CN104241628B - A kind of preparation method and its obtained product and purposes of the di-iron trioxide microballoon of titanium dioxide modification - Google Patents
A kind of preparation method and its obtained product and purposes of the di-iron trioxide microballoon of titanium dioxide modification Download PDFInfo
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- CN104241628B CN104241628B CN201410496005.8A CN201410496005A CN104241628B CN 104241628 B CN104241628 B CN 104241628B CN 201410496005 A CN201410496005 A CN 201410496005A CN 104241628 B CN104241628 B CN 104241628B
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- H—ELECTRICITY
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- 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
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- H01M4/366—Composites as layered products
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- H—ELECTRICITY
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- 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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- 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
- H01M4/36—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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- 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
A kind of preparation method of the di-iron trioxide microballoon of titanium dioxide modification, it is that sucrose or D/W are put into hydrothermal reaction kettle after hydro-thermal reaction at a temperature of 180 220 DEG C, with deionized water and ethanol filtering and washing, drying, obtain the homogeneous carbon ball of particle diameter distribution, then by carbon ball ultrasonic disperse in the mixed solution of ferric nitrate ethanol solution and butyl titanate, stir at room temperature, it is to be mixed uniformly to be stirred after 60 80 DEG C, reaction uses absolute ethyl alcohol and deionized water filtering and washing after terminating, and intermediate product is made in 100 DEG C of drying；Intermediate product is placed in tube furnace at a temperature of 400 600 DEG C, is calcined 24 hours under air atmosphere, and the di-iron trioxide microballoon of titanium dioxide modification is made.The inventive method is easy to operate, and condition is easily-controllable, reproducible, and negative material of the obtained product as lithium ion battery, and making lithium ion battery has excellent charge-discharge performance, energy storage capacity height.
Description
Technical field
The present invention relates to a kind of di-iron trioxide microballoon of titanium dioxide modification, it can be used as negative electrode of lithium ion battery material
Material.
Background technology
It will be exhausted and can produce a large amount of greenhouse gases during its use the problems such as due to fossil energy be present, greatly
The emerging energy of amount has come into the visual field of people, such as wind energy, tide energy, solar energy, nuclear energy, biomass energy.These energy are big
Need to be converted into electric energy can just be utilized.On the other hand, it is necessary to could quilt after caused unstable electrical power storage is got up
Utilize.So moveable power supply has obtained rapidly developing.Lithium rechargeable battery therein relies on its higher specific capacity
With energy density and have extended cycle life, operating voltage is high, memory-less effect the features such as have been widely used for mobile phone, it is portable/
In the portable electronic devices such as tablet personal computer, and in the electrical source of power such as electric automobile, and the large-scale energy storage electricity such as power station
Also its good potentiality has been presented in source, be expected to substitute traditional NI-G, lead-acid battery and as the master of Green Chemistry power supply
Lead.The commercial anode material for lithium-ion batteries of in the market is mainly：Cobalt acid lithium, LiMn2O4, LiFePO4 and nickle cobalt lithium manganate
Ternary material；Commercially use negative material is mainly graphite material.Worldwide researcher is all for can
To carry out deep research and development applied to the new material of lithium ion cell electrode.
In commercial li-ion battery, production cost is mainly derived from electrode material.So how to prepare cheap, ring
Border is friendly and the electrode material of electrochemical performance turns into the most important thing that lithium ion battery develops.Only negative material is come
Say, the graphite that commercialization uses just occupies the market share of thumping majority with its cheap price and stable cycle performance.
But because its specific capacity is relatively low (theoretical specific capacity 372mAh/g, actual specific capacity are not higher than 350mAh/g), and embedding lithium electricity
Position causes easily to form Li dendrite in long-term cyclic process, causes battery short circuit, or even can cause close to the current potential of lithium metal
The serious consequences such as blast on fire.Based on this, the research and development of novel anode material have good prospect.
Working mechanism is that the oxide such as metal oxide, iron, manganese, molybdenum of " transformant " reaction relies on its higher theoretical ratio
The features such as capacity, cheap price, environment-friendly and rich reserves, enters the visual field of vast researcher.With three oxidations
Exemplified by two iron, its theoretical specific capacity is 1005mAh/g, almost the three of graphite times, and ferro element is as content in the earth's crust second
The metallic element of position is widely present in nature, easily obtains.Yet with the working mechanism of its " transformant ", it is circulated throughout in lithium
Cheng Zhong, Volume Changes are larger, easily cause material structure efflorescence and its poor ion, electronic conduction performance also cause battery
Cycle performance it is poor, finally hinder its practical application.In view of the above-mentioned problems, researcher to material by carrying out
Exquisite structure design, as by microemulsion hydro-thermal method di-iron trioxide hollow ball has been made in David Lou et al.
(J.Am.Chem.Soc.2011,133,17146-17148), by test, the cycle performance of the battery charging and discharging of this material
Good lifting is obtained.
Titanium dioxide has very good lithium cyclicity as a kind of metal oxide of " slotting insert-type " working mechanism
Can, but its theoretical specific capacity is relatively low.Embedded titanium dioxide, passes through dioxy on the spherical shell of di-iron trioxide hollow ball
Jie's sight chemiluminescence of change titanium and di-iron trioxide suppresses the composite oxides structure that its structure efflorescence is a kind of innovation and set
Meter.
The content of the invention
It is an object of the invention to provide the preparation method of di-iron trioxide microballoon of a kind of titanium dioxide modification and made
The product obtained and the purposes as lithium ion battery negative material.
Technical scheme is as follows：
A kind of preparation method of the di-iron trioxide microballoon of titanium dioxide modification, it comprises the following steps：
Step 1, by concentration be 1.5-3mol/L sucrose or D/W be put into hydrothermal reaction kettle in 180-220
At a temperature of DEG C after hydro-thermal reaction 1-4 hours, with deionized water and ethanol filtering and washing, dried at 80 DEG C, obtain particle diameter distribution
Homogeneous carbon ball；
Step 2,80ml ethanol solutions and 1- by obtained carbon ball ultrasonic disperse in iron nitrate concentration for 1.5-5mol/L
In the mixed solution of 5ml butyl titanates, magnetic agitation 0.5-2 hours, to be mixed uniformly to be stirred after 60-80 DEG C of magnetic force at room temperature
Mix 4-12 hours, reaction uses absolute ethyl alcohol and deionized water filtering and washing after terminating, and intermediate product is made in 100 DEG C of drying；
Step 3, intermediate product made from step 2 is placed in tube furnace at a temperature of 400-600 DEG C, roasted under air atmosphere
2-4 hours are burnt, the di-iron trioxide microballoon of titanium dioxide modification is made.
The di-iron trioxide microballoon that titanium dioxide made from a kind of above-mentioned preparation method is modified.
The di-iron trioxide microballoon of above-mentioned titanium dioxide modification is preparing lithium ion as lithium ion battery negative material
Application in battery.
The present invention prepares out intermediate product using carbon from template method is sacrificed, and then carries out intermediate product in air atmosphere
Roasting, the di-iron trioxide microballoon of generation titanium dioxide modification.Method is easy, reproducible, and preparation process is nontoxic.System
Into product there is high lithium storage content and good cycle performance.
The carbosphere pattern that the present invention prepares is unified, and particle diameter distribution is uniform, and its surface has a large amount of functional groups and micropore
Later stage mixed solution can be caused to immerse.Solution diffusion temperature, the time, concentration difference directly with immerse carbon ball shell depth namely
The thickness of hollow ball shell is closely related in product, while the thickness of spherical shell determines the chemical property of material again.
Butyl titanate and ethanol solution feed intake volume ratio as 1.25~6.25 in the mixed solution:100, the rate of charge
The ratio of titanium dioxide and ferric oxide in final products is determined, the addition of appropriate titanium dioxide can lift the electrification of material
Property is learned, but if titanium dioxide addition is excessive, its specific capacity can significantly decrease.
The calcination atmosphere of the intermediate product is air, and sintering temperature is 400-600 DEG C, soaking time 2-4 hours.It is above-mentioned
Condition is to remove carbon template in product from complete, obtains the metal oxide products of higher crystallinity and specific surface area.The present invention
Obtained microspherulite diameter is about 20 nanometers.
The lithium ion battery storage prepared using the di-iron trioxide microballoon of the titanium dioxide modification of the present invention as negative material
Energy is high, and charge-discharge performance is good.
Brief description of the drawings
Fig. 1 is the SEM and TEM image of product, it can be seen that the pattern of product is the tiny balloon of about 2 μm of diameter,
Shell thickness about 500nm.Its pattern is homogeneous, Stability Analysis of Structures.Fig. 1 upper lefts are the monomer SEM image of product, it can be seen that it is hollow micro-
Ball.Upper right is the product SEM image to condense together, it can be seen that its pattern is homogeneous.Lower-left is the macroscopic view that product is largely assembled
SEM image, it can be seen that product on the whole flocks together, even size distribution.Bottom right is the monomer TEM image of product,
The outer surface of its microballoon is bobbles shape as we know from the figure.
Fig. 2 is the EDX-mapping images of product, it can be seen that microballoon is made up of Ti/Fe/O elements, and element point
Cloth is uniform.
A is that product is made into half-cell in voltage is electrochemistry under 200mA/g speed in the range of 0.005-3V in Fig. 3
Cycle performance curve, b are common di-iron trioxide correlation curve, are understood according to Fig. 3, and the more common di-iron trioxide of the material is compared and followed
Ring performance and capacity are greatly improved, and also have the specific capacity of nearly 1000 every gram of MAH in 100 circulations.
Fig. 4 is the XRD spectrum of product, public by Scherrer by collection of illustrative plates it can be seen that the crystallinity of its di-iron trioxide is fine
Formula understands that its crystallite dimension is about 20 nanometers, and because the titanium dioxide amount for modifying used is seldom, and its particle may be smaller, so
The crystal information of titanium dioxide can not be found out in XRD spectrum.
Fig. 5 is the specific surface area result of product.It is computed, product is calcined 4 hours at 550 DEG C still 50m2/ g ratio table
Area, and the mesoporous of average pore size 14nm be present.
Embodiment
In line with the target of the purpose of the clear interpretation present invention, technical scheme and product performance, with reference to embodiments to this
Invention is further described
Embodiment 1
1) from the synthesis for sacrificing carbon ball template：In 150ml water heating kettles, be put into 100ml deionized waters, after weigh sucrose
52g, it is dissolved in deionized water, seals reactor and be placed in 200 DEG C of baking oven, heating is taken out after 2 hours, and alcohol is washed 5 times after suction filtration,
It is put into 80 DEG C of baking ovens overnight.
2) synthesis of intermediate product：80ml absolute ethyl alcohols are added in beaker, 60.2g Fe(NO3)39H2Os is weighed and is dissolved in
Wherein, 2ml butyl titanates, magnetic agitation 30 minutes are added after appropriate heating and magnetic agitation cause it fully to dissolve.
Separately take 0.8g carbon balls to be put into mixed solution, after being heated 4 hours at 80 DEG C, washed by filtering and washing alcohol, be put into 100 DEG C of bakings
Intermediate product is obtained after case drying.
3) acquisition of final products：Intermediate product is put into tube furnace, is warming up to 500 DEG C in air atmosphere, insulation 3 is small
When, furnace cooling afterwards, you can obtain the di-iron trioxide microballoon of final products titanium dioxide modification.
4) product 160mg is taken, before being poured into conductive agent acetylene black 20mg ground and mixeds 10min by evenly mixing
In 20mg binding agents Kynoar (PVDF) and 1ml N- methyl-pyrrolidons (NMP) solution, to obtain slurry.This is starched
Material is equably coated on copper current collector, and is dried at 80 DEG C.Punching is carried out afterwards, and the good cathode pole piece of punching is existed
Be dried in vacuo under the conditions of 120 DEG C, after be put into glove box.：By obtained lithium ion battery negative electrode, barrier film, lithium piece successively
Lamination is good, and with the ethylene carbonate of the lithium hexafluoro phosphate (LiPF6) containing 1 mol/L:Methyl ethyl carbonate:Carbonic acid two
Ethyl ester (EC/EMC/DEC) is 1 by volume:1:1 electrolyte being made into seals after being sufficiently mixed, and 2032 type lithium ions are made
Button cell,
Embodiment 2
1) from the synthesis for sacrificing carbon ball template：In 150ml water heating kettles, be put into 100ml deionized waters, after weigh glucose
60g, it is dissolved in deionized water, seals reactor and be placed in 200 DEG C of baking oven, heating is taken out after 3 hours, and alcohol is washed 5 times after suction filtration,
It is put into 80 DEG C of baking ovens overnight.
2) synthesis of intermediate product：50ml absolute ethyl alcohols are added in beaker, 60.2g Fe(NO3)39H2Os is weighed and is dissolved in
Wherein, 1ml butyl titanates, magnetic agitation 30 minutes are added after appropriate heating and magnetic agitation cause it fully to dissolve.
Separately take 0.6g carbon balls to be put into mixed solution, after being heated 4 hours at 80 DEG C, washed by filtering and washing alcohol, be put into 100 DEG C of bakings
Intermediate product is obtained after case drying.
3) acquisition of final products：Intermediate product is put into tube furnace, is warming up to 550 DEG C in air atmosphere, insulation 2 is small
When, furnace cooling afterwards, you can obtain the di-iron trioxide microballoon of final products titanium dioxide modification.Product 160mg is taken, with leading
Before electric agent acetylene black 20mg ground and mixeds 10min is poured into 20mg binding agents Kynoar (PVDF) by evenly mixing with
In 1ml N- methyl-pyrrolidons (NMP) solution, to obtain slurry.The slurry is equably coated on copper current collector,
And dried at 80 DEG C.Carry out punching afterwards, the good cathode pole piece of punching be dried in vacuo under the conditions of 120 DEG C, after be put into hand
In casing.：Obtained lithium ion battery negative electrode, barrier film, lithium piece successively lamination is good, and with the hexafluoro containing 1 mol/L
The ethylene carbonate of lithium phosphate (LiPF6):Methyl ethyl carbonate:Diethyl carbonate (EC/EMC/DEC) is 1 by volume:1:
1 electrolyte being made into seals after being sufficiently mixed, and 2032 type lithium-ion button batteries are made,
Embodiment 3
1) from the synthesis for sacrificing carbon ball template：In 150ml water heating kettles, be put into 100ml deionized waters, after weigh sucrose
62g, it is dissolved in deionized water, seals reactor and be placed in 190 DEG C of baking oven, heating is taken out after 4 hours, and alcohol is washed 5 times after suction filtration,
It is put into 80 DEG C of baking ovens overnight.
2) synthesis of intermediate product：100ml absolute ethyl alcohols are added in beaker, weigh the dissolving of 60.2g Fe(NO3)39H2Os
In wherein, 3ml butyl titanates are added after appropriate heating and magnetic agitation cause it fully to dissolve, magnetic agitation 30 is divided
Clock.Separately take 1g carbon balls to be put into mixed solution, after being heated 8 hours at 70 DEG C, washed by filtering and washing alcohol, be put into 100 DEG C
Intermediate product is obtained after oven for drying.
3) acquisition of final products：Intermediate product is put into tube furnace, is warming up to 400 DEG C in air atmosphere, insulation 4 is small
When, furnace cooling afterwards, you can obtain the di-iron trioxide microballoon of final products titanium dioxide modification.
4) product 160mg is taken, before being poured into conductive agent acetylene black 20mg ground and mixeds 10min by evenly mixing
In 20mg binding agents Kynoar (PVDF) and 1ml N- methyl-pyrrolidons (NMP) solution, to obtain slurry.This is starched
Material is equably coated on copper current collector, and is dried at 80 DEG C.Punching is carried out afterwards, and the good cathode pole piece of punching is existed
Be dried in vacuo under the conditions of 120 DEG C, after be put into glove box.：By obtained lithium ion battery negative electrode, barrier film, lithium piece successively
Lamination is good, and with the ethylene carbonate of the lithium hexafluoro phosphate (LiPF6) containing 1 mol/L:Methyl ethyl carbonate:Carbonic acid two
Ethyl ester (EC/EMC/DEC) is 1 by volume:1:1 electrolyte being made into seals after being sufficiently mixed, and 2032 type lithium ions are made
Button cell,
Embodiment 4
1) from the synthesis for sacrificing carbon ball template：In 150ml water heating kettles, be put into 100ml deionized waters, after weigh glucose
90g, it is dissolved in deionized water, seals reactor and be placed in 220 DEG C of baking oven, heating is taken out after 1 hour, and alcohol is washed 5 times after suction filtration,
It is put into 80 DEG C of baking ovens overnight.
2) synthesis of intermediate product：100ml absolute ethyl alcohols are added in beaker, weigh the dissolving of 60.2g Fe(NO3)39H2Os
In wherein, 4ml butyl titanates are added after appropriate heating and magnetic agitation cause it fully to dissolve, magnetic agitation 30 is divided
Clock.Separately take 1.2g carbon balls to be put into mixed solution, after being heated 12 hours at 60 DEG C, washed by filtering and washing alcohol, be put into 100
Intermediate product is obtained after DEG C oven for drying.
3) acquisition of final products：Intermediate product is put into tube furnace, is warming up to 400 DEG C in air atmosphere, insulation 4 is small
When, furnace cooling afterwards, you can obtain the di-iron trioxide microballoon of final products titanium dioxide modification.4) product 160mg is taken, with
Conductive agent acetylene black 20mg ground and mixeds 10min pours into 20mg binding agents Kynoar (PVDF) by evenly mixing before
With in 1ml N- methyl-pyrrolidons (NMP) solution, to obtain slurry.The slurry is equably applied on copper current collector
Cover, and dried at 80 DEG C.Carry out punching afterwards, the good cathode pole piece of punching be dried in vacuo under the conditions of 120 DEG C, after be put into
In glove box.：Obtained lithium ion battery negative electrode, barrier film, lithium piece successively lamination is good, and with six containing 1 mol/L
The ethylene carbonate of lithium fluophosphate (LiPF6):Methyl ethyl carbonate:Diethyl carbonate (EC/EMC/DEC) is 1 by volume:
1:1 electrolyte being made into seals after being sufficiently mixed, and 2032 type lithium-ion button batteries are made.
Claims (1)
1. a kind of preparation method for the di-iron trioxide microballoon that titanium dioxide applied to lithium ion battery negative material is modified, its
It is characterized in：It comprises the following steps：
Step 1, by aqueous sucrose solution that concentration is 1.5-3mol/L, to be put into hydrothermal reaction kettle hydro-thermal at a temperature of 180-220 DEG C anti-
After answering 1-4 hours, with deionized water and ethanol filtering and washing, dried at 80 DEG C, obtain the homogeneous carbon ball of particle diameter distribution；
Step 2, by obtained carbon ball ultrasonic disperse in Fe(NO3)39H2O concentration be 1.5-5mol/L 80ml ethanol solutions and
In the mixed solution of 1-5ml butyl titanates, magnetic agitation 0.5-2 hours, to be mixed uniformly after 60-80 DEG C of magnetic force at room temperature
Stir 4-12 hours, reaction uses absolute ethyl alcohol and deionized water filtering and washing after terminating, and intermediate product is made in 100 DEG C of drying；
Step 3, intermediate product made from step 2 is placed in tube furnace at a temperature of 400-600 DEG C, 2- is calcined under air atmosphere
4 hours, the di-iron trioxide microballoon of titanium dioxide modification is made.
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| CN104766953B (en) * | 2015-03-31 | 2017-02-01 | 浙江大学 | Preparation method of titanium dioxide/iron oxide composite anode material |
| CN108598449A (en) * | 2018-06-28 | 2018-09-28 | 西南石油大学 | High-performance hollow silicon-carbon graphene tri compound negative material and preparation method |
| CN108914706B (en) * | 2018-07-26 | 2020-06-16 | 山东汇高智慧纺织科技有限公司 | Environment-friendly wallpaper capable of adsorbing formaldehyde |
| CN115057471B (en) * | 2022-05-23 | 2023-07-14 | 山东大学 | Lithium ion battery negative electrode material and preparation method thereof |
| CN115472801B (en) * | 2022-10-11 | 2023-06-30 | 扬州工业职业技术学院 | Preparation method and application of hydrogenated titanium dioxide modified core-shell structure carbon coated porous ferroferric oxide and nickel oxide |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101465419A (en) * | 2009-01-05 | 2009-06-24 | 宁波职业技术学院 | Method for preparing cathode material of high capacity tin-nickel composite oxides lithium ion battery |
| CN102824884A (en) * | 2012-05-14 | 2012-12-19 | 无锡润鹏复合新材料有限公司 | TiO2/Fe2O3 composite hollow microsphere and preparation method thereof |
| CN104037398A (en) * | 2014-03-12 | 2014-09-10 | 华中师范大学 | TiO2@Fe2O3 layered multistage composite nanometer array material and preparation method and applications thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101465419A (en) * | 2009-01-05 | 2009-06-24 | 宁波职业技术学院 | Method for preparing cathode material of high capacity tin-nickel composite oxides lithium ion battery |
| CN102824884A (en) * | 2012-05-14 | 2012-12-19 | 无锡润鹏复合新材料有限公司 | TiO2/Fe2O3 composite hollow microsphere and preparation method thereof |
| CN104037398A (en) * | 2014-03-12 | 2014-09-10 | 华中师范大学 | TiO2@Fe2O3 layered multistage composite nanometer array material and preparation method and applications thereof |
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