ash, crystal faces such as (200), the particle that proves carbon fiber surface is tin ash really.
Comparative example:
Step in embodiment 1 (7) changes in air calcines 6h at 500 ℃, and all the other are all identical with embodiment 1.By air calcination, remove the native cellulose as template, what prepare is tin dioxide nanometer tube material.
The transmission electron microscope photo of tin dioxide nanometer tube material prepared by comparative example as shown in Figure 4, compared with the carbon fibre material of the tin ash parcel of preparing with embodiment, the particle diameter of the nano particle of tin dioxide nanometer tube prepared by comparative example is larger, and the distribution of grain diameter is even not.
Application examples:
Materials A is ground in agate mortar to 2h, weigh 40mg and mix with conductive agent acetylene black and binding agent PVDF with mass ratio 75:15:10, furnishing pasty slurry, is applied in nickel foam, vacuumize 12 hours, compressing tablet.
When materials A is the carbon fibre material of the tin ash parcel for preparing of embodiment, the anode plate for lithium ionic cell being prepared into is designated as 1;
When materials A be comparative example prepare tin dioxide nanometer tube material time, the anode plate for lithium ionic cell being prepared into is designated as 2;
Anode plate for lithium ionic cell 1,2 is assembled respectively in the glove box that is full of argon gas with positive plate-lithium sheet respectively, obtained CR2025 type button cell 1,2.The electrolyte using is with LiPF
6for solute, ethylene carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) take volume ratio as 1:1:1 are solvent, and the barrier film of use is Celgard2300.
Button cell to assembling is tested, and adopts the battery system charge-discharge performance of test battery 1,2 under constant current and different multiplying respectively, and charge and discharge voltage range is 0.01～3.0V.
Battery 1 under the constant current of 100mA/g charge-discharge performance and coulomb efficiency as shown in Figure 5, first lap specific discharge capacity is 1970mAh/g, first lap charge ratio capacity is 1046mAh/g, coulomb efficiency 53%.Circulate after 50 circles, specific discharge capacity still has 633mAh/g, and the coulomb efficiency after stablizing remains on more than 98%.The lithium battery that the carbon fibre material assembling of tin ash parcel prepared by embodiment is described has larger specific capacity and cyclical stability preferably.
As shown in Figure 6, ten circles that circulate successively under the current density of 100mA/g, 200mA/g, 500mA/g, 1000mA/g, finally return 100mA/g to the charge-discharge performance of battery 1 under different multiplying.During 1000mA/g, specific capacity still has 345mAh/g, gets back to after 100mA/g, more than specific capacity is got back to 600mAh/g again.
The contrast of the constant current charge-discharge cycle performance of battery 1,2 as shown in Figure 7.Due to support and the cushioning effect of carbon in the carbon fibre material of tin ash parcel, tin dioxide thin film is difficult for subsiding in cyclic process, and material is difficult for pulverizing and comes off, so have good cyclical stability.As can be seen from the figure, after circulation 50 circles, the specific capacity of battery 1 still has 633mAh/g, and the specific capacity of battery 2 has been down to 330mAh/g.
Claims (10)
1. the preparation method of the carbon fibre material of a tin ash parcel; it is characterized in that; take stannic acid four isopropyl esters as precursor; native cellulose is template and carbon source; first through sol-gel process at native cellulose surface deposition tin dioxide thin film, then calcining obtains the carbon fibre material of described tin ash parcel under inert gas shielding.
2. the preparation method of the carbon fibre material of tin ash parcel as claimed in claim 1, is characterized in that, described native cellulose, before use through preliminary treatment, is specially: described native cellulose is stand-by after ethanol cleaning, suction filtration.
3. the preparation method of the carbon fibre material of tin ash parcel as claimed in claim 2, is characterized in that, described native cellulose is quantitative filter paper or absorbent cotton.
4. the preparation method of the carbon fibre material of tin ash parcel as claimed in claim 3, is characterized in that, described native cellulose is quantitative filter paper.
5. the preparation method of the carbon fibre material of tin ash parcel as claimed in claim 2, is characterized in that, described sol-gel process in the concrete steps of the tin dioxide thin film of native cellulose surface deposition nanometer layer is:
(1) stannic acid four isopropyl esters are mixed with isopropyl alcohol/methyl alcohol mixed liquor, configuration stannic acid four isopropyl ester solution, and be heated to 40～60 ℃ stand-by;
The concentration of described stannic acid four isopropyl ester solution is 5～20mM;
(2) pretreated native cellulose is immersed in described stannic acid four isopropyl ester solution, keeps the upper surface of liquid level higher than native cellulose, standing deposition;
(3) post-depositional native cellulose is first through isopropyl alcohol/methyl alcohol mixed liquor washing of 40～60 ℃ at least 3 times, then after the pure water rinse of 40～60 ℃ at least 3 times, standing hydrolysis;
(4) after the process 10～20 times of repeating step (2)～(3), then through suction filtration, dry processing.
6. the preparation method of the carbon fibre material of tin ash parcel as claimed in claim 5, is characterized in that, the preliminary treatment of described native cellulose and the deposition process of tin dioxide thin film are all carried out in suction filtration device, are specially:
(1) preliminary treatment of native cellulose: native cellulose is placed in to suction filtration device, with ethanol cleaning at least 3 times, is still placed in suction filtration device after vacuum filtration stand-by;
(2) at the nano level tin dioxide thin film of native cellulose fibre surface deposition: add described stannic acid four isopropyl ester solution in suction filtration device, suction filtration solution is to the upper surface of liquid level higher than native cellulose, make solution impregnation native cellulose, and standing deposition; Wash away unnecessary stannic acid four isopropyl ester solution with isopropyl alcohol/methyl alcohol mixed solution of 40～60 ℃; Use again after the pure water rinse of 40～60 ℃ standing hydrolysis; Cyclic deposition, hydrolytic process 10～20 times.
7. the preparation method of the carbon fibre material of tin ash parcel as claimed in claim 6, is characterized in that, the volume ratio of described isopropyl alcohol/methyl alcohol mixed liquor is 1:1, and the concentration of stannic acid four isopropyl ester solution is 10mM.
8. the preparation method of the carbon fibre material of tin ash parcel as claimed in claim 7, is characterized in that, described calcination condition is: 400～500 ℃ of calcining heats, and calcination time 5～10h, heating rate is 1～5 ℃/min.
9. the carbon fibre material of the tin ash parcel that the preparation method as described in a claim as arbitrary in claim 1～8 obtains.
10. the application of the carbon fibre material of a tin ash parcel as claimed in claim 9 in lithium ion battery.
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| CN104051718A (en) * | 2014-06-26 | 2014-09-17 | 南京师范大学 | Preparation method for negative electrode material three-dimensional nanometer porous tin dioxide-based composite oxide of lithium ion battery |
| CN104766963A (en) * | 2015-04-22 | 2015-07-08 | 安徽理工大学 | Method for preparing metal oxide-carbon fiber nano composite material |
| CN106206060A (en) * | 2016-09-25 | 2016-12-07 | 桂林理工大学 | The preparation of cobalt hydroxide@carbon fiber nanometer composite material and electrode material for super capacitor application |
| CN106299306A (en) * | 2016-09-30 | 2017-01-04 | 江苏长园华盛新能源材料有限公司 | A kind of stannum/carbon composite of nanostructured and its preparation method and application |
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