CN109841819B - Iron selenide/carbon composite material and application thereof - Google Patents
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Abstract
The invention relates to an iron selenide/carbon composite material and application thereof, wherein the iron selenide/carbon composite material contains iron selenide and carbon, the iron selenide/carbon composite material is in a uniform lamellar structure, and porous structures are uniformly distributed in the lamellar structure.
Description
Technical Field
The invention belongs to the technical field of ceramics, and particularly relates to an iron selenide/carbon composite functional ceramic and a preparation method for preparing the iron selenide/carbon composite functional ceramic by in-situ coating of a precursor.
Background
At present, a lithium ion battery is a high-energy battery system with the best development prospect, but with the aggravation of the dependence of industries such as digital and traffic digital on the lithium ion battery, the lithium battery faces the problem of serious resource shortage. Research and development of sodium ion batteries can alleviate, to some extent, the limited development of batteries due to shortage of lithium resources. If an electrode material with excellent battery performance, safety and stability is developed on the basis, the sodium ion battery has greater market competitive advantage than the lithium ion battery. Metal selenides as metalsOne class of sulfides, the selenium atom being larger in diameter and more metallic than the sulfur atom, allows metal selenides to have greater interlayer spacing and higher electrical conductivity than metal sulfides. FeSe iron diselenide2Has a narrow energy gap (Eg. 1.0eV), a high conductivity, and FeS2The crystal is similar and has the potential of being applied to a sodium ion battery. Other iron selenide compounds also have similar electrochemical sodium storage activity, so the research of metal selenides is continuously needed to be explored and researched.
Disclosure of Invention
In view of the above problems, the present invention aims to provide an iron selenide/carbon composite material with excellent electrochemical properties, and a preparation method and applications thereof.
In a first aspect, the present invention provides an iron selenide/carbon composite material, which contains iron selenide and carbon, wherein the iron selenide/carbon composite material has a uniform lamellar structure, and pore structures are uniformly distributed in the lamellar structure.
According to the invention, the iron selenide/carbon composite material is in a uniform lamellar structure, and the lamellar structure is uniformly distributed with the porous structures, the lamellar porous structure can effectively promote the electrolyte to diffuse to the surface of the material, so that the charge transfer speed is accelerated, and simultaneously, the migration path of charges to active components is remarkably shortened, the charges can be rapidly migrated to realize electrochemical reaction. Therefore, the material has higher theoretical capacity, good rate capability and better cycle stability in the charge-discharge process.
Preferably, the iron selenide is coated by carbon to form a spherical shape and grows between the lamellar structures at the same time, so that an in-situ carbon-coated iron selenide composite ceramic material structure is formed.
Preferably, in the iron selenide/carbon composite material, the mass ratio of iron selenide to carbon is 7: 1-3: 1.
preferably, the size of the sheet in the sheet-like structure is 200 nm-3 μm, and the thickness is 10-50 nm.
Preferably, the pore diameter of the porous structure is 5-30 nm.
Preferably, the iron selenide is FeSe or FeSe2And Fe7Se8One or a mixture of several of (a) and (b).
In a second aspect, the present invention provides a method for preparing the iron selenide/carbon composite material, including the following steps:
(1) adding a dopamine source and an iron source into a solvent which dissolves the dopamine source and does not dissolve the iron source, uniformly mixing, and removing the solvent to obtain powder A;
(2) pyrolyzing the powder A at 400-700 ℃ under vacuum to obtain powder B;
(3) and mixing the powder B with selenium powder, and pyrolyzing at 600-900 ℃ to obtain the iron selenide/carbon composite material.
According to the invention, a liquid phase coating method and a high-temperature solid phase method are utilized, a precursor with a lamellar porous structure morphology is prepared from a dopamine source and an iron source through a high-temperature solid phase reaction in a short time at a high temperature, and then the lamellar porous structure iron selenium compound/carbon composite material with a uniform morphology is obtained through solid phase selenization treatment, so that the electrical conductivity of the material is enhanced. The preparation method is simple to operate, low in cost, safe and nontoxic, and is expected to realize industrial production.
Preferably, the dopamine source is selected from at least one of dopamine and dopamine salt, preferably, the dopamine salt is dopamine hydrochloride.
Preferably, the iron source is an organic acid salt of iron, preferably at least one selected from iron oxalate, iron acetate, ferric ammonium oxalate and ferric ammonium citrate.
Preferably, in the step (1), the mass ratio of the dopamine source to the iron source is 1:3 to 1: 10.
Preferably, the solvent is selected from at least one of isopropanol, n-butanol, n-octanol, and n-hexanol.
Preferably, the uniform mixing is performed by stirring at a rotation speed of 100 to 800r/min for 8 to 24 hours, preferably 18 to 24 hours.
Preferably, in the step (2), the vacuum degree is-0.1 to-0.05 MPa, the temperature is raised to 400 to 700 ℃ at the temperature rise rate of 5 to 15 ℃/min, and the heat preservation time is 0.01 to 2 hours, preferably 0.1 to 2 hours.
Preferably, in the step (3), the mass ratio of the powder B to the selenium powder is 1: 2-1: 5.
preferably, in the step (3), the vacuum degree is-0.1 to-0.05 MPa, the temperature is raised to 600 to 900 ℃ at the temperature rise rate of 5 to 15 ℃/min, and the heat preservation time is 0.01 to 2 hours, preferably 0.1 to 2 hours.
Preferably, in step (3), after the heat preservation is finished, an inert gas is added to make the pressure of the reaction system consistent with the air pressure.
In a third aspect, the present invention provides a sodium ion battery cathode comprising any one of the iron selenide/carbon composites described above.
In a fourth aspect, the present invention provides a sodium ion battery comprising the sodium ion battery negative electrode.
The sodium ion battery has the advantages of low cost, higher theoretical capacity in the charging and discharging process, good rate capability and better cycling stability.
In the synthesis technology, the composite ceramic structure of the carbon-coated iron selenide is realized by a precursor in-situ synthesis method, multi-step operation is not needed, the synthesis technology is simple, the synthesis cost is low, and the preparation process is easy to regulate and control. The carbon and the iron selenide form an in-situ composite structure in the product obtained by in-situ synthesis, the material is tightly combined, the electrical property and the mechanical strength of the product are promoted, and an important structural basis is provided for later application of the product.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of example 1 of the present invention.
FIG. 2 is a Scanning Electron Microscope (SEM) image of example 1 of the present invention.
FIG. 3 is a graph showing electrochemical properties of example 1 of the present invention.
FIG. 4 is a Scanning Electron Microscope (SEM) image of example 2 of the invention.
FIG. 5 is an electrochemical performance chart of the electrochemical performance charts of examples 3 and 4 of the present invention.
Detailed Description
The present invention is further described below in conjunction with the following embodiments and the accompanying drawings, it being understood that the drawings and the following embodiments are illustrative of the invention only and are not limiting thereof.
Disclosed herein is an iron selenide/carbon composite. Fig. 2 shows an SEM photograph of an iron selenide/carbon composite according to an embodiment of the present invention. As shown in fig. 2, the iron selenide/carbon composite material has a uniform lamellar/spherical composite growth structure, and pore structures are uniformly distributed in the lamellar structure. The iron selenide/carbon composite material contains iron selenide and carbon, wherein the iron selenide is dispersed on the surface of a lamellar porous carbon structure in small particles. Compared with a sheet-shaped iron selenide structure, the structure provided by the invention can effectively improve the conductivity and the charging and discharging structural stability of the material, and further improve the sodium storage performance of the material.
The size of the sheet in the sheet layered structure can be 200 nm-3 μm, and the thickness can be 10-50 nm. With such dimensions, the structural stability of the material can be ensured while maintaining a short charge diffusion path to realize a high-speed electrochemical reaction process. The distance between the lamellae in the lamellar structure can be 10-200 nm.
The pore diameter in the porous structure can be 5-30 nm. Under the size, the contact between the material and the electrolyte can be further improved, the path of charge migration is shortened, the time of charge migration is shortened, and the electrochemical reaction process is accelerated.
The ratio of iron selenide to carbon in the iron selenide/carbon composite material is adjustable, for example, the mass ratio of the iron selenide to the carbon can be 10: 1-3: 1. under the proportion, the sodium storage performance of the iron selenide can be effectively shown, and the two structures are mutually promoted to synergistically improve the overall performance of the composite structure by means of the supporting effect of the porous sheet carbon structure.
The chemical composition of the iron selenide may be Fe7Se8、FeSe、FeSe2。Fe7Se8Can simultaneously embody the sodium storage performance of the metallicity and the selenide of the material.
The iron selenide/carbon composite material disclosed by the invention can be prepared by a precursor in-situ coating method. Hereinafter, the production method thereof will be specifically described as an example.
Firstly, adding a dopamine source and an iron source into a solvent which is soluble to the dopamine source and insoluble to the iron source, uniformly mixing, and removing the solvent to obtain powder A. The effective coating of the dopamine on the surface of the iron source is realized through the process, the in-situ uniform coating of the dopamine on the iron source can be realized only through the process, and compared with direct mixing, the coating effect is more uniform.
The dopamine source may be selected from at least one of dopamine and dopamine salts. Preferably, dopamine salts are used, more preferably dopamine hydrochloride.
The iron source must be an organic acid salt of iron while satisfying the characteristic of not being easily soluble in an organic solvent. The organic acid salt of iron can be at least one selected from iron oxalate, iron acetate, ferric ammonium oxalate and ferric ammonium citrate.
The mass ratio of the dopamine source to the iron source can be 1: 3-1: 10. The full coating of the dopamine raw material on the iron source can be ensured in the mass ratio, and the problem of capacity reduction of the composite structure caused by excessive carbon content in the later period due to excessive coating can be solved.
The solvent is not particularly limited as long as the dopamine source is dissolved and the dopamine source is insoluble to the iron source, and under the condition, the dopamine source can be coated on the surface of the iron source and the iron source is not changed, so that a structural basis is provided for the in-situ synthesis of the iron selenide in the later stage. The solvent may be, for example, at least one of isopropyl alcohol, cyclohexanol, and n-octyl alcohol.
After the dopamine source and the iron source are added into a solvent which can dissolve the dopamine source and can not dissolve the iron source, the dopamine source is dissolved, and the iron source is kept insoluble, so that suspension is obtained. And stirring the suspension for a period of time, and removing the solvent to obtain powder A. The stirring condition is, for example, stirring for 8-24 h, preferably 18-24 h, at a rotating speed of 100-800 r/min under the stirrer. The solvent may be removed by suction filtration and then evaporated to dryness. In the powder A, an iron source is coated by a dopamine source.
Then, the powder a is pyrolyzed. The pyrolysis can be carried out under vacuum, for example, at a vacuum of-0.1 to-0.05 MPa. The apparatus used may be, for example, a vacuum tube furnace. The vacuum tube furnace can work under various atmospheres and vacuum. The temperature rising rate of the reaction can be effectively controlled under the vacuum condition. The pyrolysis temperature can be 400-700 ℃. If the temperature is too low, the carbonization degree of the dopamine is insufficient, and the graphitization degree is low; if the temperature is too high, the carbonization reaction violently causes the structural destruction of the carbon layer. In some embodiments, the temperature can be increased from room temperature to the pyrolysis temperature at a temperature increase rate of 5-15 ℃/min. The heating rate can ensure that the decomposition reaction of the dopamine and the iron source is carried out simultaneously so as to meet the requirement of the in-situ selenization reaction. The pyrolysis time can be 0.1-2 hours.
The powder A is easy to generate a lamellar structure in the heat treatment process, and a plurality of porous structures are uniformly distributed in the lamellar structure. Specifically, hydroxyl and amino of the dopamine source are subjected to dehydration condensation and the dopamine source forms lamellar poly-dopamine through self-polymerization, the lamellar poly-dopamine is further carbonized into a nitrogen-doped carbon lamellar structure in the high-temperature pyrolysis process, and meanwhile, decomposed gas escapes to bring a porous structure. And the iron source surface is coated with the dopamine in a relatively tight manner, and then the dopamine is coated on the iron source surface in situ to form a spherical carbon-coated iron oxide structure. The carbon coated on the surface and the lamellar carbon are not separated in the pyrolysis process, are fully bonded through early-stage polymerization, and still keep a continuous structure in the carbonization and pyrolysis process, so that the shapes of the porous lamellar carbon and the spherical carbon coated iron oxide are formed. And pyrolyzing the powder A to obtain powder B. The powder B contains Fe3O4the/C composite is of a uniform lamellar structure, and pore structures are uniformly distributed in the lamellar structure.
And then, mixing the powder B with selenium powder for reaction to obtain the iron selenide/carbon composite material.
After the powder B reacts with the selenium powder, the iron oxide is converted into iron selenide, and the microscopic morphology of the powder B basically keeps unchanged, namely the iron selenide/carbon composite material is also in a uniform lamellar structure, and pore structures are uniformly distributed in the lamellar structure.
The mass ratio of the powder B to the selenium powder can be 1: 2-1: 5. by adopting the mass ratio, the selenization of the iron oxide can be effectively realized without residual selenium powder.
The reaction of the powder B and the selenium powder can be carried out under vacuum condition, and the vacuum degree is, for example, -0.1 to-0.05 MPa. The apparatus used may be, for example, a vacuum tube furnace. The vacuum tube furnace can work under various atmospheres and vacuum. The temperature rising rate of the reaction can be effectively controlled under the vacuum condition. The reaction temperature can be 600-900 ℃. If the temperature is too low, the selenium cannot be fully selenized, and meanwhile, the residual selenium causes performance damage in the product; if the temperature is too high, the original structure is broken. In some embodiments, the temperature can be increased from room temperature to the reaction temperature at a temperature increase rate of 5-15 ℃/min. By adopting the heating rate, the situation that a sample is subjected to a selenylation reaction at a stable reaction rate, a side reaction is generated due to an excessively slow rate, effective selenylation cannot be realized due to selenium volatilization, and the phenomenon that the selenium powder is not timely diffused after being liquefied to react due to an excessively fast heating rate can be guaranteed, so that the uniformity of a product is influenced. The reaction time may be 1 hour. After the heat preservation is finished, inert gas such as argon can be supplemented to enable the pressure in the tube to be consistent with the air pressure, so that the air is not easy to suck backwards when the temperature in the furnace is reduced to influence the structure of the product.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1
According to the mass ratio of 3: 1, dispersing dopamine hydrochloride and ferric ammonium oxalate in an isopropanol solution, stirring and uniformly mixing for 24 hours on a magnetic stirrer at a rotating speed of 200r/min to dissolve the dopamine hydrochloride, keeping the ferric ammonium oxalate insoluble to obtain a light green suspension, and performing suction filtration and evaporation to dryness on the solution to obtain light green powder A1.
Heating the powder A1 to 600 ℃ for pyrolysis for 1h from room temperature at 10 ℃/min under the condition of vacuum degree (about-0.1 MPa of pressure gauge) in a low-temperature tube furnace to obtain iron oxide/carbon precursor powder B1.
Mixing the product B1 with selenium powder according to the mass ratio of 1: 2 weighing, grinding the product B1 and selenium powder, placing the ground product B1 and selenium powder in a crucible, placing the crucible in a tube furnace, vacuumizing (the pressure gauge is about-0.1 MPa), heating to 600 ℃ from room temperature at the heating rate of 5 ℃/min, preserving heat for 1h, and supplementing argon to ensure that the pressure in the tube is zero after the heat preservation is finished. And obtaining the layered carbon composite iron selenide composite material sodium ion battery cathode material.
The resultant product particles were subjected to a sample analysis using a Japanese science D/max2000 PCX-ray diffractometer, and the product was found to contain iron selenide (Fe)7Se8) See fig. 1. When the obtained product was observed with a scanning electron microscope of JSM-6700F type produced by japan electronics, as shown in fig. 2, it was found that the product was a lamellar structure having a uniform morphology, and many pore structures were uniformly distributed in the lamellar structure. As seen from the SEM image, the size of the sheet is 1 to 2 μm and the thickness is 20 to 50 nm. The pore diameter in the porous structure is 20-30 nm.
Example 2
According to the mass ratio of 5: 1, dispersing dopamine hydrochloride and ferric ammonium citrate in an isopropanol solution, stirring for 18 hours on a magnetic stirrer, uniformly mixing to obtain light green suspension, and drying the solution by distillation after suction filtration to obtain light green powder A2.
Heating the powder A2 in a low-temperature tube furnace at the vacuum degree of about-0.08 MPa from room temperature at 15 ℃/min to 700 ℃ for pyrolysis for 1h to obtain Fe3O4the/C precursor powder B2.
Mixing the product B2 with selenium powder according to the mass ratio of 1:3, grinding the product B and selenium powder, placing the ground product B and selenium powder in a crucible, placing the crucible in a tube furnace, vacuumizing (the pressure gauge is about-0.08 MPa), heating to 700 ℃ from room temperature at the heating rate of 7 ℃/min, preserving heat for 1h, and supplementing argon to ensure that the pressure in the tube is zero after the heat preservation is finished. And obtaining the layered carbon composite iron selenide composite material sodium ion battery cathode material.
The SEM image of the resultant product is shown in fig. 4, and it can be seen that the product is a lamellar structure with uniform morphology, and many pore structures are uniformly distributed in the lamellar structure. The size of the sheet is 2 to 3 μm and the thickness is 40 to 50 nm. The pore diameter in the porous structure is 30-50 nm.
Example 3
According to the mass ratio of 8: 1, dispersing ferric oxalate and dopamine hydrochloride in an isopropanol solution, stirring on a magnetic stirrer for 24 hours, uniformly mixing to obtain a light green suspension, and carrying out suction filtration on the solution and then evaporating to dryness to obtain light green powder A3.
Heating the powder A3 in a low-temperature tube furnace at the vacuum degree of about-0.06 MPa of a pressure gauge from room temperature at 7 ℃/min to 500 ℃ for pyrolysis for 1h to obtain Fe3O4the/C precursor powder B3.
Mixing the product B3 with selenium powder according to the mass ratio of 1: 5, grinding the product B3 and selenium powder, placing the ground product B3 and selenium powder in a crucible, placing the crucible in a tube furnace, vacuumizing (the pressure gauge is about-0.07 MPa), heating to 900 ℃ from room temperature at the heating rate of 15 ℃/min, preserving heat for 1h, and supplementing argon to ensure that the pressure in the tube is zero after the heat preservation is finished. And obtaining the layered carbon composite iron selenide composite material sodium ion battery cathode material.
The results of the structural and compositional testing of the resulting product were similar to those of example 1.
Example 4
According to the mass ratio of 10: 1, dispersing iron acetate and dopamine hydrochloride in an isopropanol solution, stirring for 20 hours on a magnetic stirrer, uniformly mixing to obtain light green suspension, and evaporating the solution to dryness to obtain light green powder A4.
Heating the powder A4 to 400 ℃ for pyrolysis for 1h from room temperature at 5 ℃/min under the condition of vacuum degree (about-0.06 MPa of pressure gauge) in a low-temperature tube furnace to obtain Fe3O4the/C precursor powder B4.
Mixing the product B4 with selenium powder according to the mass ratio of 1: 4, grinding the product B4 and selenium, placing the ground product B4 and selenium into a crucible, placing the crucible into a tube furnace, vacuumizing (about-0.06 MPa of a pressure gauge), heating to 800 ℃ from room temperature at the heating rate of 10 ℃/min, preserving heat for 1h, and supplementing argon to ensure that the pressure in the tube is zero after the heat preservation is finished. And obtaining the layered carbon composite iron selenide composite material sodium ion battery cathode material.
The results of the structural and compositional testing of the resulting product were similar to those of example 1.
Electrochemical performance test
The product obtained in each example is prepared into a button sodium-ion battery, and the specific packaging steps are as follows: mixing active powder, a conductive agent (super-p) and a binding agent (carboxymethyl cellulose CMC) according to a mass ratio of 8: 1:1, grinding uniformly to prepare slurry, uniformly coating the slurry on a copper foil by using a film coater, and drying for 12 hours in a vacuum drying oven at 80 ℃. Then assembling the electrode plates into a sodium ion half-cell, and carrying out constant-current charge-discharge test on the cell by adopting a Xinwei electrochemical workstation, wherein the test voltage is 0.01-3.0V, and the test current density is 0.1-10A g-1The test results of example 1 are shown in fig. 3, the test results of example 3 are shown in fig. 5, and the test results of example 4 are shown in fig. 5. From the test results, it can be seen that the samples of the different examples all exhibit excellent rate capability.
Claims (4)
1. The iron selenide/carbon composite material is characterized by comprising lamellar carbon layer structures which are distributed at a certain interval and connected among different areas and spherical morphological structures which grow among the lamellar carbon layer structures and are formed by carbon-coated iron selenide;
wherein, pore structures with the aperture of 5-30 nm are uniformly distributed on the lamellar carbon layer structure; the size of the sheet in the sheet-shaped carbon layer structure is 200 nm-3 mu m, and the thickness is 10-50 nm; the distance between the lamella is 10-200 nm;
the iron selenide/carbon composite material contains iron selenide and carbon, and the mass ratio of the iron selenide to the carbon is 7: 1-3: 1.
2. the iron selenide/carbon composite according to claim 1, wherein the iron selenide is FeSe, FeSe2And Fe7Se8One or a mixture of several of (a) and (b).
3. A sodium ion battery negative electrode comprising the iron selenide/carbon composite material according to claim 1 or 2.
4. A sodium ion battery comprising the negative electrode for a sodium ion battery according to claim 3.
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