CN102569783A - Preparation method and application of Fe3O4-Co3O4 porous magnetic composite material - Google Patents
Preparation method and application of Fe3O4-Co3O4 porous magnetic composite material Download PDFInfo
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Abstract
The invention discloses a preparation method of a Fe3O4-Co3O4 porous magnetic composite material. The preparation method comprises the following steps of (a) blending, (b) heating, (c) drying and (d) calcining. In comparison with the prior art, the invention has the following advantages: (1) other oxides are not found in the product, and the product is a heterogeneous material and has uniform particle size, special morphology, high activity, simple one-step synthesis method, large apparent density, and good magnetic performance; (2) the method has high yield, low cost, short production flow and is convenient in scale-up experiment; (3) the method is simple and controllable, and has low demand for equipment, so that the method is suitable for industrial production; and (4) the magnetic material with a heterogeneous oxide core-shell structure provided by the invention can be effectively applied to lithium-ion and fuel cell materials.
Description
Technical field:
The present invention relates to the preparation and the application thereof of nano-metal-oxide, the preparation method of a kind of tri-iron tetroxide-cobaltosic oxide yolk-shell porous magnetic composite material is provided.
Technical background:
Nucleocapsid structure and hollow shell structure can prevent the gathering examined, and this type material often is used in controlled release, in the application of controlled catalysis and light and electricity.The place that the Yolk-shell structure is different from nucleocapsid and hollow shell structure is, when it has the shell of a sky, has the nuclear that can move freely in the ghost simultaneously.And a heterogeneous Yolk-shell structure; Because the peculiar property of the nuclear that they move freely, the gap between nucleocapsid and functional shell make them become nano-reactor; Bio-pharmaceuticals, the potential material during lithium ion battery and photocatalysis etc. are used.
The preparation method of a Yolk-shell structure of relatively using always is the auxiliary selective etch method of template, and promptly middle nuclear particle is coated the shell of double-deck different materials, and the shell of internal layer is by a kind of solvent or through the calcining removal.But said method efficient is low, and process is complicated; Have also that big ear effect and Oswald your moral effect realizes synthesizing through agreeing, but these methods are only limited to the material that is used for the nucleocapsid homogeneity.It is the heterogeneous nucleocapsid structure of shell with silicon that Dongsheng Xu and Xue-Jun Wu (X.J.Wu, D.S.Xu, J.Am.Chem.Soc.2009,131,2774.) have synthesized in the aqueous solution of dodecyl sodium sulfonate betaine (LSB) and neopelex (SDS).But need extra interpolation structure directing agent in the entire reaction, like 3-aminopropyltriethoxywerene werene (APTES), and shell is a non-porous.
Summary of the invention
It is a kind of simple that the present invention provides, and environmental protection is efficient, the synthetic method of ferromagnetic tri-iron tetroxide-cobaltosic oxide yolk-shell structure porous magnetic composite material; A kind of composite material of the novel magnetic porous structure of heterogeneous oxide yolk-shell, and the application of above-mentioned material on lithium ion battery, fuel cell, and demonstrate the half wave potential of calibration, reached the half wave potential of Precious Metals-Gold.
The present invention solves above-mentioned technical problem through following technical scheme, and the preparation method of a kind of tri-iron tetroxide-cobaltosic oxide porous magnetic composite comprises following operation:
(a) blend step: at room temperature divalent cobalt and divalent iron salt mixture are added in the mixed solvent, and add urea and trisodium citrate, fully stir and process yellow-brownish solution;
The mass ratio of divalent cobalt, divalent iron salt, urea, trisodium citrate is 1: 0.36-0.65: 1-2: 0.84;
Described mixed solvent is the mixed solvent of water, ethanol, butanols, and its volume ratio is 100-150: 100: 0.1-5; The volume/mass of mixed solvent and divalent cobalt (ml/g) is than being 1: 0.01-0.016.
Different water alcohol is than controlling the big or small of space between nuclear and shell and having or not.
As important morphology control agent, its existence is that the preparation of the heterogeneous spherical flower-shaped material of nucleocapsid is crucial to trisodium citrate in entire reaction.And urea is being controlled the pH value of solution, and speed, direction and size that pH is worth the affects nuclear particle to be assembled.
(b) heating steps: the prepared solution of step (a) is heated to 100-200 ℃, reaction time 1-24 hour;
(c) drying steps: with the cooling of the resulting sediment of (b) heating steps, filter, washing is to neutral, 60 ℃ of vacuumizes are to constant weight, get final product the yolk-shell material of atresia;
(d) calcining step: the product that (c) obtained places 200-500 ℃ of temperature lower calcination, and calcination time is 0.5-3 hour, and calcining is without any need for protection gas, and heating gets final product in the air, is cooled to room temperature.This process is the tri-iron tetroxide-cobaltosic oxide yolk-shell structure magnetic micro-flowers that is converted into porous for the presoma that will obtain in (c) stage.
The pH value of the solution in the preferred step (a) is 5-7;
Water, ethanol, butanols are 100-130 by volume: 100: 0.1-3;
Divalent cobalt and divalent iron salt mol ratio are 6-4: 2;
Reaction temperature in the preferred step (b) is 120-160 ℃, and the reaction time is 4-12 hour.
The uniform tri-iron tetroxide of the particle diameter-cobaltosic oxide yolk-shell porous magnetic composite material the key technical indexes of the present invention's preparation:
The key technical indexes of the multi-functional tri-iron tetroxide of table 1-cobaltosic oxide yolk-shell porous magnetic composite material
The advantage that the present invention gives prominence to is:
1. in product, do not find other oxide, and particle diameter is even, pattern is special, activity is good, a simple step of method is synthetic, apparent density is big, magnetic property good and be dissimilar materials;
2. cost is low, and production procedure is short, is easy to amplification test;
3. this method simple controllable, equipment requirements is not high, is fit to suitability for industrialized production;
4. heterogeneous oxide yolk-shell structure magnetic material of the present invention can effectively be applied to lithium ion battery; Simultaneously but effective application is in fuel cell, the comparable Precious Metals-Gold of its half wave potential, and its preparation method is simple more than gold; Cost is lower than gold, and productive rate is big more than gold; Simultaneously than pure tri-iron tetroxide and pure cobaltosic oxide function admirable.
5. use the formation agent of trisodium citrate in this method, and make the size of water alcohol than specificity control material space as the material pattern.
Description of drawings
Fig. 1 is X-ray diffraction (XRD) figure that embodiment 1 makes tri-iron tetroxide-cobaltosic oxide yolk-shell porous magnetic composite material.
Fig. 2 is scanning electron microscopy (SEM) photo that embodiment 1 makes tri-iron tetroxide-cobaltosic oxide yolk-shell porous magnetic composite material.The multiplication factor of two width of cloth pictures is respectively 4,500 times and 30,000 times.Illustration among the figure (b) is the enlarged drawing on flower shell surface, and multiplication factor is 200,000 times.
Fig. 3 is transmission electron microscopy (TEM) photo that embodiment 1 makes tri-iron tetroxide-cobaltosic oxide yolk-shell porous magnetic composite material.
Fig. 4 is the photo that embodiment 1 makes the linear scan volt-ampere curve of tri-iron tetroxide-cobaltosic oxide yolk-shell porous magnetic composite material.
Fig. 5 is that embodiment 1 makes the photo that concerns between discharge capacity and the cycle-index of tri-iron tetroxide-cobaltosic oxide yolk-shell porous magnetic composite material.
Embodiment
Be described further below in conjunction with the technical scheme of specific embodiment invention.
Embodiment 1
1, the preparation of tri-iron tetroxide-cobaltosic oxide yolk-shell porous magnetic composite material:
(a) blend step: at room temperature 0.1221g cobalt chloride and ferrous sulfate 0.0634g being added to the 20ml volume ratio is in 120: 100: 1 the mixed solvent of water, ethanol, butanols; And adding 0.16g urea and 0.10g trisodium citrate; Fully stir and process yellow-brownish solution, pH is 5;
(b) heating steps: the prepared solution of step (a) is heated to 120 ℃, 10 hours reaction time;
(c) drying steps: with the cooling of the resulting sediment of (b) heating steps, filter, washing is to neutral, 60 ℃ of dryings, get final product the yolk-shell material of atresia;
(d) product that (c) is obtained places 300 ℃ of temperature lower calcinations, and calcination time is 1 hour, and calcining is without any need for protection gas, and the empty heating of air gets final product, and is cooled to room temperature.This process is the tri-iron tetroxide-cobaltosic oxide yolk-shell magnetic composite that is converted into porous for the pore-free material that will obtain in (c) stage.
The gained material is spherical flower-shaped, and size is about 2-3 μ m evenly, and the space is arranged between nucleocapsid.
2, electrochemical property test:
Tri-iron tetroxide-cobaltosic oxide yolk-shell porous magnetic composite material the 4mg that gets preparation is scattered in the ethanolic solution of 1mL; Getting 20 μ L drips on the saturated calomel electrode that cleans up; Dripping the naphthols of 10 μ L after 1 hour; After treating that electrode is done, in the KOH of 1M solution, detect with linear scan volt-ampere curve method, the rotating speed of disk electrode is 1000 commentaries on classics.The evaluation method of performance is half wave potential and current corresponding density thereof.
As shown in Figure 4: the half wave potential of this material is at-0.44V, and is approaching with the half wave potential-0.43V of gold.It is the non-noble metal fuel cell material of function admirable.
3, electrochemical property test:
Tri-iron tetroxide-cobaltosic oxide yolk-shell porous magnetic the composite material of preparation is mixed by 50: 40: 10 mass ratio with acetylene black, polytetrafluoroethylene; Under the pressure of 20 MPas, electrode active material is pressed on the copper sheet; The work electrode diameter of making is 1cm; Metal lithium sheet is as auxiliary electrode, and diameter is 1cm, and calomel electrode is as reference electrode; Electrolyte is that the 1mol/L lithium hexafluoro phosphate is dissolved in ethylene carbonate and the dimethyl carbonate mixed solution, and the mol ratio of ethylene carbonate and dimethyl carbonate is 1: 1; The battery assembling: entire cell is assembled in the glove box that is full of argon gas and accomplishes; Electrochemical property test: entire cell is accomplished with the LAND battery test system.
As shown in Figure 5, material still presents good specific discharge capacity after 20 circulations, and this material has demonstrated the good ability that recycles.
Embodiment 2
1, the preparation of tri-iron tetroxide-cobaltosic oxide yolk-shell porous magnetic composite material:
(a) blend step: at room temperature 0.1223g cobalt chloride and 0.0634g ferrous sulfate mixture being added to volume ratio is in 100: 100: 3 the water, ethanol, butanols solvent; And adding 0.16g urea and 0.10g trisodium citrate; Fully stir and process yellow-brownish solution, pH is 5;
(b) heating steps: the prepared solution of step (a) is heated to 120 ℃, 5 hours reaction time;
(c) drying steps: with the cooling of the resulting sediment of (b) heating steps, filter, washing is to neutral, 60 ℃ of dryings, get final product the yolk-shell material of atresia;
(d) product that (c) is obtained places 300 ℃ of temperature lower calcinations, and calcination time is 1 hour, and calcining is without any need for protection gas, and the empty heating of air gets final product, and is cooled to room temperature.This process is the tri-iron tetroxide-cobaltosic oxide yolk-shell magnetic composite that is converted into porous for the pore-free material that will obtain in (c) stage.
1, the preparation of tri-iron tetroxide-cobaltosic oxide yolk-shell porous magnetic composite material:
(a) blend step: at room temperature 0.1465g cobalt chloride and 0.0645g ferrous sulfate mixture being added to volume ratio is in 120: 100: 1 the water, ethanol, butanols solvent; And adding 0.16g urea and 0.10g trisodium citrate; Fully stir and process yellow-brownish solution, pH is 5;
(b) heating steps: the prepared solution of step (a) is heated to 150 ℃, 10 hours reaction time;
(c) drying steps: with the cooling of the resulting sediment of (b) heating steps, filter, washing is to neutral, 60 ℃ of dryings, get final product the yolk-shell material of atresia;
(d) product that (c) is obtained places 300 ℃ of temperature lower calcinations, and calcination time is 1 hour, and calcining is without any need for protection gas, and the empty heating of air gets final product, and is cooled to room temperature.This process is the tri-iron tetroxide-cobaltosic oxide yolk-shell magnetic composite that is converted into porous for the pore-free material that will obtain in (c) stage.
1, the preparation of tri-iron tetroxide-cobaltosic oxide yolk-shell porous magnetic composite material:
(a) blend step: at room temperature 0.1221g cobalt chloride and 0.0634g ferrous sulfate mixture being added to volume ratio is in 120: 100: 1 the water, ethanol, butanols solvent; And adding 0.16g urea and 0.10g trisodium citrate; Fully stir and process yellow-brownish solution, pH is 5;
(b) heating steps: the prepared solution of step (a) is heated to 150 ℃, 5 hours reaction time;
(c) drying steps: with the cooling of the resulting sediment of (b) heating steps, filter, washing is to neutral, 60 ℃ of dryings, get final product the yolk-shell material of atresia;
(d) product that (c) is obtained places 300 ℃ of temperature lower calcinations, and calcination time is 2 hours, and calcining is without any need for protection gas, and the empty heating of air gets final product, and is cooled to room temperature.This process is the tri-iron tetroxide-cobaltosic oxide yolk-shell magnetic composite that is converted into porous for the pore-free material that will obtain in (c) stage.
1, the preparation of tri-iron tetroxide-cobaltosic oxide yolk-shell porous magnetic composite material:
(a) blend step: at room temperature 0.1221g cobalt chloride and 0.0634g ferrous sulfate mixture being added to volume ratio is in 120: 100: 1 the water, ethanol, butanols solvent; And adding 0.16g urea and 0.10g trisodium citrate; Fully stir and process yellow-brownish solution, pH is 5;
(b) heating steps: the prepared solution of step (a) is heated to 120 ℃, 5 hours reaction time;
(c) drying steps: with the cooling of the resulting sediment of (b) heating steps, filter, washing is to neutral, 60 ℃ of dryings, get final product the yolk-shell composite material of atresia;
(d) product that (c) is obtained places 400 ℃ of temperature lower calcinations, and calcination time is 1 hour, and calcining is without any need for protection gas, and the empty heating of air gets final product, and is cooled to room temperature.This process is the tri-iron tetroxide-cobaltosic oxide yolk-shell magnetic composite that is converted into porous for the pore-free material that will obtain in (c) stage.
Embodiment 6
1, the preparation of tri-iron tetroxide-cobaltosic oxide yolk-shell porous magnetic composite material:
(a) blend step: at room temperature 0.0977g cobalt chloride and 0.0951g ferrous sulfate mixture being added to volume ratio is in 100: 100: 2 the water, ethanol, butanols solvent; And adding 0.16g urea and 0.10g trisodium citrate; Fully stir and process yellow-brownish solution, pH is 5;
(b) heating steps: the prepared solution of step (a) is heated to 120 ℃, 10 hours reaction time;
(c) drying steps: with the cooling of the resulting sediment of (b) heating steps, filter, washing is to neutral, 60 ℃ of dryings, get final product the yolk-shell material of atresia;
(d) product that (c) is obtained places 300 ℃ of temperature lower calcinations, and calcination time is 1 hour, and calcining is without any need for protection gas, and the empty heating of air gets final product, and is cooled to room temperature.This process is the tri-iron tetroxide-cobaltosic oxide yolk-shell magnetic composite that is converted into porous for the pore-free material that will obtain in (c) stage.
The electrochemical experimental implementation of embodiment 2-6 is identical with embodiment 1, and demonstrates identical experimental result.
Embodiment 7: (Comparative Examples 1)
The preparation of composite material:
(a) blend step: at room temperature 0.1221g cobalt chloride and 0.0634g ferrous sulfate mixture being added to volume ratio is in 120: 100: 1 the water, ethanol, butanols solvent; And adding 0.16g urea and 0g trisodium citrate; Fully stir and process yellow-brownish solution, PH is 5;
(b) heating steps: the prepared solution of step (a) is heated to 120 ℃, 10 hours reaction time;
(c) drying steps: to neutral, 60 ℃ of dryings obtain the flower-shaped yolk-shell structure of non-sphere with the resulting sediment cooling of (b) heating steps, filtration, washing, but the material precursor of simple one dimension wire.The importance that has also shown simultaneously trisodium citrate material structure control in synthetic.
Embodiment 8: (Comparative Examples 2)
The preparation of composite material:
(a) blend step: at room temperature 0.1221g cobalt chloride and 0.0634g ferrous sulfate mixture being added to volume ratio is in 120: 100: 0 the water, ethanol, butanols solvent; And adding 0.16g urea and 0.10g trisodium citrate; Fully stir and process yellow-brownish solution, pH is 5;
(b) heating steps: the prepared solution of step (a) is heated to 120 ℃, 10 hours reaction time;
(c) drying steps: to neutral, 60 ℃ of dryings obtain spherical flower-shaped material with the resulting sediment cooling of (b) heating steps, filtration, washing, and the material size is even, but nuclear does not have shell, does not have the space, is simple spherical micron order material.Also highlight water outlet alcohol than interstitial importance in material is synthetic.
Claims (6)
1. the preparation method of tri-iron tetroxide-cobaltosic oxide porous magnetic composite is characterized in that: comprise following operation:
(a) blend step: at room temperature divalent cobalt and divalent iron salt mixture are added in the mixed solvent, and add urea and trisodium citrate, fully stir and process yellow-brownish solution;
The mass ratio of divalent cobalt, divalent iron salt, urea, trisodium citrate is 1: 0.36-0.65: 1-2: 0.84;
Described mixed solvent is the mixed solvent of water, ethanol, butanols, and its volume ratio is 100-150: 100: 0.1-5; The volume/mass of mixed solvent and divalent cobalt (ml/g) is than being 1: 0.01-0.016;
(b) heating steps: the prepared solution of step (a) is heated to 100-200 ℃, reaction time 1-24 hour;
(c) drying steps: with the cooling of the resulting sediment of (b) heating steps, filter, washing is to neutral, 60 ℃ of vacuumizes are to constant weight, get final product the yolk-shell material of atresia;
(d) calcining step: the product that (c) obtained places 200-500 ℃ of temperature lower calcination, and calcination time is 0.5-3 hour.
2. the preparation method of a kind of tri-iron tetroxide according to claim 1-cobaltosic oxide porous magnetic composite is characterized in that: the pH value of the solution in the step (a) is 5-7.
3. the preparation method of a kind of tri-iron tetroxide according to claim 1-cobaltosic oxide porous magnetic composite is characterized in that: water, ethanol, butanols are 100-130 by volume in the step (a): 100: 0.1-3.
4. the preparation method of a kind of tri-iron tetroxide according to claim 1-cobaltosic oxide porous magnetic composite is characterized in that: divalent cobalt and divalent iron salt mol ratio are 6-4 in the step (a): 2.
5. the preparation method of a kind of tri-iron tetroxide according to claim 1-cobaltosic oxide porous magnetic composite is characterized in that: the reaction temperature in the step (b) is 120-160 ℃, and the reaction time is 4-12 hour.
6. the described tri-iron tetroxide of claim 1-cobaltosic oxide porous magnetic composite is in the application on lithium ion battery, fuel cell.
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Cited By (3)
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| CN103214038A (en) * | 2013-04-08 | 2013-07-24 | 严百坤 | Preparation method for carbon-coated ferroferric oxide-cobaltosic oxide composite negative electrode material |
| CN105417589A (en) * | 2015-09-21 | 2016-03-23 | 华南师范大学 | Preparation method for shuttle-shaped ferroferric oxide-cobaltosic oxide self-assembly structure compound |
| CN112588256A (en) * | 2021-01-28 | 2021-04-02 | 华东交通大学 | Magnetic nano bimetal oxide adsorbent and application thereof |
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Cited By (4)
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| CN103214038A (en) * | 2013-04-08 | 2013-07-24 | 严百坤 | Preparation method for carbon-coated ferroferric oxide-cobaltosic oxide composite negative electrode material |
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| CN105417589A (en) * | 2015-09-21 | 2016-03-23 | 华南师范大学 | Preparation method for shuttle-shaped ferroferric oxide-cobaltosic oxide self-assembly structure compound |
| CN112588256A (en) * | 2021-01-28 | 2021-04-02 | 华东交通大学 | Magnetic nano bimetal oxide adsorbent and application thereof |
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