CN110212188B - Metal iron oxide growing by taking carbon as framework support and preparation method and application thereof - Google Patents
Metal iron oxide growing by taking carbon as framework support and preparation method and application thereof Download PDFInfo
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- CN110212188B CN110212188B CN201910514580.9A CN201910514580A CN110212188B CN 110212188 B CN110212188 B CN 110212188B CN 201910514580 A CN201910514580 A CN 201910514580A CN 110212188 B CN110212188 B CN 110212188B
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- 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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Abstract
The invention discloses a metallic iron oxide growing by taking carbon as a framework support, a preparation method and application thereof, wherein the preparation method comprises the following steps: 1) according to the mass ratio of 1: 1 weighing ferric ammonium oxalate and bis (trifluoromethylbenzene) carbodiimide, mixing and fully grinding to obtain a green mixture A; 2) preparing two crucibles, one large crucible and one small crucible, sleeving the small crucible into the large crucible, filling the mixture A into the small crucible, and filling urea between the large crucible and the small crucible; 3) putting the sample in a low-temperature tubular furnace for pyrolysis to obtain metallic iron oxide which grows by taking carbon as a framework support; the flower-like ferric oxide cathode material with the carbon skeleton as the support is synthesized by using a simple solid phase method, and the flower-like structure can provide more channels, thereby being beneficial to the transmission of electrons and improving the conductivity of the material.
Description
Technical Field
The invention belongs to the technical field of electrochemistry, and particularly relates to a metallic iron oxide growing by using carbon as a framework support, and a preparation method and application thereof.
Background
Energy is the most important factor in the development process of human beings, and throughout the world, green energy replaces oil and natural gas with electric energy, and the key point for developing electric vehicles is the battery. Since lithium reserves are limited and cannot be used in large quantities in automobiles, sodium batteries have large reserves, and are the most promising battery materials, see document [1 ]]. The metal oxide is also a hot spot of a high-capacity cathode material of a sodium ion battery, mainly faces the problems of volume expansion and capacity attenuation, and can inhibit the volume expansion of the material and improve the conductivity of the material by compounding with carbon, preparing an electrochemical active/inactive composite material, synthesizing a special-morphology nano material and other methods so as to overcome the problems, thereby realizing the alloy materialHigh specific capacity, stable cycling and excellent rate capability, see document [2 ]]. Hematite (alpha-Fe) as the most stable iron oxide2O3) Due to its capacity of up to 1007mAh/g, its non-toxicity, low cost and abundance are of particular interest.
[1]Hui T,Hu G H,Hu G R,et al.Synthesis research of lithium ion battery cathode material LiFePO4/C[J].Journal of Chinese Inorganic Chemistry,2006,12(2):2159-2164.
[2]Veronica Palomares,Paula Serras,Irune Villaluenga,et al.Na-ion batteries,recent advances and present challenges to become low cost energy storage systems[J].Energy Environment Society,2012,5:5884-5901.
Disclosure of Invention
The invention aims to provide the metallic iron oxide growing by taking carbon as a framework support, and the preparation method and the application thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of metallic iron oxide growing by taking carbon as a framework support comprises the following steps:
1) according to the mass ratio of 1: 1 weighing ferric ammonium oxalate and bis (trifluoromethylbenzene) carbodiimide, mixing and fully grinding to obtain a green mixture A, and then weighing urea with the mass 2-7 times that of the ferric ammonium oxalate for later use;
2) preparing two crucibles, one large crucible and one small crucible, sleeving the small crucible into the large crucible, filling the mixture A into the small crucible, filling urea between the large crucible and the small crucible, and covering the large crucible and the small crucible with a cover;
3) and (3) putting the sample into a low-temperature tubular furnace for pyrolysis, raising the temperature to 500-700 ℃ at the heating rate of 5-15 ℃/min under the mixed atmosphere of 5% oxygen and 95% argon, and preserving the temperature for 1h to obtain the metal iron oxide which grows by taking carbon as a framework support.
A metallic iron oxide growing with carbon as skeleton support is used as the negative electrode material of Na-ion battery.
Compared with the prior art, the invention has the following beneficial effects:
the flower-like ferric oxide cathode material with the carbon skeleton as the support is synthesized by using a simple solid phase method, the flower-like structure can provide more channels, the transmission of electrons is facilitated, the conductivity of the material is improved, the flower-like structure can provide larger specific surface area, the exposure of a single crystal face of a metal oxide is facilitated, the large specific surface area has more reaction active sites, the de-intercalation of sodium ions in the charging and discharging process is facilitated, meanwhile, a certain structure is maintained in the process of embedding and de-intercalating the sodium ions, and the problems of poor cycle performance, low first coulomb efficiency and the like of the sodium ions due to the expansion effect of the volume are solved.
The raw materials adopted by the invention have the advantages of environmental friendliness, wide sources, low cost and the like, and the adopted preparation method is easy to operate.
Drawings
FIG. 1 is an XRD pattern of the product of example 1;
FIG. 2 is a scanning electron micrograph of a product prepared in example 2;
FIG. 3 is a graph of electrochemical rate performance of the product prepared in example 3 as a negative electrode material of a sodium-ion battery
Detailed Description
The present invention will be described in further detail with reference to the following examples, which are not intended to limit the invention thereto.
Example 1:
1) weighing 2g of ferric ammonium oxalate and 2g of bis (trifluoromethylbenzene) carbodiimide, placing the materials in a glass mortar, fully grinding the materials to obtain a green mixture A, and weighing 4g of urea for later use.
2) Preparing two crucibles, one large crucible and one small crucible, sleeving the small crucible into the large crucible, filling the mixture A into the small crucible, filling urea into two sides of the large crucible, and covering with a cover.
3) And (3) putting the sample into a low-temperature tube furnace for pyrolysis, raising the temperature to 700 ℃ at the heating rate of 5 ℃/min under the mixed atmosphere of 5% oxygen and 95% argon, and preserving the temperature for 1h to obtain a product C.
Fig. 1 preparation of flower-like Fe2O3XRD pattern of the composite electrode material, from which the success can be seenPreparation of Fe2O3A composite electrode material. The diffraction peak corresponds to the 33-0664 standard card.
Example 2:
1) weighing 2g of ferric ammonium oxalate and 2g of bis (trifluoromethylbenzene) carbodiimide, placing the materials in a glass mortar, fully grinding the materials to obtain a green mixture A, and weighing 10g of urea for later use.
2) Preparing two crucibles, one large crucible and one small crucible, sleeving the small crucible into the large crucible, filling the mixture A into the small crucible, filling urea into two sides of the large crucible, and covering with a cover.
3) And (3) putting the sample into a low-temperature tube furnace for pyrolysis, raising the temperature to 600 ℃ at a heating rate of 10 ℃/min under the mixed atmosphere of 5% oxygen and 95% argon, and preserving the temperature for 1h to obtain a product C.
When the sample is observed under a scanning electron microscope, as can be seen from fig. 2, the product is in a flower cluster shape and grows uniformly.
Example 3:
1) weighing 2g of ferric ammonium oxalate and 2g of bis (trifluoromethylbenzene) carbodiimide, placing the materials in a glass mortar, fully grinding the materials to obtain a green mixture A, and weighing 14g of urea for later use.
2) Preparing two crucibles, one large crucible and one small crucible, sleeving the small crucible into the large crucible, filling the mixture A into the small crucible, filling urea into two sides of the large crucible, and covering with a cover.
3) And (3) putting the sample into a low-temperature tube furnace for pyrolysis, raising the temperature to 500 ℃ at a heating rate of 15 ℃/min under the mixed atmosphere of 5% oxygen and 95% argon, and preserving the temperature for 1h to obtain a product C.
Preparing the obtained product into a button type sodium ion battery, and specifically packaging the button type sodium ion battery by the following steps: directly slicing the product, assembling into a sodium ion half cell, performing constant current charge and discharge test on the cell by adopting a Xinwei electrochemical workstation, wherein the test voltage is 0.01V-3.0V, assembling the obtained material into a button cell, testing the performance of the sodium ion cell cathode material, and obtaining the product with 350 mAh.g under the current density of 2A, wherein the electrochemical multiplying power performance diagram is shown in figure 3-1Capacity, from which Fe can be seen2O3The composite negative electrode material has outstanding rate performance.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting the same, and although the present invention is described in detail with reference to the above embodiments, those of ordinary skill in the art should understand that: modifications and equivalents may be made to the embodiments of the invention without departing from the spirit and scope of the invention, which is to be covered by the claims.
Claims (3)
1. A preparation method of metallic iron oxide growing by taking carbon as a framework support is characterized by comprising the following steps:
1) according to the mass ratio of 1: 1 weighing ferric ammonium oxalate and bis (trifluoromethylbenzene) carbodiimide, mixing and fully grinding to obtain a green mixture A, and then weighing urea with the mass 2-7 times that of the ferric ammonium oxalate for later use;
2) preparing two crucibles, one large crucible and one small crucible, sleeving the small crucible into the large crucible, filling the mixture A into the small crucible, filling urea between the large crucible and the small crucible, and covering the large crucible and the small crucible with a cover;
3) and (3) putting the sample into a low-temperature tubular furnace for pyrolysis, raising the temperature to 500-700 ℃ at the heating rate of 5-15 ℃/min under the mixed atmosphere of 5% oxygen and 95% argon, and preserving the temperature for 1h to obtain the metal iron oxide which grows by taking carbon as a framework support.
2. A carbon-based skeletal support grown metallic iron oxide prepared according to the method of claim 1.
3. Use of the carbon-supported grown iron oxide of claim 2 as a negative electrode material for sodium ion batteries.
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