CN106992295A - A kind of preparation method of single dispersing α ferric oxide nano pieces - Google Patents
A kind of preparation method of single dispersing α ferric oxide nano pieces Download PDFInfo
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- CN106992295A CN106992295A CN201710120611.3A CN201710120611A CN106992295A CN 106992295 A CN106992295 A CN 106992295A CN 201710120611 A CN201710120611 A CN 201710120611A CN 106992295 A CN106992295 A CN 106992295A
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- ferric oxide
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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
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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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- 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 present invention relates to a kind of preparation method of single dispersing α ferric oxide nano pieces, comprise the following steps：1) P123 is dissolved in ethylene glycol, stirred, ferric nitrate is dissolved in ethylene glycol by continuation, obtains settled solution；The molar concentration of ferric nitrate is 0.5~2mol/L in the settled solution；2) the KOH aqueous solution is added to step 1) in settled solution, obtain precursor solution russet；3) by step 2) in precursor solution reaction temperature be 180~200 DEG C, carry out 24~30h of hydro-thermal reaction, obtain single dispersing α ferric oxide nano pieces.The preparation method technical process is simple, it is easy to control, non-environmental-pollution, cost is low, it is easy to large-scale production；Gained single dispersing α ferric oxide nanos piece has outstanding cycle performance as lithium ion battery negative material simultaneously.
Description
Technical field
Field is synthesized the present invention relates to inorganic material, and in particular to a kind of preparation side of single dispersing alpha-ferric oxide nanometer sheet
Method.
Background technology
The situation of environmental pollution and energy crisis is increasingly serious, forces the mankind to change tradition based on fossil fuel
Energy consumption structure, while actively finding regenerative resource as the replacement of fossil energy.But compared to traditional fossil energy, newly
The regenerative resource of type, such as solar energy, wind energy, tide energy, geothermal energy etc. are seriously limited by the uncontrollability of environment and inconsistent
Property.Therefore, effective energy storage and easily transport transmission battery are realized, can be portable by electric energy Efficient Conversion as one kind
Electrochemical system with chemical energy, progresses into the research vision of global scientist.
Lithium ion battery is with its high working voltage platform and energy density, and memory-less effect, low cost, low stain is micro-
The features such as weak self discharge, good safety, it is widely used in portable electric appts, such as mobile phone, notebook computer, and next
For in the development of electric automobile and large-scale static energy storage system, huge application potential is shown.
At present on the positive and negative pole material for focusing on battery of Study on Li-ion batteries, researcher wants to look for
To a kind of there is high specific capacity cycle performance excellent electrode material prepares lithium ion battery simultaneously.α-Fe2O3Because its is special
Redox machinery 1007mAh/g theoretical capacity is held up to as lithium ion battery negative material, but be used as electrode
Its cycle performance of material is poor, in order to improve α-Fe2O3It is used as the cycle performance of lithium ion battery negative material.Researcher wishes
Prestige can prepare the α-Fe of nano-scale2O3Particle, improves lithium ion diffusion coefficient and electron conductivity, final to obtain electricity
The good lithium ion battery negative material of chemical property.
The content of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a kind of preparation of single dispersing alpha-ferric oxide nanometer sheet
Method, the single dispersing alpha-ferric oxide prepared has nano-scale, improves its cycle performance.
The present invention solves the technical scheme of above-mentioned technical problem：
A kind of preparation method of single dispersing alpha-ferric oxide nanometer sheet, comprises the following steps：
1) P123 is dissolved in ethylene glycol, stirred, ferric nitrate is dissolved in ethylene glycol by continuation, obtains settled solution；
The molar concentration of ferric nitrate is 0.5~2mol/L in the settled solution；
2) the KOH aqueous solution is added to step 1) in settled solution, obtain precursor solution russet；
3) by step 2) in precursor solution reaction temperature be 180~200 DEG C, carry out 24~30h of hydro-thermal reaction, obtain
To single dispersing alpha-ferric oxide nanometer sheet.
In above-mentioned technical proposal, P123 is a kind of triblock copolymer, and full name is PEO-PPOX-poly-
Oxirane triblock copolymer, its molecular formula is:PEO-PPO-PEO.P123 has the effect of regulation and control alpha-ferric oxide pattern,
P123 can be coated on ferric oxide nano piece surface in hydrothermal reaction process, reduce the reunion of ferric oxide nano piece, and in heat
One layer of unbodied C can be left after processing in alpha-ferric oxide nanometer sheet so that alpha-ferric oxide nanometer sheet is used as lithium-ion electric
Pond negative material has outstanding cycle performance；Secondly, by controlling the addition of ferric nitrate, size uniformity can be obtained, and
The smaller alpha-ferric oxide of particle size.
Preferably, the hydro-thermal reaction is carried out in ptfe autoclave, hydro-thermal reaction product is filtered, clearly
Wash, be dried to obtain single dispersing alpha-ferric oxide nanometer sheet.
Preferably, the step 1) in P123 is dissolved in ethylene glycol, 20-30h is stirred at room temperature.By it is long when
Between stirring P123 can be evenly dispersed in ethylene glycol, advantageously in the preparation of single dispersing α-ferric oxide nano piece.
Preferably, the step 1) in settled solution P123 mass concentration be 30~80g/L.
Preferably, the step 2) in precursor solution the volume fraction of ethylene glycol be 60~80%.Pass through control
The volume ratio of ethylene glycol and water in precursor solution, can play the effect that ethylene glycol regulates and controls alpha-ferric oxide pattern, avoid simultaneously
Excessive ethylene glycol makes Fe3+Being reduced prevents from obtaining Fe3O4, ensure to obtain single-phase alpha-ferric oxide with this.
Preferably, the step 2) in ferric nitrate and KOH mol ratio be：0.25~1.25:1.
Preferably, the step 2) in the KOH aqueous solution molar concentration be 4~6mol/L.
Preferably, the step 3) in hydro-thermal reaction reaction temperature be 190~200 DEG C, the reaction time be 26~
30h.Under the reaction temperature and reaction time, the Morphological control of single dispersing alpha-ferric oxide nanometer sheet is more favorable for so that product
Pattern it is more regular, size is more homogeneous.
Preferably, the preparation method of described single dispersing alpha-ferric oxide nanometer sheet, comprises the following steps：
1) P123 is dissolved in ethylene glycol, 23-24h is stirred at room temperature, ferric nitrate is dissolved in ethylene glycol by continuation,
Obtain settled solution；The molar concentration of ferric nitrate is 0.5~0.6mol/L in the settled solution；P123 in the settled solution
Mass concentration be 30~35g/L；
2) the KOH aqueous solution is added to step 1) in settled solution, obtain precursor solution russet；The forerunner
The volume fraction of ethylene glycol is 70~80% in liquid solution；The mol ratio of the ferric nitrate and KOH is：0.3~0.4:1；
3) by step 2) in precursor solution reaction temperature be 190~200 DEG C, carry out 28~30h of hydro-thermal reaction, obtain
To single dispersing alpha-ferric oxide nanometer sheet.
Compared with the existing technology, beneficial effects of the present invention are embodied in：
(1) present invention process process is simple, it is easy to control, and non-environmental-pollution, cost is low, it is easy to large-scale production；
(2) size diameter of single dispersing alpha-ferric oxide nanometer sheet produced by the present invention is about 100nm, and thickness is about 50nm,
Product quality is stable, and purity is high, powder granule good dispersion.
(3) present invention single dispersing alpha-ferric oxide nanometer sheet Surface coating for preparing P123, after heat treatment can α-
One layer of unbodied C is left on ferric oxide nano piece so that alpha-ferric oxide nanometer sheet has as lithium ion battery negative material
Outstanding cycle performance.
Brief description of the drawings
Fig. 1 is the X-ray diffractogram for the single dispersing alpha-ferric oxide nanometer sheet that embodiment 1 is synthesized；
Fig. 2 is the scanning electron microscope diagram for the single dispersing alpha-ferric oxide nanometer sheet that embodiment 1 is synthesized；
Fig. 3 is first three charging and discharging curve of the single dispersing alpha-ferric oxide nanometer sheet that embodiment 1 is synthesized；
Fig. 4 is the scanning electron microscope diagram for the alpha-ferric oxide nanometer sheet that comparative example 1 is synthesized；
Fig. 5 is first three charging and discharging curve of the alpha-ferric oxide nanometer sheet that comparative example 1 is synthesized；
Fig. 6 be comparative example it is 2-in-1 into alpha-ferric oxide particulate scanning electron microscope diagram；
Fig. 7 is the Fe that comparative example 3 is synthesized3O4Scanning electron microscope diagram.
Embodiment
The invention will be further described with Figure of description with reference to embodiments.
Embodiment 1
1) take 1g P123 to be dissolved in 30ml ethylene glycol, at room temperature by 24h stirring, form settled solution；Take
0.015mol Fe(NO3)39H2Os are dissolved in above-mentioned P123 ethylene glycol solutions；
2) while taking 0.04mol KOH to be dissolved in 10ml deionized water, it is sufficiently stirred for, forms settled solution；
3) the above-mentioned KOH aqueous solution is slowly dropped in P123 ethylene glycol solution to form presoma russet molten
Liquid, precursor solution is transferred in 50ml ptfe autoclaves and carries out 200 DEG C, 30h hydro-thermal reactions produce hydro-thermal reaction
Thing is filtered, cleaning, is dried to obtain single dispersing alpha-ferric oxide nanometer sheet.
Single dispersing alpha-ferric oxide nanometer sheet to the gained of embodiment 1 carries out XRD signs, as shown in figure 1, X-ray diffraction is surveyed
Bright product of taking temperature is pure phase, in the absence of dephasign Fe3O4, it was demonstrated that the product crystallinity prepared is good, is not introduced into course of reaction
Impurity.
Single dispersing alpha-ferric oxide nanometer sheet to the gained of embodiment 1 carries out SEM signs, as shown in Fig. 2 product is single dispersing
Alpha-ferric oxide nanometer sheet, diameter is about 100nm, and thickness is about 50nm, and product favorable dispersibility, does not occur reuniting existing
As.
Embodiment 2
1) take 1g P123 to be dissolved in 20ml ethylene glycol, at room temperature by 20h stirring, form settled solution；Take
0.02mol Fe(NO3)39H2Os are dissolved in P123 ethylene glycol solutions；
2) while taking 0.035mol KOH to be dissolved in 10ml deionized water, it is sufficiently stirred for, forms settled solution；
3) the above-mentioned KOH aqueous solution is slowly dropped to formation bronzing precursor solution in P123 ethylene glycol solution,
Precursor solution is transferred in 50ml ptfe autoclaves and carries out 200 DEG C, 24h hydro-thermal reactions, by hydro-thermal reaction product
Filtering, cleaning, is dried to obtain single dispersing alpha-ferric oxide nanometer sheet.
Embodiment 3
1) take 2g P123 to be dissolved in 25ml ethylene glycol, at room temperature by 30h stirring, form settled solution；Take
0.02mol Fe(NO3)39H2Os are dissolved in P123 ethylene glycol solutions；
2) while taking 0.06molKOH to be dissolved in 10ml deionized water, it is sufficiently stirred for, forms settled solution；
3) the above-mentioned KOH aqueous solution is slowly dropped to formation bronzing precursor solution in P123 ethylene glycol solution,
Precursor solution is transferred in 50ml ptfe autoclaves and carries out 200 DEG C, 24h hydro-thermal reactions, by hydro-thermal reaction product
Filtering, cleaning, is dried to obtain single dispersing alpha-ferric oxide nanometer sheet.
Comparative example 1：
1) 0.015mol Fe(NO3)39H2Os are taken to be dissolved in 30ml ethylene glycol solutions；
2) while taking 0.04mol KOH to be dissolved in 10ml deionized water, it is sufficiently stirred for, forms settled solution；
3) by the above-mentioned KOH aqueous solution be slowly dropped in the ethylene glycol solution of ferric nitrate formed bronzing presoma it is molten
Liquid, precursor solution is transferred in 50ml ptfe autoclaves and carries out 200 DEG C, 24h hydro-thermal reactions produce hydro-thermal reaction
Thing is filtered, cleaning, is dried to obtain alpha-ferric oxide nanometer sheet.
The alpha-ferric oxide nanometer sheet of the gained of comparative example 1 carries out SEM signs, as shown in Figure 4.
It can be clearly seen that by Fig. 2 and Fig. 4, although alpha-ferric oxide nanometer can be obtained in the case of being not introduced into P123
Piece, but the reunion of alpha-ferric oxide nanometer sheet is very serious, these alpha-ferric oxides reunited together can discharge and recharge process
In rapid loss capacity (as shown in Figure 5), only maintain 500mAh/g capacity after 3 circulations, and add after P123, water
P123 can suppress the reunion of alpha-ferric oxide nanometer sheet as surfactant in thermal process reactor, obtain favorable dispersibility
Alpha-ferric oxide nanometer sheet (as shown in Figure 2), and be assembled into battery there is excellent cycle performance, under same cycle-index
Capacity with 900mAh/g, and there is no in cyclic process obvious capacity attenuation.
Comparative example 2：
1) 0.01mol Fe(NO3)39H2Os are taken to be dissolved in 30ml ethylene glycol solutions；
2) while taking 0.04mol KOH to be dissolved in 10ml deionized water, it is sufficiently stirred for, forms settled solution；
3) by the above-mentioned KOH aqueous solution be slowly dropped in the ethylene glycol solution of ferric nitrate formed bronzing presoma it is molten
Liquid, precursor solution is transferred in 50ml ptfe autoclaves and carries out 200 DEG C, 24 h hydro-thermal reactions, by hydro-thermal reaction
Product is filtered, cleaning, is dried to obtain alpha-ferric oxide particulate.
The alpha-ferric oxide particulate of the gained of comparative example 2 carries out SEM signs, as shown in Figure 6, it can be seen that obtained pattern is micro-
Grain, alpha-ferric oxide particle size is in 1 microns, it is impossible to obtain the alpha-ferric oxide of nano-scale.Improve and add in water-heat process
Fe (the NO entered3)3Amount, can lift the nucleus number formed in alpha-ferric oxide crystallization process, suppress entering for alpha-ferric oxide crystal grain
One step-length is big, the final alpha-oxidation iron plate for obtaining nano-scale, and due to the Fe (NO of addition in comparative example 23)3Amount it is very few, obtain
Less than alpha-ferric oxide nanometer sheet.
Comparative example 3：
0.015mol Fe(NO3)39H2Os are taken to be dissolved in 40ml ethylene glycol solutions, while taking 0.04molKOH to be dissolved in
In the ethylene glycol solution for stating ferric nitrate, it is sufficiently stirred for, forms black precursor solution, precursor solution is transferred to 50ml poly- four
200 DEG C are carried out in PVF reactor, 24h hydro-thermal reactions filter hydro-thermal reaction product, cleaning is dried to obtain Fe3O4。
The Fe of the gained of comparative example 33O4SEM signs are carried out, as shown in fig. 7, being understood by comparative example 3 in pure ethylene glycol solution
Excessive ethylene glycol can cause part Fe in middle carry out hydro-thermal reaction, hydrothermal system3+It is reduced, the product finally obtained is size
It is distributed very uneven Fe3O4, it is impossible to used as lithium ion battery negative material.
Performance test：Battery material chemical property is evaluated using button cell.
When preparing electrode plates, selection PVDF and second block are black respectively as binding agent and conductive agent, according to active material：It is viscous
Tie agent：Conductive agent 75:15:10 mass ratio weighs three kinds of materials in agate mortar, dry grinding, and appropriate NMP wet-millings are added afterwards
Homogeneous slurry is formed, is coated uniformly on afterwards on copper foil, is finally transferred in 70 DEG C of vacuum drying chambers and dries.
After the completion of coating and drying process, the sequin that pole piece is punched to tests electrode used therein pole piece.
After pole piece is weighed, it is transferred in vacuum drying chamber and dries, be transferred to afterwards in the glove box full of argon gas, with lithium piece
Electrode as a comparison, type polypropylene perforated membrane is as battery diaphragm, and concentration is 1mol/L LiPF6/DMC/EMC (1:1:1) mix
Solution is closed as electrolyte, is sequentially placed, assembles battery, after plate pressing machine is sealed and is stood, battery can be carried out accordingly
Electro-chemical test.
Example 1 and the products therefrom of comparative example 1 carry out electro-chemical test as active material respectively, as a result such as Fig. 3 and
Shown in Fig. 5, although alpha-ferric oxide nanometer sheet can be obtained in the case of being not introduced into P123, the reunion of alpha-ferric oxide nanometer sheet
Very serious, these alpha-ferric oxides reunited together can lose capacity (as shown in Figure 5) rapidly during discharge and recharge,
500mAh/g capacity is only maintained after 3 circulations；And add after P123, P123 is used as surface-active in hydrothermal reaction process
Agent, can suppress the reunion of alpha-ferric oxide nanometer sheet, obtain the alpha-ferric oxide nanometer sheet of favorable dispersibility, and be assembled into battery
With excellent cycle performance (as shown in Figure 3), there is 900mAh/g capacity under same cycle-index, and in circulation
During there is no obvious capacity attenuation.
Claims (8)
1. a kind of preparation method of single dispersing alpha-ferric oxide nanometer sheet, it is characterised in that comprise the following steps：
1) P123 is dissolved in ethylene glycol, stirred, ferric nitrate is dissolved in ethylene glycol by continuation, obtains settled solution；It is described
The molar concentration of ferric nitrate is 0.5~2mol/L in settled solution；
2) the KOH aqueous solution is added to step 1) in settled solution, obtain precursor solution russet；
3) by step 2) in precursor solution reaction temperature be 180~200 DEG C, carry out 24~30h of hydro-thermal reaction, obtain list
Scattered alpha-ferric oxide nanometer sheet.
2. the preparation method of single dispersing alpha-ferric oxide nanometer sheet according to claim 1, it is characterised in that the step 1)
It is middle that P123 is dissolved in ethylene glycol, 20-30h is stirred at room temperature.
3. the preparation method of single dispersing alpha-ferric oxide nanometer sheet according to claim 1, it is characterised in that the step 1)
P123 mass concentration is 30~80g/L in middle settled solution.
4. the preparation method of single dispersing alpha-ferric oxide nanometer sheet according to claim 1, it is characterised in that the step 2)
The volume fraction of ethylene glycol is 60~80% in middle precursor solution.
5. the preparation method of single dispersing alpha-ferric oxide nanometer sheet according to claim 1, it is characterised in that the step 2)
The mol ratio of middle ferric nitrate and KOH is：0.25~1.25:1.
6. the preparation method of single dispersing alpha-ferric oxide nanometer sheet according to claim 5, it is characterised in that the step 2)
The molar concentration of the middle KOH aqueous solution is 4~6mol/L.
7. the preparation method of single dispersing alpha-ferric oxide nanometer sheet according to claim 1, it is characterised in that the step 3)
The reaction temperature of middle hydro-thermal reaction is 190~200 DEG C, and the reaction time is 26~30h.
8. the preparation method of single dispersing alpha-ferric oxide nanometer sheet according to claim 1, it is characterised in that including following step
Suddenly：
1) P123 is dissolved in ethylene glycol, 23-24h is stirred at room temperature, ferric nitrate is dissolved in ethylene glycol, obtained by continuation
Settled solution；The molar concentration of ferric nitrate is 0.5~0.6mol/L in the settled solution；P123 matter in the settled solution
Amount concentration is 30~35g/L；
2) the KOH aqueous solution is added to step 1) in settled solution, obtain precursor solution russet；The presoma is molten
The volume fraction of ethylene glycol is 70~80% in liquid；The mol ratio of the ferric nitrate and KOH is：0.3~0.4:1；
3) by step 2) in precursor solution reaction temperature be 190~200 DEG C, carry out 28~30h of hydro-thermal reaction, obtain list
Scattered alpha-ferric oxide nanometer sheet.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108217715A (en) * | 2018-02-24 | 2018-06-29 | 厦门大学 | A kind of preparation method of two-dimensional metallic oxide nano-slice |
| CN110690466A (en) * | 2019-11-07 | 2020-01-14 | 南京晓庄学院 | Preparation method and application of pyrolite oxide nanosheet |
| CN111193026A (en) * | 2020-01-08 | 2020-05-22 | 河南城建学院 | Preparation method of fusiform iron oxide single crystal nano material |
| CN114471612A (en) * | 2022-01-28 | 2022-05-13 | 中国科学技术大学 | Amorphous iron oxide nanosheet composite material, and preparation method and application thereof |
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| CN102936033A (en) * | 2012-12-04 | 2013-02-20 | 九江学院 | Method for preparing monodisperse zinc oxide ultrathin nanosheets |
| CN106082353A (en) * | 2016-06-12 | 2016-11-09 | 常州大学 | A kind of preparation method of ferric oxide nano sheet |
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| CN102936033A (en) * | 2012-12-04 | 2013-02-20 | 九江学院 | Method for preparing monodisperse zinc oxide ultrathin nanosheets |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108217715A (en) * | 2018-02-24 | 2018-06-29 | 厦门大学 | A kind of preparation method of two-dimensional metallic oxide nano-slice |
| CN108217715B (en) * | 2018-02-24 | 2019-10-15 | 厦门大学 | A kind of preparation method of two-dimensional metallic oxide nano-slice |
| CN110690466A (en) * | 2019-11-07 | 2020-01-14 | 南京晓庄学院 | Preparation method and application of pyrolite oxide nanosheet |
| CN111193026A (en) * | 2020-01-08 | 2020-05-22 | 河南城建学院 | Preparation method of fusiform iron oxide single crystal nano material |
| CN114471612A (en) * | 2022-01-28 | 2022-05-13 | 中国科学技术大学 | Amorphous iron oxide nanosheet composite material, and preparation method and application thereof |
| CN114471612B (en) * | 2022-01-28 | 2023-03-28 | 中国科学技术大学 | Amorphous iron oxide nanosheet composite material, and preparation method and application thereof |
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