CN103746099B - The preparation method of the carbon fibre material of a kind of tin ash parcel, product and application - Google Patents
The preparation method of the carbon fibre material of a kind of tin ash parcel, product and application Download PDFInfo
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- CN103746099B CN103746099B CN201410019983.3A CN201410019983A CN103746099B CN 103746099 B CN103746099 B CN 103746099B CN 201410019983 A CN201410019983 A CN 201410019983A CN 103746099 B CN103746099 B CN 103746099B
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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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses the preparation method of the carbon fibre material of a kind of tin ash parcel, product and application; the concrete steps of described preparation method are: with stannic acid four isopropyl ester for 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.Preparation method of the present invention selects native cellulose to be raw material, as template and carbon source, and native cellulose wide material sources, cheap; Preparation method is simple, low cost, pollution-free; The carbon fibre material of the tin ash parcel prepared is as the negative material of lithium ion battery, and have specific capacity large, cyclical stability is high, and the advantage such as have extended cycle life.
Description
Technical field
The present invention relates to field of lithium ion battery, be specifically related to the preparation method of the carbon fibre material of a kind of tin ash parcel, product and application.
Background technology
Along with the fast development of science and technology, various electronic equipment and electric automobile have had to be applied widely, also more and more higher to the requirement of chemical power source.Lithium ion battery due to its volume little, specific capacity is high, environmental protection, can the repeatedly advantage such as discharge and recharge, has been widely used in electronic equipment.The negative material of current commercial lithium ion battery mostly is graphite, but the theoretical specific capacity that graphite is lower (372mAh/g), limit further developing of high-capacity lithium ion cell.Research finds, the reversible lithium storage capacity of tinbase, silica-based and other alloy materials 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 how reducing these materials has become the hot issue in current Study on Li-ion batteries.
In non-graphite system negative material, SnO
2because theoretical specific capacity higher (781mAh/g), stability is high, safe, pollution-free etc., advantage obtains pays close attention to widely.But in lithium ion deintercalation process, volumetric expansion is serious with contraction, and material disintegrating can be caused to come off, specific capacity declines fast, and cyclical stability is poor.Complex carbon material or to SnO
2the control of material microstructure effectively can improve the cycle performance of material.
As the publication number Chinese patent literature that is CN101462045B discloses the composite material of a kind of tin ash and carbon, 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 and being contacted with alkaline solution by the carbon fiber of surface oxidation, then contacts with butter of tin in the basic conditions.The people such as Du Kai (Du Kai, Wei Ronghui, Wei Shizhong, Li Liben, Yang Haibin. the structure of carbon fiber/tin dioxide composite material and relevant nature. Journal of Henan University, 41st volume the 4th phase, in July, 2011) carbon fiber surface is modified, prepare carbon fiber/tin dioxide composite material by the low temperature liquid phase precipitation method.
All directly adopt carbon fiber to be raw material in above-mentioned disclosed document, production cost is high.
Summary of the invention
The present invention proposes the preparation method of the carbon fibre material of a kind of tin ash parcel, product and application.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 prepared is as the negative material of lithium ion battery, and have specific capacity large, cyclical stability is high, and the advantage such as have extended cycle life.
The invention discloses the preparation method of the carbon fibre material of a kind of tin ash parcel; with stannic acid four isopropyl ester for 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 adopted in the present invention is calcined charing by native cellulose and is obtained, native cellulose is a kind of straight-chained polysaccharide, carbon containing, hydrogen, oxygen three kinds of elements, heat in inert gas, starting stage is by the moisture evaporation in native cellulose, when after arrival 275 DEG C, namely spontaneous charing is started, only there are the carbon of fraction and other composition to be burnt when anoxic, carbonize when temperature reaches 400 ~ 500 DEG C, obtain carbon fiber, described carbon fiber remains 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 is after ethanol purge 3 times, more stand-by after vacuum filtration.
As preferably, described native cellulose is the natural fiber material such as quantitative filter paper, absorbent cotton, described native cellulose more preferably quantitative filter paper.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 layer level structure, there is very large specific area, be conducive to the transmission of electronics, improve the conductivity of material, effectively can 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 ester is mixed with isopropyl alcohol/methyl alcohol mixed liquor, configuration stannic acid four isopropyl ester solution, be heated to 40 ~ 60 DEG C 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 liquid level higher than the upper surface of native cellulose, leave standstill deposition;
(3) post-depositional native cellulose is first through isopropyl alcohol/methyl alcohol mixed liquor washing at least 3 times of 40 ~ 60 DEG C, then after the pure water rinse at least 3 times of 40 ~ 60 DEG C, leaves standstill hydrolysis;
(4) after repeating the process 10 ~ 20 times of step (2) ~ (3), then through suction filtration, dry process.
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 Suction filtration device, with ethanol purge 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 leave standstill deposition; Unnecessary stannic acid four isopropyl ester solution is washed away with the isopropyl alcohols of 40 ~ 60 DEG C/methyl alcohol mixed solution; After using the pure water rinse of 40 ~ 60 DEG C again, leave standstill hydrolysis; Cyclic deposition, hydrolytic process several times.
Above-mentioned process is all carried out in Suction filtration device, can save the transfer of the native cellulose after each step process, avoid 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 uneven; 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, and the average grain diameter of tin oxide nano particles is about 8nm.
Described inert gas can be nitrogen or helium.
As preferably, described calcination condition is: calcining heat 400 ~ 500 DEG C, calcining 5 ~ 10h.
As preferably, the heating rate of described calcination process is 1 ~ 5 DEG C/min; More preferably 2 DEG C/min.
The invention also discloses the carbon fibre material of the tin ash parcel that the preparation method described in employing obtains.
The invention also discloses the application of carbon fibre material in lithium ion battery of described tin ash parcel.The carbon fibre material of the tin ash parcel specifically the present invention prepared, 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 cellulosic materials, wide material sources, price is low, the quantitative filter paper selected is interwoven by many micron order fleeces, and these micron order fibers are interwoven by many nano-scale fiber bindings, have fibrous layer level structure, there is very large specific area, be conducive to the transmission of electronics, improve the conductivity of material, effectively can improve the specific capacity of material.
2, the preparation method in the present invention is simple, low cost, pollution-free.
3, the lithium ion battery assemble as negative material of carbon fibre material of tin ash parcel for preparing of the present invention, have specific capacity greatly, cyclical stability is high, and the advantage such as have extended cycle life.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph of carbon fibre material under different amplification of tin ash parcel prepared by embodiment;
Fig. 2 is the transmission electron microscope photo of the carbon fibre material of tin ash parcel prepared by embodiment;
Fig. 3 is the high-resolution-ration transmission electric-lens photo of the carbon fibre material of tin ash parcel prepared by embodiment;
Fig. 4 is the transmission electron microscope photo of tin dioxide nanometer tube material prepared by comparative example;
Fig. 5 is constant current charge and discharge cycle performance and the coulombic 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) take volume ratio as the isopropyl alcohol of 1:1 and methyl alcohol be solvent, configuration concentration is the stannic acid four isopropyl ester solution of 10mM, and at room temperature stirs 1 hour, is heated to 50 DEG C.
(2) quantitative filter paper is commonly used in laboratory and be placed in Suction filtration device, with ethanol purge filter paper 3 times, vacuum is drained.
(3) be wrapped in heating tape by Suction filtration device, holding device temperature is at 50 DEG C.
(4) in the Suction filtration device of step (3), add the stannic acid four isopropyl ester solution that 20mL step (1) configures, suction filtration half solution, makes solution impregnation native cellulose, and remains the surface of liquid level higher than native cellulose, leave standstill 3 minutes, this is deposition process.
(5) low vacuum suction filtration stannic acid isopropyl ester solution to liquid level a little more than its surface, add rapidly that temperature is 50 DEG C, volume ratio is the isopropyl alcohol of 1:1 and the mixed solvent of methyl alcohol, rinse 6 times, and add this solvent of 20mL, leave standstill 3 minutes, low vacuum suction filtration, adding temperature is again 50 DEG C of pure water rinses 4 times, and add the pure water of 20mL50 DEG C, leave standstill 3 minutes, this is hydrolytic process.Vacuum filtration 15 minutes in atmosphere after hydrolysis, dry to filter paper.
(6) step (4) and (5) middle liquid level should all the time higher than its 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 that thickness is about 20nm.
(7) filter paper that deposited tin dioxide thin film in step (6) is placed in vacuum drying chamber dried overnight; In argon gas, calcine 6h at 500 DEG C, heating rate is 2 DEG C/min, obtains the carbon fibre material of tin ash parcel.
As shown in Figure 1, Fig. 1 (A) amplifies 10k stereoscan photograph doubly to the stereoscan photograph of the carbon fibre material of tin ash parcel prepared by the present embodiment, and interior accompanying drawing is the photo of material; Fig. 1 (B) amplifies 50k stereoscan photograph doubly.Observe Fig. 1 can see, the carbon fibre material of tin ash parcel replicates 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 of fiber is about 150nm, and fiber surface is wrapped in the stannic oxide particle that diameter is about 8nm, and these stannic oxide particles define at carbon fiber surface the film that a layer thickness is about 20nm.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), proves that the particle of carbon fiber surface is tin ash really.
Comparative example:
In embodiment 1, step (7) changes into and calcines 6h at 500 DEG C in atmosphere, and all the other are all identical with embodiment 1.By the native cellulose of air calcination removing 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 that the tin ash prepared with embodiment wraps up, 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 2h in agate mortar, weighs 40mg and mix with conductive agent acetylene black and binding agent PVDF with mass ratio 75:15:10, furnishing pasty slurry, being applied in nickel foam, vacuumize 12 hours, compressing tablet.
When materials A is the carbon fibre material of the tin ash parcel that embodiment prepares, the anode plate for lithium ionic cell be 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 be prepared into is designated as 2;
Anode plate for lithium ionic cell 1,2 is assembled respectively with positive plate-lithium sheet respectively in the glove box being full of argon gas, obtains CR2025 type button cell 1,2.The electrolyte used is with LiPF
6for solute, take volume ratio as the ethylene carbonate (EC) of 1:1:1, dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) be solvent, the barrier film of use is Celgard2300.
Test the button cell of assembling, adopt the battery system charge-discharge performance of test battery 1,2 under constant current and different multiplying respectively, 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 5, first lap specific discharge capacity is 1970mAh/g, first lap charge specific capacity is 1046mAh/g, coulombic efficiency 53%.Circulate after 50 circles, specific discharge capacity still has 633mAh/g, and the coulombic efficiency after stable remains on more than 98%.Illustrate that the lithium battery of the carbon fibre material assembling of tin ash parcel prepared by embodiment has larger specific capacity and good cyclical stability.
As shown in Figure 6, circulate successively the charge-discharge performance of battery 1 under different multiplying ten circles under the current density of 100mA/g, 200mA/g, 500mA/g, 1000mA/g, finally returns 100mA/g.During 1000mA/g, specific capacity still has 345mAh/g, and after getting back to 100mA/g, specific capacity gets back to more than 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 not easily subsides in cyclic process, and material is not easily pulverized and come off, so have good cyclical stability.As can be seen from the figure, after circulation 50 circle, the specific capacity of battery 1 still has 633mAh/g, and the specific capacity of battery 2 is down to 330mAh/g.
Claims (6)
1. the preparation method of the carbon fibre material of a tin ash parcel, it is characterized in that, with stannic acid four isopropyl ester for 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;
Described native cellulose is quantitative filter paper or absorbent cotton;
Described native cellulose, before use through preliminary treatment, is specially: described native cellulose is stand-by after ethanol purge, suction filtration;
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 ester is mixed with isopropyl alcohol/methyl alcohol mixed liquor, configuration stannic acid four isopropyl ester solution, and be heated to 40 ~ 60 DEG C 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 liquid level higher than the upper surface of native cellulose, leave standstill deposition;
(3) post-depositional native cellulose is first through isopropyl alcohol/methyl alcohol mixed liquor washing at least 3 times of 40 ~ 60 DEG C, then after the pure water rinse at least 3 times of 40 ~ 60 DEG C, leaves standstill hydrolysis;
(4) after repeating the process 10 ~ 20 times of step (2) ~ (3), then through suction filtration, dry process.
2. the preparation method of the carbon fibre material of tin ash parcel as claimed in claim 1, it is characterized in that, described native cellulose is quantitative filter paper.
3. the preparation method of the carbon fibre material of tin ash parcel as claimed in claim 1, it 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.
4. the preparation method of the carbon fibre material of tin ash parcel as claimed in claim 3, it is characterized in that, described calcination condition is: calcining heat 400 ~ 500 DEG C, calcination time 5 ~ 10h, and heating rate is 1 ~ 5 DEG C/min.
5. the carbon fibre material of the tin ash parcel that the preparation method as described in a claim as arbitrary in Claims 1 to 4 obtains.
6. the application of carbon fibre material in lithium ion battery of a tin ash parcel as claimed in claim 5.
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| CN113097482B (en) * | 2021-03-04 | 2022-06-24 | 江苏师范大学 | Negative electrode material, preparation method thereof and lithium battery with negative electrode material |
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