CN105070889B - A kind of preparation method, product and the application of the carbon fibre material of carried titanium dioxide nano thin-film and ferroferric oxide nano granules - Google Patents
A kind of preparation method, product and the application of the carbon fibre material of carried titanium dioxide nano thin-film and ferroferric oxide nano granules Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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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
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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
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron 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
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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 a kind of carried titanium dioxide nano thin-film and the carbon fibre material of ferroferric oxide nano granules, using butyl titanate as precursor, native cellulose is template, through surface sol-gal process in template surface deposition of titanium oxide nano thin-film, it is immersed in again in ferric chloride aqueous solutionses, the carbon fibre material of described carried titanium dioxide nano thin-film and ferroferric oxide nano granules is most obtained after drying, calcining afterwards.The present invention uses native cellulose for raw material, it is used as template and carbon source simultaneously, and titanium dioxide nano-film and ferriferrous oxide nano-particle are compounded with by quick-reading flow sheets, the composite prepared as lithium ion battery negative material, with high specific capacity, stable circulation performance is superior, has extended cycle life, the advantage such as specific discharge capacity stabilization under high magnification.
Description
Technical field
The present invention relates to field of lithium ion battery, and in particular to a kind of carried titanium dioxide nano thin-film and ferroso-ferric oxide
Preparation method, product and the application of the carbon fibre material of nano particle.
Background technology
With flourishing for modern science and technology, each class of electronic devices and electric automobile, which have, to be widely applied, right
The requirement of electrochmical power source also more and more higher.Can discharge and recharge the service life grown due to it of lithium ion battery, the density of high energy with
And it is small to the pollution of environment, have become a strong electric power resource and apply in all trades and professions.At present, market is for height
The demand of the material of energy li-ion electrode has caused the concern of Many researchers.Therefore, their urgent searchings are electrochemical
Learn superior performance and the negative material of the lithium ion battery with high storage capacity and current density can be realized on a large scale.
However, among numerous negative materials, the real ion cathode material lithium for commercialization is generally graphite, due to
Its rich reserves in nature, it is cheap and easy to get, and with superior kinetic constant and relatively stable cycle performance.
But it is disadvantageous in that the embedding and removing usually less than 0.2V of its operating voltage, and this also brings along a series of safety and asked
Topic；Relatively low theoretical specific capacity (372mAh/g) and the serious situation of loss of charge is all limited in SEI film forming processes
Application among reality.In order to overcome this defect, it is proposed that many strategies solve this problem.Research discovery, 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.By
In with very high storage lithium ability (theoretical specific capacity 926mAh/g), good bio-compatibility and electro-chemical activity, nano junction
The Fe of structure3O4It is of great interest.
Chinese patent literature such as Publication No. CN103241777A discloses a kind of carbon-ferriferrous oxide composite material
Preparation method, the composite contains ferroso-ferric oxide and carbon, and carbon is carbon ball or carbon fiber, and preparation method includes poly- with chlorination
Vinyl chloride is as synthesis carbon material or the carbon source material of carbon-iron compound composite, under the quick catalysis of iron compound,
Chliorinated polyvinyl chloride carries out dehydrochlorination and crosslinked action during combustion reaction, synthesizes carbon-ferriferrous oxide composite material
Or carbon material.And for example Ma Chuanguo et al. (Ma Chuanguo Lu Wei Zheng naval king Ya Zhenluo inflammation carbon/ferriferrous oxide nano composite
Study on the synthesis inorganic chemicals industries, the 4th phase of volume 41, in April, 2009) oxygen of activated carbon/tetra- is prepared for using homogeneous precipitation method
Change three-iron (AC/Fe3O4) particle and CNT/ferroso-ferric oxide (CNTs/Fe3O4) two kinds of composites of particle.
But the raw material type in document disclosed above needed for synthetic material is more, and synthesis step is numerous and diverse, production cost is high.And
And, volumetric expansion easily occurs in charge and discharge process for the material of synthesis and agglomeration causes storage lithium ability drastically to decline, no
Beneficial to commercialization.
The content of the invention
The present invention proposes the carbon fibre material of a kind of carried titanium dioxide nano thin-film and ferroferric oxide nano granules
Preparation method, native cellulose is used for raw material, while being compounded with titanium dioxide as template and carbon source, and by quick-reading flow sheets
Titanium nano thin-film and ferriferrous oxide nano-particle, the composite prepared are used as the negative material of lithium ion battery, tool
There is high specific capacity, stable circulation performance is superior, has extended cycle life, the advantage such as specific discharge capacity stabilization under high magnification.
A kind of preparation method of the carbon fibre material of carried titanium dioxide nano thin-film and ferroferric oxide nano granules, with
Butyl titanate is precursor, and native cellulose is template, is received through surface sol-gel method in template surface deposition of titanium oxide
Rice film, then be immersed in ferric chloride aqueous solutionses, most obtain described carried titanium dioxide nanometer thin after drying, calcining afterwards
The carbon fibre material of film and ferroferric oxide nano granules.
The serious bulk effect that the present invention is produced for ferroso-ferric oxide in lithium deintercalation, support and buffering using carbon material
Effect, keeps the agraphitic carbon that fibrin gasification is produced in the characteristic of ferroso-ferric oxide height ratio capacity, carbonization process to be covered in whole
The surface of individual material, greatly adds its cyclical stability.The titanium dioxide layer of Nano grade can dramatically increase four oxygen simultaneously
Change the load of three iron particles.
The carbon material used in the present invention is obtained by native cellulose calcining charing, and native cellulose is a kind of straight chain poly
Sugar, carbon containing, hydrogen, three kinds of elements of oxygen are heated in inert gas, the starting stage by the moisture evaporation in native cellulose, when up to
To after 275 DEG C, that is, start spontaneous charing, the carbon and other compositions for only having fraction in the case of anoxic are burned off, when
Charing is completed when temperature reaches 400~500 DEG C, obtains carbon fiber, described carbon fiber remains native cellulose on microcosmic
Original multi-level network structure.Preferably, the native cellulose is quantitative filter paper or absorbent cotton, it is more preferably fixed
Measure filter paper.Quantitative filter paper is interwoven by many micron order webs, and these micron order fibers are by many nano-scale fibers
Binding is interwoven, with fibrous layer level structure, with very big specific surface area, is conducive to the transmission of electronics, improves material
Electric conductivity, the specific capacity of material can be effectively improved.
Preferably, the native cellulose is specially using preceding preprocessed：Described native cellulose is through ethanol
It is stand-by after cleaning, suction filtration.
Preferably, it is described through surface sol-gel method template surface deposition of titanium oxide nano thin-film specific step
Suddenly it is：
(1) butyl titanate is mixed with the mixed liquor of ethanol/toluene, configuration obtains the metatitanic acid that concentration is 100~400mM
Four butyl acetate solutions；
(2) pretreated native cellulose is immersed in solution of tetrabutyl titanate, keeps liquid level to be higher than natural fiber
The upper surface of element, stands deposition；
(3) post-depositional native cellulose keeps liquid level to be higher than the upper table of native cellulose first after ethanol filtering and washing
Face, stands deposition；Hydrolysis is stood after being washed again through deionized water, is most drained afterwards through ethanol washing；
(4) process of repeat step (2)~(3) 15~25 times, then carry out suction filtration, drying process.
Preferably, in step (1), the volume ratio of ethanol and toluene is 1:1, configuration obtains the dense of solution of tetrabutyl titanate
Spend for 100mM.Concentration is too low, and the cladding of carbon fiber surface titanium dioxide is uneven；Titanium dioxide in excessive concentration, clad
It is in granular form.Under the preferred concentration, deposition is evenly coated, nano level titanium dioxide nano-film.After testing,
The thickness of the individual layer titanium dioxide nano-film is about 0.5nm, the average grain diameter about 10nm of titania nanoparticles.
Preferably, the pretreatment of described native cellulose and the deposition process of titanium dioxide nano-film are in suction filtration
Carried out in device, be specially：
(A) pretreatment of native cellulose：Native cellulose is placed in Suction filtration device, 3 are at least washed with absolute ethyl alcohol
It is secondary, still it is positioned over after vacuum filtration stand-by in Suction filtration device；
(B) deposition of titanium dioxide nano-film：Described solution of tetrabutyl titanate, suction filtration titanium are added into Suction filtration device
Sour four butyl acetate solutions are higher than the upper surface of native cellulose to liquid level, it is ensured that infiltration native cellulose, and stand deposition；Use second
Alcoholic solution washes away unnecessary solution of tetrabutyl titanate, and suction filtration ethanol solution to liquid level is higher than the upper surface of native cellulose, stands
Afterwards；Deionized water rinse is used again, and suction filtration deionized water to liquid level is higher than the upper surface of native cellulose, stands after hydrolysis；Follow again
Ring deposition, hydrolytic process.
Above-mentioned process is carried out in Suction filtration device, can save the transfer of the native cellulose after being handled through each step,
Avoid to its structural damage.
Preferably, the preparation process of load ferroferric oxide nano granules, is specially：
Configuration concentration is 1~5M ferric chloride aqueous solutionses, after being uniformly dispersed, by surface deposition of titanium oxide nano thin-film
The described ferric chloride aqueous solutionses of template immersion in, loaded again through calcination processing after reacting 12~36h at 70~90 DEG C
The carbon fibre material of titanium dioxide nano-film and ferroferric oxide nano granules.
Preferably, the condition of the calcination processing is：500~600 DEG C of calcining heat, 5~10h of calcination time, heating
Speed is 1~5 DEG C/min.Further preferred calcining heat is 500 DEG C, and heating rate is 1 DEG C/min.
The invention also discloses the carried titanium dioxide nano thin-film obtained using described preparation method and four oxidations three
The carbon fibre material of iron nano-particle.
The invention also discloses described carried titanium dioxide nano thin-film and the carbon fiber of ferroferric oxide nano granules
Application of the material in lithium ion battery.Specifically as the negative material of lithium ion battery, with current commercial Li-ion
The graphite negative electrodes material commonly used in battery, which is compared, has bigger specific capacity.
Compared with prior art, the present invention has advantages below：
1st, the present invention selects natural cellulosic materials, and wide material sources, price is low, and quantitative filter paper preferably is by many micron orders
Web is interwoven, and these micron order fibers are interwoven by the binding of many nano-scale fibers, with fibrous level
Structure, with very big specific surface area, is conducive to the transmission of electronics, improves the electric conductivity of material, can effectively improve the ratio of material
Capacity.
2nd, the preparation method in the present invention is simple and easy to apply, inexpensive, pollution-free.
3rd, the carried titanium dioxide nano thin-film and the carbon fiber of ferroferric oxide nano granules prepared with the present invention
The lithium ion battery that material is assembled as negative material, big with specific capacity, cyclical stability is high, the advantages of having extended cycle life.
Brief description of the drawings
Fig. 1 is the carbon fibre material of carried titanium dioxide nano thin-film prepared by embodiment and ferroferric oxide nano granules
Stereoscan photograph under different amplification；
Fig. 2 is the carbon fibre material of carried titanium dioxide nano thin-film prepared by embodiment and ferroferric oxide nano granules
Transmission electron microscope photo；
Fig. 3 is the carbon fibre material of carried titanium dioxide nano thin-film prepared by embodiment and ferroferric oxide nano granules
High-resolution-ration transmission electric-lens under different multiplying；
Fig. 4 is scanned photograph of the carbon fiber of ferriferrous oxide particles load prepared by comparative example under different multiplying；
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 ferroso-ferric oxide particle；
Fig. 7 is the coulombic efficiency curve of battery 1,2 and 3；
Fig. 8 is the comparison diagram of 1,2 and 3 charging and discharging curve under different multiplying of battery.
Embodiment
Embodiment：
(1) using volume ratio as 1:1 absolute ethyl alcohol and toluene is solvent, and configuration concentration is molten for 100mM butyl titanate
Liquid, and 1 hour is stirred at room temperature.
(2) laboratory is often placed in Suction filtration device with quantitative filter paper, filter paper is cleaned with ethanol 3 times, vacuum is drained.
(3) solution of tetrabutyl titanate of 10mL steps (1) configuration, suction filtration half are added into the Suction filtration device of step (2)
Solution, makes solution impregnation native cellulose, and remains that liquid level is higher than the surface of native cellulose, stands 3 minutes, this is heavy
Product process.
(4) low vacuum suction filtration solution of tetrabutyl titanate to liquid level is slightly above its surface, rapid anhydrous ethanol solvent, rinse
4~6 times, 3 minutes are stood, low vacuum suction filtration；Pure water rinse 4~6 times, stands 3 minutes, this is hydrolytic process.Added after hydrolysis
Ethanol is washed, and is filtered by vacuum 15 minutes in atmosphere, is dried to filter paper.
(5) liquid level should be consistently higher than its surface in step (3) and (4).This deposits, is hydrolyzed to cyclic process, deposition one
The thickness of layer titanium deoxid film is 0.5nm, circulates 20 times, obtains thickness about 10nm titanium deoxid film.
(6) filter paper that titanium dioxide nano-film is deposited in step (5) is placed in vacuum drying chamber and be dried overnight.
(7) compound concentration is 80mM, and volume is 40mL ferric chloride aqueous solutionses, and ultrasound 10 minutes is made into homogeneous orange
The yellow aqueous solution.
(8) the filter paper fibre cellulosic material of carried titanium dioxide nano thin-film dried in (6) is placed in the molten of above-mentioned (7)
In liquid, react 12 hours under conditions of 80 DEG C in an oven.Obtain the titanium dioxide nano-film fiber of hydrated ferric oxide load
Cellulosic material, and the color of the filter paper fibre element of titanium dioxide nano-film load is changed into orange-yellow from original white.After cooling
Washed after 4~6 times, be dried overnight in the vacuum drying chamber for being placed in 80 DEG C with deionized water and absolute ethyl alcohol.
(9) desciccate obtained in above-mentioned (8) is placed in argon atmosphere and calcined, the calcination condition is：Calcining temperature
500 DEG C of degree, heating rate is 1 DEG C/min, and calcination time is 6 hours.Carried titanium dioxide nano thin-film and four oxidations are obtained
The carbon fibre material of three iron nano-particles.
The carbon fibre material of carried titanium dioxide nano thin-film and ferroferric oxide nano granules manufactured in the present embodiment is swept
Electromicroscopic photograph is retouched as shown in figure 1, a is the stereoscan photograph of 45k times of amplification；B is the stereoscan photograph of 120k times of amplification.See
Examine Fig. 1 can see, the carbon fibre material for being loaded with titanium dioxide nano-film and ferroferric oxide nano granules is multiple well
Made the filamentary structure of filter paper, and ferroso-ferric oxide uniform particle be supported on the filter paper fibre element of every titanium dioxide parcel
Above.
The carbon fibre material of carried titanium dioxide nano thin-film and ferroferric oxide nano granules manufactured in the present embodiment is saturating
Electromicroscopic photograph is penetrated as shown in Fig. 2 being the single carbon for being loaded with titanium dioxide nano-film and ferroferric oxide nano granules in figure
Fibrous material, the length of the ferriferrous oxide particles of load is 70~100nm, and diameter is between 20~60nm.Fig. 3 is product
High-resolution-ration transmission electric-lens photo, spacing of lattice is 0.253nm, (311) crystal face of correspondence ferroso-ferric oxide.And in the outer layer of particle
Due to decomposition of the cellulose in calcination process so that material surface covers a thin layer of carbon, and thickness is in 3~5nm.
Comparative example：
In this comparative example, step (1)~(6) in embodiment are omitted, filter paper is directly placed in the tri-chlorination prepared
In water solution, remaining step (7)~(9) is identical with embodiment, obtains the carbon fiber of ferroso-ferric oxide load, wherein, in material
Expect that thermal decomposition of the surface due to cellulose in calcination process covers one layer of very thin carbon film, thickness is in 3~5nm.Make simultaneously
For contrast, the size of commercially available ferriferrous oxide nano-particle is between 50~100nm.
Comparative example prepare ferriferrous oxide particles load carbon fiber stereoscan photograph as shown in figure 4, with implementation
Carried titanium dioxide nano thin-film prepared by example is compared with the carbon fibre material of ferroferric oxide nano granules, prepared by comparative example
The particle diameter of the nano particle of ferroso-ferric oxide is bigger, and length is in 60~120nm, and diameter is in 200nm or so, from Fig. 5 transmission electricity
Mirror photo can be seen that ferroso-ferric oxide particle and tend to be embedded into carbon fiber, and the tight ness rating of arrangement is also without in embodiment
Ferroso-ferric oxide particle alignment is close.On the carbon fiber for being covered in sheet uniform particle.And from Fig. 6 scanning nuclear microprobe
Photo finds out commercially available ferriferrous oxide nano-particle due to agglomerate grain, it is fusion together together, it is and scattered uneven.
Application examples：
Materials A is ground into 1h in agate mortar, 40mg is weighed and with mass ratio 80:10:10 with conductive agent acetylene black and
Binding agent PVDF is mixed, and is dried in vacuum overnight at 80 DEG C；After be tuned into pasty slurry, ultrasonic 1h adds magneton and is stirred overnight, rear to apply
In in nickel foam, it is dried in vacuo 12 hours, tabletting.
When the carbon that materials A is the carried titanium dioxide nano thin-film that embodiment is prepared and ferroferric oxide nano granules
During fibrous material, the anode plate for lithium ionic cell being prepared into is designated as 1；
When materials A is the carbon fibre material for the ferriferrous oxide particles load that comparative example is prepared, the lithium being prepared into
Ion battery negative plate is designated as 2；
When materials A is commercially available ferriferrous oxide nano-particle, the anode plate for lithium ionic cell being prepared into is designated as 3；
By anode plate for lithium ionic cell 1,2 and 3 respectively with positive plate-lithium piece in the glove box full of argon gas group respectively
Dress, obtains CR2025 types button cell 1,2 and 3.The electrolyte used is with LiPF6For solute, using volume ratio as 1:1:1 carbonic acid
Vinyl acetate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) are solvent, and the barrier film used is Celgard 2300.
The button cell of assembling is tested, battery 1,2 and 3 is tested respectively using battery system in constant current and difference
Charge-discharge performance under multiplying power, charge and discharge voltage range is 0.01~3.0V.
Battery 1 under 100mA/g constant current charge-discharge performance and coulombic efficiency as shown in fig. 7, first lap discharge
Specific capacity is 1340mAh/g, and first lap charge specific capacity is 614mAh/g, coulombic efficiency 47%.After the circle of circulation 100, electric discharge ratio
Capacity still has the coulombic efficiency after 565mAh/g, stabilization to be maintained at more than 98%.Illustrate carried titanium dioxide prepared by embodiment
The lithium battery of the carbon fibre material assembling of nano thin-film and ferroferric oxide nano granules has larger 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 7.It can be seen that circulation 100 is enclosed
After, the specific capacity of battery 1 still has a 565mAh/g, and the specific capacity of battery 2 has fallen to 317mAh/g, and ferroso-ferric oxide grain
The specific capacity of son only has 232mAh/g.
Charge-discharge performance of the battery 1 under different multiplying is as shown in figure 8, in 0.1C, 0.2C, 0.5C, 1C, 2C, 5C
Current density under circulate ten circles successively, specific capacity still has 275mAh/g when finally returning 0.1C.1C, returns to after 100mA/g,
Specific capacity is returned to more than 550mAh/g.
The contrast of 2,3 charge-discharge performance under different multiplying of battery is as shown in Figure 8.Because filter paper is in carbonisation
In the reason for a thin layer of carbon film, buffered ferroso-ferric oxide particle on the area load of ferriferrous oxide particles and filling
The change of volume in discharge process, while using filter paper as template, its three-dimensional mesh structural porous structure can effectively improve electronics and
The transport and diffusion of lithium ion, increase the electric conductivity of material, so the cyclical stability of battery 1 and 2 will be apparently higher than buying
Ferroso-ferric oxide particle.But it is fine to be loaded with the carbon of titanium dioxide nano-film and ferroferric oxide nano granules due to battery 1
Material is tieed up, titanium deoxid film layer can effectively increase the amount of the hydrated ferric oxide in load, therefore can further carry again
Height ratio capacity and multiplying power stability.
Claims (7)
1. a kind of preparation method of the carbon fibre material of carried titanium dioxide nano thin-film and ferroferric oxide nano granules, it is special
Levy and be, using butyl titanate as precursor, native cellulose is template, deposited through surface sol-gel method in template surface
Titanium dioxide nano-film, then be immersed in ferric chloride aqueous solutionses, most obtain described load dioxy after drying, calcining afterwards
Change the carbon fibre material of titanium nano thin-film and ferroferric oxide nano granules；
The native cellulose is quantitative filter paper；
500~600 DEG C of the calcining heat, 5~10h of calcination time, heating rate is 1~5 DEG C/min；
The carried titanium dioxide nano thin-film for preparing and the carbon fibre material surface of ferroferric oxide nano granules covered with
Carbon-coating；
The length of the ferriferrous oxide particles of the load be 70~100nm, diameter between 20~60nm, ferroso-ferric oxide
(311) the corresponding spacing of lattice of crystal face is 0.253nm；The carbon layers having thicknesses of covering are 3~5nm.
2. the carbon fibre material of carried titanium dioxide nano thin-film according to claim 1 and ferroferric oxide nano granules
Preparation method, it is characterised in that the native cellulose is specially using preceding preprocessed：Described native cellulose
Cleaned through ethanol, it is stand-by after suction filtration.
3. the carbon fibre material of carried titanium dioxide nano thin-film according to claim 2 and ferroferric oxide nano granules
Preparation method, it is characterised in that it is described through surface sol-gel method template surface deposition of titanium oxide nano thin-film tool
Body step is：
(1) butyl titanate is mixed with the mixed liquor of ethanol/toluene, configuration obtains the fourth of metatitanic acid four that concentration is 100~400mM
Ester solution；
(2) pretreated native cellulose is immersed in solution of tetrabutyl titanate, keeps liquid level higher than native cellulose
Upper surface, stands deposition；
(3) post-depositional native cellulose keeps liquid level to be higher than the upper surface of native cellulose first after ethanol filtering and washing, quiet
Put deposition；Hydrolysis is stood after being washed again through deionized water, is most drained afterwards through ethanol washing；
(4) process of repeat step (2)~(3), then carry out suction filtration, drying process.
4. the carbon fibre material of carried titanium dioxide nano thin-film according to claim 3 and ferroferric oxide nano granules
Preparation method, it is characterised in that in step (1), the volume ratio of ethanol and toluene is 1:1, it is molten that configuration obtains butyl titanate
The concentration of liquid is 100mM.
5. the carbon fibre material of carried titanium dioxide nano thin-film according to claim 3 and ferroferric oxide nano granules
Preparation method, it is characterised in that the pretreatment of described native cellulose and the deposition process of titanium dioxide nano-film are equal
Carried out in Suction filtration device, be specially：
(A) pretreatment of native cellulose：Native cellulose is placed in Suction filtration device, 3 times are at least washed with absolute ethyl alcohol, very
Still it is positioned over after empty suction filtration stand-by in Suction filtration device；
(B) deposition of titanium dioxide nano-film：Described solution of tetrabutyl titanate, suction filtration metatitanic acid four are added into Suction filtration device
Butyl acetate solution is higher than the upper surface of native cellulose to liquid level, it is ensured that infiltration native cellulose, and stands deposition；Use ethanol solution
Unnecessary solution of tetrabutyl titanate is washed away, suction filtration ethanol solution to liquid level is higher than after the upper surface of native cellulose, standing；Use again
Deionized water rinse, suction filtration deionized water to liquid level is higher than the upper surface of native cellulose, stands after hydrolysis；Recycling deposition,
Hydrolytic process.
6. the carbon fibre material of carried titanium dioxide nano thin-film according to claim 1 and ferroferric oxide nano granules
Preparation method, it is characterised in that load ferroferric oxide nano granules preparation process, be specially：
Configuration concentration is 1~5M ferric chloride aqueous solutionses, after being uniformly dispersed, by the mould of surface deposition of titanium oxide nano thin-film
In the described ferric chloride aqueous solutionses of plate immersion, reacted at 70~90 DEG C and obtain load dioxy through calcination processing again after 12~36h
Change the carbon fibre material of titanium nano thin-film and ferroferric oxide nano granules.
7. a kind of carried titanium dioxide nano thin-film and ferriferrous oxide nano prepared according to the method described in claim 1
Application of the carbon fibre material of grain in lithium ion battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510423068.5A CN105070889B (en) | 2015-07-17 | 2015-07-17 | A kind of preparation method, product and the application of the carbon fibre material of carried titanium dioxide nano thin-film and ferroferric oxide nano granules |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510423068.5A CN105070889B (en) | 2015-07-17 | 2015-07-17 | A kind of preparation method, product and the application of the carbon fibre material of carried titanium dioxide nano thin-film and ferroferric oxide nano granules |
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| Publication Number | Publication Date |
|---|---|
| CN105070889A CN105070889A (en) | 2015-11-18 |
| CN105070889B true CN105070889B (en) | 2017-08-15 |
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| CN109908866B (en) * | 2019-03-28 | 2021-12-31 | 中国科学院兰州化学物理研究所 | Method for preparing two-dimensional magnetic porous carbon composite material through calcination and application thereof |
| CN111769263B (en) * | 2020-06-18 | 2022-06-07 | 合肥国轩高科动力能源有限公司 | Three-dimensional C/Fe3O4Lithium ion battery cathode material and preparation method thereof |
| CN113097646B (en) * | 2021-04-09 | 2022-09-20 | 山东星能安新能源科技有限公司 | Preparation method of lithium-sulfur battery diaphragm |
| CN113793931B (en) * | 2021-11-18 | 2022-02-08 | 河南电池研究院有限公司 | Iron oxide negative electrode material for lithium ion battery and preparation method thereof |
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| CN102683710B (en) * | 2012-05-21 | 2014-08-20 | 北京化工大学 | Carbon nanofiber load titanium dioxide thin film anode material and preparation method thereof |
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