The preparation method of the carbon fibre material of a kind of carried titanium dioxide nano thin-film and ferroferric oxide nano granules, product and application
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 carried titanium dioxide nano thin-film and ferroferric oxide nano granules, product and application.
Background technology
Flourish along with modern science and technology, each class of electronic devices and electric automobile have had to be applied widely, also more and more higher to the requirement of chemical power source.Can the lithium ion battery of discharge and recharge due to its long useful life, the density of high energy and little to the pollution of environment, has become a strong electric power resource and has been applied in all trades and professions.At present, market has caused the concern of Many researchers for the demand of the material of high-performance lithium ion electrode.Therefore, their urgent searching chemical property is superior and can realize the negative material of the lithium ion battery with high storage capacity and current density on a large scale.
But, in the middle of numerous negative materials, mostly really be graphite for commercial ion cathode material lithium, because it is at occurring in nature rich reserves, cheap and easy to get, and there is superior kinetic constant and relatively stable cycle performance.But its weak point is that the embedding lithium of its operating voltage and de-lithium are usually less than 0.2V, and this also can bring a series of safety problem; Lower theoretical specific capacity (372mAh/g) and the situation that loss of charge is serious in SEI film forming process all limit the application in the middle of reality.In order to overcome this defect, proposing many strategies and solving this problem.Research finds, transition metal has very high storage lithium ability and green non-pollution, cheap and easy to get, is one of optimal selection of ion cathode material lithium.Owing to there is very high storage lithium ability (theoretical specific capacity 926mAh/g), good bio-compatibility and electro-chemical activity, the Fe of nanostructure
3o
4receive and paid close attention to widely.
As the publication number Chinese patent literature that is CN103241777A discloses a kind of preparation method of carbon-ferriferrous oxide composite material, this composite material contains tri-iron tetroxide and carbon, carbon is carbon ball or carbon fiber, preparation method comprises using chliorinated polyvinyl chloride as the carbon source material synthesizing material with carbon element or carbon-iron compound composite material, under the quick catalysis of iron compound, in combustion reaction process, chliorinated polyvinyl chloride carries out dehydrochlorination and crosslinked action, synthesis carbon-ferriferrous oxide composite material or material with carbon element.And for example the people such as Ma Chuanguo (Ma Chuanguo Lu Wei Zheng naval king Ya Zhenluo is scorching. carbon/ferriferrous oxide nano composite material study on the synthesis. inorganic chemicals industry, 41st volume the 4th phase, in April, 2009) active carbon/tri-iron tetroxide (AC/Fe that adopted homogeneous precipitation method to prepare
3o
4) particle and carbon nano-tube/tri-iron tetroxide (CNTs/Fe
3o
4) particle two kinds of composite materials.
But the raw material type in above-mentioned disclosed document needed for synthetic material is many, and synthesis step is numerous and diverse, and production cost is high.Further, volumetric expansion easily occurs the material of synthesis in charge and discharge process and agglomeration makes storage lithium ability sharply decline, and is unfavorable for commercialization.
Summary of the invention
The present invention proposes the preparation method of the carbon fibre material of a kind of carried titanium dioxide nano thin-film and ferroferric oxide nano granules, employing native cellulose is raw material, simultaneously as template and carbon source, and be compounded with titanium dioxide nano-film and ferriferrous oxide nano-particle by quick-reading flow sheets, the composite material prepared, as the negative material of lithium ion battery, has high specific capacity, and stable circulation performance is superior, have extended cycle life, the advantages such as the specific discharge capacity under high magnification is stable.
The preparation method of the carbon fibre material of a kind of carried titanium dioxide nano thin-film and ferroferric oxide nano granules, take butyl titanate as precursor, native cellulose is template, through surface sol-gel method at template surface deposition of titanium oxide nano thin-film, be immersed in again in ferric chloride aqueous solutions, obtain described carried titanium dioxide nano thin-film and the carbon fibre material of ferroferric oxide nano granules finally by after drying, calcining.
The present invention is directed to the serious bulk effect that tri-iron tetroxide produces in lithium deintercalation, utilize support and the cushioning effect of material with carbon element, keep the characteristic of tri-iron tetroxide height ratio capacity, the agraphitic carbon that in carbonization process, fibrin gasification produces covers the surface of whole material, adds its cyclical stability greatly.The titanium dioxide layer of Nano grade significantly can increase the load of tri-iron tetroxide particle simultaneously.
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, after reaching 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 is quantitative filter paper or absorbent cotton, 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.
As preferably, described native cellulose, before use through preliminary treatment, is specially: described native cellulose is stand-by after ethanol purge, suction filtration.
As preferably, describedly through surface sol-gel method in the concrete steps of template surface deposition of titanium oxide nano thin-film be:
(1) mixed with the mixed liquor of ethanol/toluene by butyl titanate, configuration obtains the butyl titanate solution that concentration is 100 ~ 400mM;
(2) pretreated native cellulose is immersed in butyl titanate solution, keeps liquid level higher than the upper surface of native cellulose, leave standstill deposition;
(3) post-depositional native cellulose is first after ethanol filtering and washing, keeps liquid level higher than the upper surface of native cellulose, leaves standstill deposition; After deionized water washing, leave standstill hydrolysis again, drain finally by ethanol washing;
(4) repeat the process 15 ~ 25 times of step (2) ~ (3), then carry out suction filtration, dry process.
As preferably, in step (1), the volume ratio of ethanol and toluene is 1:1, and the concentration that configuration obtains butyl titanate solution is 100mM.Concentration is too low, carbon fiber surface titanium dioxide coated uneven; Excessive concentration, the titanium dioxide in coating layer is graininess.Under described preferred concentration, deposition obtains coated even, nano level titanium dioxide nano-film.After testing, the thickness of this individual layer titanium dioxide nano-film is about 0.5nm, and the average grain diameter of titania nanoparticles is about 10nm.
As preferably, the preliminary treatment of described native cellulose and the deposition process of titanium dioxide nano-film are all carried out in Suction filtration device, are specially:
(A) preliminary treatment of native cellulose: native cellulose is placed in Suction filtration device, at least washs 3 times with absolute ethyl alcohol, is still positioned in Suction filtration device stand-by after vacuum filtration;
(B) deposition of titanium dioxide nano-film: add described butyl titanate solution in Suction filtration device, suction filtration butyl titanate solution, to the upper surface of liquid level higher than native cellulose, ensures to infiltrate native cellulose, and leaves standstill deposition; Wash away unnecessary butyl titanate solution with ethanolic solution, suction filtration ethanolic solution to the upper surface of liquid level higher than native cellulose, after leaving standstill; Use deionized water rinse again, suction filtration deionized water to the upper surface of liquid level higher than native cellulose, after leaving standstill hydrolysis; Recirculation deposition, hydrolytic process.
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 preparation process of load ferroferric oxide nano granules, is specially:
Configuration concentration is the ferric chloride aqueous solutions of 1 ~ 5M, after being uniformly dispersed, in ferric chloride aqueous solutions described in the template of surface deposition titanium dioxide nano-film being immersed, after reacting 12 ~ 36h at 70 ~ 90 DEG C, obtain the carbon fibre material of carried titanium dioxide nano thin-film and ferroferric oxide nano granules again through calcination processing.
As preferably, the condition of described calcination processing is: calcining heat 500 ~ 600 DEG C, calcination time 5 ~ 10h, and heating rate is 1 ~ 5 DEG C/min.Preferred calcining heat is 500 DEG C further, and heating rate is 1 DEG C/min.
The invention also discloses the carbon fibre material of carried titanium dioxide nano thin-film that the preparation method described in employing obtains and ferroferric oxide nano granules.
The invention also discloses the application of carbon fibre material in lithium ion battery of described carried titanium dioxide nano thin-film and ferroferric oxide nano granules.Specifically it can be used as the negative material of lithium ion battery, compared with graphite negative electrodes material conventional in current commercial Li-ion batteries, there is larger specific capacity.
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, preferred 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.
2, the preparation method in the present invention is simple, low cost, pollution-free.
3, the lithium ion battery that the carried titanium dioxide nano thin-film prepared using the present invention and the carbon fibre material of ferroferric oxide nano granules are assembled as negative material, have specific capacity large, 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 the carried titanium dioxide nano thin-film prepared of embodiment and ferroferric oxide nano granules;
Fig. 2 is the transmission electron microscope photo of the carbon fibre material of the carried titanium dioxide nano thin-film prepared of embodiment and ferroferric oxide nano granules;
Fig. 3 is the high-resolution-ration transmission electric-lens of carbon fibre material under different multiplying of the carried titanium dioxide nano thin-film prepared of embodiment and ferroferric oxide nano granules;
Fig. 4 is the scanned photograph of carbon fiber under different multiplying of ferriferrous oxide particles load prepared by comparative example;
Fig. 5 is the transmission photo of the carbon fiber of ferriferrous oxide particles load prepared by comparative example;
Fig. 6 is the scanning nuclear microprobe photo of commercially available tri-iron tetroxide particle;
Fig. 7 is the coulombic efficiency curve of battery 1,2 and 3;
Fig. 8 is the comparison diagram of the charging and discharging curve of battery 1,2 and 3 under different multiplying.
Embodiment
Embodiment:
(1) take volume ratio as the absolute ethyl alcohol of 1:1 and toluene be solvent, configuration concentration is the butyl titanate solution of 100mM, and at room temperature stirs 1 hour.
(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) in the Suction filtration device of step (2), add the butyl titanate solution that 10mL 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.
(4) low vacuum suction filtration butyl titanate solution to liquid level a little more than its surface, rapid anhydrous ethanol solvent, rinse 4 ~ 6 times, leave standstill 3 minutes, low vacuum suction filtration; Pure water rinse 4 ~ 6 times, leave standstill 3 minutes, this is hydrolytic process.Ethanol washing is added, vacuum filtration 15 minutes in atmosphere after hydrolysis, dry to filter paper.
(5) step (3) and (4) middle liquid level should all the time higher than its surface.This deposits, is hydrolyzed to cyclic process, and the thickness of deposition layer of titanium dioxide film is 0.5nm, circulates 20 times, obtains the titanium deoxid film that thickness is about 10nm.
(6) filter paper that deposited titanium dioxide nano-film in step (5) is placed in vacuum drying chamber dried overnight.
(7) compound concentration is 80mM, and volume is the ferric chloride aqueous solutions of 40mL, ultrasonic 10 minutes, is made into the homogeneous orange-yellow aqueous solution.
(8) the filter paper fibre cellulosic material of carried titanium dioxide nano thin-film dried in (6) is placed in the solution of above-mentioned (7), reaction 12 hours under the condition of 80 DEG C in an oven.Obtain the titanium dioxide nano-film cellulosic material of hydrated ferric oxide load, and the color of the filter paper fibre element of titanium dioxide nano-film load becomes from original white orange-yellow.After cooling rear deionized water and absolute ethanol washing 4 ~ 6 times, be placed in the vacuum drying chamber dried overnight of 80 DEG C.
(9) desciccate obtained in above-mentioned (8) is placed in argon atmosphere to calcine, described calcination condition is: calcining heat 500 DEG C, and heating rate is 1 DEG C/min, and calcination time is 6 hours.Obtain the carbon fibre material of carried titanium dioxide nano thin-film and ferroferric oxide nano granules.
As shown in Figure 1, a amplifies 45k stereoscan photograph doubly to the carbon fibre material stereoscan photograph of carried titanium dioxide nano thin-film prepared by the present embodiment and ferroferric oxide nano granules; B amplifies 120k stereoscan photograph doubly.Observe Fig. 1 can see, load has the carbon fibre material of titanium dioxide nano-film and ferroferric oxide nano granules to replicate the filamentary structure of filter paper well, and the ground load of tri-iron tetroxide uniform particle is on the filter paper fibre element that every root titanium dioxide wraps up.
The carbon fibre material transmission electron microscope photo of carried titanium dioxide nano thin-film prepared by the present embodiment and ferroferric oxide nano granules as shown in Figure 2, for single load has the carbon fibre material of titanium dioxide nano-film and ferroferric oxide nano granules in figure, the length of the ferriferrous oxide particles of load is 70 ~ 100nm, and diameter is between 20 ~ 60nm.Fig. 3 is the high-resolution-ration transmission electric-lens photo of product, and spacing of lattice is 0.253nm, (311) crystal face of corresponding tri-iron tetroxide.And at the skin of particle due to the decomposition of cellulose in calcination process, make material surface cover the carbon of thin layer, thickness is at 3 ~ 5nm.
Comparative example:
In this comparative example, step (1) ~ (6) in embodiment are omitted, directly filter paper is placed in the ferric chloride aqueous solutions prepared, all the other steps (7) ~ (9) are identical with embodiment, obtain the carbon fiber of tri-iron tetroxide load, wherein, at material surface because the thermal decomposition of cellulose in calcination process covers the very thin carbon film of one deck, thickness is at 3 ~ 5nm.As a comparison, the size of commercially available ferriferrous oxide nano-particle is between 50 ~ 100nm simultaneously.
The stereoscan photograph of the carbon fiber of ferriferrous oxide particles load prepared by comparative example as shown in Figure 4, the carried titanium dioxide nano thin-film prepared with embodiment is compared with the carbon fibre material of ferroferric oxide nano granules, the particle diameter of the nano particle of tri-iron tetroxide prepared by comparative example is larger, length is at 60 ~ 120nm, diameter is at about 200nm, as can be seen from the transmission electron microscope photo of Fig. 5, tri-iron tetroxide particle tends to be embedded in carbon fiber, and the tightness of arrangement does not have tri-iron tetroxide particle alignment in embodiment tight yet.Cover on large stretch of carbon fiber uniform particle.And find out that commercially available ferriferrous oxide nano-particle is due to agglomerate grain from the scanning nuclear microprobe photo of Fig. 6, together fusion together, and disperse uneven.
Application examples:
Materials A is ground 1h in agate mortar, weighs 40mg and mix with conductive agent acetylene black and binding agent PVDF with mass ratio 80:10:10, dried in vacuo overnight at 80 DEG C; Rear furnishing pasty slurry, ultrasonic 1h, add magneton stir spend the night, after be applied in nickel foam, vacuumize 12 hours, compressing tablet.
When materials A is the carbon fibre material of the carried titanium dioxide nano thin-film for preparing of embodiment and ferroferric oxide nano granules, the anode plate for lithium ionic cell be prepared into is designated as 1;
When materials A is the carbon fibre material of the ferriferrous oxide particles load that comparative example prepares, the anode plate for lithium ionic cell be prepared into is designated as 2;
When materials A is commercially available ferriferrous oxide nano-particle, the anode plate for lithium ionic cell be prepared into is designated as 3;
Anode plate for lithium ionic cell 1,2 and 3 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 and 3.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 and 3 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 7, first lap specific discharge capacity is 1340mAh/g, first lap charge specific capacity is 614mAh/g, coulombic efficiency 47%.After circulation 100 circle, specific discharge capacity still has 565mAh/g, and the coulombic efficiency after stable remains on more than 98%.Illustrate that the lithium battery of the carbon fibre material assembling of carried titanium dioxide nano thin-film prepared by embodiment and ferroferric oxide nano granules has larger specific capacity and good cyclical stability.
The contrast of the constant current charge-discharge cycle performance of battery 2,3 as shown in Figure 7.As can be seen from the figure, after circulation 100 circle, the specific capacity of battery 1 still has 565mAh/g, and the specific capacity of battery 2 has been down to 317mAh/g, and the specific capacity of tri-iron tetroxide particle only has 232mAh/g.
The charge-discharge performance of battery 1 under different multiplying as shown in Figure 8, at 0.1C, 0.2C, 0.5C, circulate under the current density of 1C, 2C, 5C ten circles successively, when finally returning 0.1C.1C, specific capacity still has 275mAh/g, and after getting back to 100mA/g, specific capacity gets back to more than 550mAh/g again.
The contrast of the charge-discharge performance of battery 2,3 under different multiplying as shown in Figure 8.Due to filter paper in carbonisation on the area load of ferriferrous oxide particles the reason of the carbon film of thin layer, cushion the change of tri-iron tetroxide particle volume in charge and discharge process, be simultaneously template with filter paper, the structure of its three-dimensional netted porous effectively can improve transport and the diffusion of electronics and lithium ion, increase the conductivity of material, so the cyclical stability of battery 1 and 2 will apparently higher than the tri-iron tetroxide particle bought.But due to battery 1 for load has the carbon fibre material of titanium dioxide nano-film and ferroferric oxide nano granules, titanium deoxid film layer can increase the amount of the hydrated ferric oxide in load effectively, therefore can improve specific capacity and multiplying power stability further again.