CN107123807B - FeS having a three-dimensional structure2Nano material, preparation method and application thereof - Google Patents

FeS having a three-dimensional structure2Nano material, preparation method and application thereof Download PDF

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CN107123807B
CN107123807B CN201610104100.8A CN201610104100A CN107123807B CN 107123807 B CN107123807 B CN 107123807B CN 201610104100 A CN201610104100 A CN 201610104100A CN 107123807 B CN107123807 B CN 107123807B
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nanochain
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CN107123807A (en
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张跃钢
潘争辉
杨洁
刘美男
侯远
叶方敏
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Suzhou Institute of Nano Tech and Nano Bionics of CAS
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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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • 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
    • 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
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
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    • Y02E60/10—Energy storage using batteries

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Abstract

The invention discloses a FeS with a three-dimensional structure2Nanomaterial being FeS having a three-dimensional porous structure2Nano-chain or FeS with three-dimensional structure2Nanometer petal. The invention also provides a method for preparing the FeS2Methods for nanomaterials, for example: the FeS is prepared by a magnetic field-assisted ultrasonic spray pyrolysis method2A nanochain; or the FeS is prepared by a hydrothermal synthesis method2Nanometer petal. The FeS provided by the invention2The nano material has a three-dimensional structure, high electrochemical activity, excellent electrical performance and high mechanical strength, and simultaneously has the advantages of phase purity, high crystallinity, no impurity and the like.

Description

FeS having a three-dimensional structure2Nano material, preparation method and application thereof
Technical Field
The invention belongs to the technical field of materials, and particularly relates to an electrode material, a preparation method thereof, an electrode and a battery.
Background
Ferrous disulfide (FeS)2) Due to its high theoretical specific capacity (894mAh g)-1) Safe and nontoxic, stable in structure, low in price and abundant in reserves in nature, and is more and more concerned by the academic and industrial fields. But due to FeS2The drastic volume change and some irreversible side reactions during the charge and discharge process lead to rapid capacity decay and short cycle life. It is well known that the morphology of the electrode material has an important influence on its electrochemical performance, and thus it is necessary to design FeS with a unique geometry2The influence caused by volume expansion is relieved, and the electrochemical energy storage performance is improved. Although researchers have now controlled the synthesis of FeS of various morphologies2E.g., one-dimensional nanostructured nanowires, nanoplates, nanorods, etc., but based on Li/FeS of these morphologies2The highest specific capacity achieved by the battery (maintained at 291mAh/g after 500 cycles) is still far below the requirements for commercial applications. And the existing FeS with one-dimensional nano structure2The preparation processes of nano-wires, nano-sheets and the like are complex, the cost is high, and the prepared FeS2Contains other impurities such as sulfur and the like, thereby causing unstable performance and finally failing to meet the requirements of practical application.
Disclosure of Invention
The invention mainly aims to provide FeS with a three-dimensional structure2The nanometer material, its preparation process and application are provided to overcome the demerits in available technology.
In order to achieve the purpose, the invention provides the following technical scheme:
the embodiment of the invention provides a FeS with a three-dimensional structure2Nanomaterial being FeS having a three-dimensional porous structure2Nano-chain or FeS with three-dimensional structure2Nanometer petal.
Further, the FeS2The nano material is FeS with a three-dimensional porous structure2Nanochain ofThe size is 30-50 nm, the aperture of the contained hole is 20-300 nm, the porosity is 10-30%, and the specific surface area is 30-40 m2g-1And said FeS2FeS in nano material2The content of (A) is more than 95%.
Further, the FeS2The nano material is FeS with a three-dimensional structure2The nano petals have a size of 5-20 μm and a specific surface area of 5-10 m2g-1And said FeS2FeS in nano material2The content of (A) is more than 95%.
The embodiment of the invention also provides a method for manufacturing the FeS with the three-dimensional structure2A method of preparing a nanomaterial.
For example, the manufacturing method includes: the FeS with the three-dimensional porous structure is prepared by a magnetic field-assisted ultrasonic spray pyrolysis method2And (4) nano-chains.
For another example, the manufacturing method includes: the FeS with the three-dimensional structure is prepared by a hydrothermal synthesis method2Nanometer petal.
The embodiment of the invention also provides the FeS with the three-dimensional structure2The application of the nano material, such as the application in preparing electrode materials, electrodes and batteries.
Compared with the prior art, the invention has the advantages that: provided FeS2The nano material has a three-dimensional structure, high electrochemical activity, excellent electrical performance and high mechanical strength, and simultaneously has the advantages of phase purity, high crystallinity, no impurity and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 a-FIG. 11b are respectively FeS with a three-dimensional porous structure in example 1 of the present invention2SEM and TEM images of nanochains;
FIGS. 2a to 2d are FeS in example 2 of the present invention, respectively2XRD, raman and XPS patterns of nanochains;
FIGS. 3a-3b are FeS in example 3 of the present invention2SEM pictures of the nano petals at different magnifications;
FIGS. 4 a-4 b are FeS in example 4 of the present invention2XRD pattern and Raman pattern of the nano petals;
FIGS. 5a to 5d are FeS-based data in example 5 of the present invention2Electrochemical performance test pattern of nanochain battery.
Detailed Description
One aspect of the embodiments of the present invention provides a FeS having a three-dimensional structure2Nanomaterial being FeS having a three-dimensional porous structure2Nano-chain or FeS with three-dimensional structure2Nanometer petal.
Further, the FeS2The nano material is FeS with a three-dimensional porous structure2A nanochain having a size of 30 to 50nm, a pore diameter of pores of 20 to 300nm, a porosity of 10 to 30%, and a specific surface area of 30 to 40m2g-1And said FeS2FeS in nano material2The content of (A) is more than 95%.
Further, the FeS2The nano material is FeS with a three-dimensional structure2The nano petals have a size of 5-20 μm and a specific surface area of 5-10 m2g-1And said FeS2FeS in nano material2The content of (A) is more than 95%.
An aspect of the embodiments of the present invention provides a method for preparing the FeS having a three-dimensional structure2A method of nanomaterials, comprising:
dissolving an iron source in a volatile organic solvent to form a precursor solution,
spraying the precursor solution onto a carrier with the surface temperature of 50-180 ℃ in an ultrasonic spraying manner to form Fe nano-particles,
carrying out heat treatment on the Fe nanoparticles at 200-600 ℃ for more than 10min in air atmosphere, and then cooling to form Fe with a three-dimensional porous structure2O3The nano-chain is formed by the nano-chain,
and, adding said Fe2O3Performing constant-temperature heat treatment on the nanochain at 100-400 ℃ for more than 10min in hydrogen sulfide atmosphere, and then cooling to form FeS with a three-dimensional porous structure2And (4) nano-chains.
Preferably, the ultrasonic spraying conditions adopted in the preparation method comprise: the ultrasonic spraying frequency is 1.5-2.5 MHz, the caliber of the nozzle is 0.3-1.4 mm, the included angle between the nozzle and the horizontal plane is 60-120 degrees, the applied direct current voltage is 7-30 kV, the curing distance is 5-10 cm, the temperature is 0-35 ℃, the relative humidity is 10-70%, and the flow rate of carrier gas is 10-1000 sccm. Preferably, the preparation method comprises the following steps: placing the Fe nano particles in an air atmosphere, heating to 200-600 ℃ at a heating rate of 1-10 ℃/min, carrying out constant-temperature heat treatment for 10-50 mim, and then naturally cooling to room temperature to form Fe with a three-dimensional porous structure2O3And (4) nano-chains.
Preferably, the preparation method comprises the following steps: subjecting said Fe to2O3Placing the nanochain in hydrogen sulfide atmosphere, heating to 100-400 ℃ at a heating rate of 1-10 ℃/min, carrying out constant-temperature heat treatment for 10-50 mim, and then naturally cooling to room temperature to form FeS with a three-dimensional porous structure2And (4) nano-chains.
Preferably, the concentration of the iron source contained in the precursor solution is 0.1-0.5M, wherein the adopted iron source comprises carbonyl iron or iron acetate, and the adopted organic solvent comprises acetone, but is not limited thereto.
In a more specific embodiment, a three-dimensional porous structure of FeS is provided2The preparation method of the nano-chain comprises the following steps:
mixing Fe (CO)5(0.05-0.3M) and acetone according to the volume ratio of 1:35, stirring for 10 minutes to 1 hour under magnetic stirring (50-2000 revolutions) to form a yellow transparent solution; then adding the prepared precursor solution into 2 spray barrels for ultrasonic sprayingAtomizing and spraying. The ultrasonic spraying frequency is 1.7MHz, the caliber of a nozzle is 0.3-1.4 mm, the included angle between the nozzle and the horizontal plane is adjusted to be 90 degrees, 7-30 kV direct current voltage is applied, the curing distance is 5-10 cm, the temperature is 0-35 ℃, the relative humidity is 10% -70%, and Fe (CO) generated by ultrasonic spraying5The small droplets with the diameter of about 5 mu m are taken out by compressed air (the gas flow rate is 10-1000sccm), and the droplets are sprayed on a hot plate with the surface temperature of 50-180 ℃ to generate a large amount of carbon monoxide gas and Fe nanoparticles. And then putting the Fe nano particles prepared by ultrasonic spraying into a tubular furnace to carry out heat treatment in the atmosphere of air (the gas flow rate is 10-1000sccm), wherein the reaction temperature is 200-600 ℃ (the temperature rise rate is 1-10 ℃/min), the reaction time is 10-50 minutes, and after the reaction is finished, naturally cooling to room temperature in the atmosphere of air to obtain Fe with a three-dimensional porous structure2O3And (4) nano-chains. And finally, introducing hydrogen sulfide gas (the gas flow rate is 10-1000sccm), keeping the temperature of 100-400 ℃ (the temperature rise rate is 1-10 ℃/min) for 10-50 minutes under the hydrogen sulfide atmosphere, and naturally cooling the tubular furnace to room temperature after the reaction is finished to obtain the FeS with the three-dimensional porous structure2And (4) nano-chains.
An aspect of the embodiments of the present invention provides another method for preparing the FeS having a three-dimensional structure2A method of nanomaterials, comprising:
placing a mixed solution formed by uniformly mixing an iron source, a sulfur source and ethanolamine in a closed container, reacting for more than 2 hours at 100-300 ℃, naturally cooling to room temperature, and filtering out a gel sample;
freezing the gelatinous sample at-5 to-10 ℃ for 2 to 24 hours, and then freeze-drying to obtain a freeze-dried sample;
preserving the temperature of the freeze-dried sample at 50-200 ℃ for 24-48 h in a vacuum environment to obtain FeS with a three-dimensional structure2Nanometer petal.
Preferably, the mixed solution comprises 5-40 parts by weight of iron source, 70-95 parts by weight of sulfur source and 60-95 parts by weight of ethanolamine.
Wherein the iron source includes a soluble iron salt, such as, but not limited to, ferric sulfate or ferrous chloride.
Wherein the sulfur source includes elemental sulfur, but is not limited thereto.
Preferably, the preparation method comprises the following steps: and (3) placing the mixed solution in a closed container, heating to 100-300 ℃ at a heating rate of 1-10 ℃/min, carrying out heat preservation reaction for 2-10 h, then naturally cooling to room temperature, and filtering out the gel sample.
In a more specific embodiment, a three-dimensional FeS structure is provided2The preparation method of the nano petals comprises the following steps:
FeCl is added2(5-40 parts by weight) and S (70-95 parts by weight) are dissolved in ethanolamine (60-95 parts by weight), and the mixture is stirred for 10 minutes to 24 hours under magnetic stirring (50-2000 revolutions) to form a uniform brown solution. Firstly, putting the brown solution into a polytetrafluoroethylene inner container; then placing the inner container into a reaction kettle and screwing down the reaction kettle; and finally, placing the reaction kettle in a program temperature control box type furnace, keeping the temperature at 100-300 ℃, reacting for 2-10 h, and raising the temperature at the rate of 1-10 ℃/min. After the reaction is finished and the reaction kettle is naturally cooled to room temperature, carrying out suction filtration by using an organic filter membrane (the diameter of the filter membrane is about 13mm, and the aperture is about 0.22um) to obtain a gel sample; repeatedly washing the sample by using ethanol and deionized water, freezing the cleaned sample in a refrigerating chamber at (-5 to-10 ℃) for 2 to 24 hours, and then putting the sample in a freeze dryer for freeze drying (12 to 48 hours); finally, the dried sample is placed in a vacuum drying oven to be kept at the temperature of 50-200 ℃ for 24-48 h, and the FeS with the three-dimensional structure is obtained2Nanometer petal.
The embodiment of the invention also provides the FeS with the three-dimensional structure2Use of nanomaterials.
For example, there is provided an electrode material comprising the FeS having a three-dimensional structure2And (3) nano materials.
For example, there is provided an electrode comprising the FeS having a three-dimensional structure2And (3) nano materials.
For example, there is provided a battery comprising the FeS having a three-dimensional structure2And (3) nano materials.
The invention provides a medicine with threeFeS of dimensional porous structure2Nanochain and FeS with three-dimensional structure2The nano petals can accelerate the transmission speed of ions and electrons due to the unique geometric structure of the nano petals so as to meet the requirement of quick charge and discharge of the battery, can also provide more active sites for electrochemical reaction to increase the specific capacity of the battery, and meanwhile, the three-dimensional structure also has excellent mechanical strength, so that FeS can be effectively relieved2The influence of the violent volume change in the charging and discharging process, thereby prolonging the cycle life of the battery.
In addition, the FeS is prepared and obtained by the magnetic field assisted ultrasonic spray pyrolysis and hydrothermal synthesis method respectively2Nanochains and the FeS2The nano petal has simple process, low cost, high yield and suitability for large-scale production, and the obtained product is FeS2The nano crystal has the advantages of phase purity, high crystallinity, no impurity and the like.
Those skilled in the art can modify the process parameters appropriately to achieve the desired results with reference to the disclosure herein. It is expressly intended that all such similar substitutes and modifications which would be obvious to one skilled in the art are deemed to be included in the invention. While the invention has been described in terms of preferred embodiments, it will be apparent to those skilled in the art that the techniques of the invention can be implemented and applied by modifying or appropriately combining the applications described herein without departing from the spirit, scope and spirit of the invention.
For a further understanding of the present invention, reference will now be made in detail to the following examples. The reagents used in the following examples were all analytical grade.
Example 1: mixing Fe (CO)5(0.06M) and acetone in a volume ratio of 1:35, stirring for 20 minutes under magnetic stirring (100 revolutions) to form a yellow transparent solution; and then adding the prepared precursor solution into 2 spray barrels for ultrasonic spraying to carry out atomization spraying. Ultrasonic spray frequency is 1.7MHz, nozzle caliber is 0.4mm, an included angle between the nozzle and the horizontal plane is adjusted to 90 degrees, 8kV direct current voltage is applied, curing distance is 6cm, temperature is 5 ℃, relative humidity is 5 percent, and Fe (CO) generated by ultrasonic spray5The diameter of the small liquid drop is about5 μm, taken by compressed air (gas flow rate 30sccm), and the droplets were sprayed onto a hot plate having a surface temperature of 60 c, to generate a large amount of carbon monoxide gas and Fe nanoparticles. Putting the Fe nano-particles prepared by ultrasonic spraying into a tubular furnace to carry out heat treatment in the atmosphere of air (the gas flow rate is 50sccm), wherein the reaction temperature is 250 ℃ (the heating rate is 2 ℃/min) and the time is 15 minutes, and naturally cooling to room temperature in the atmosphere of air after the reaction is finished to obtain Fe with a three-dimensional porous structure2O3And (4) nano-chains. Finally, introducing hydrogen sulfide gas (the gas flow rate is 20sccm), keeping the temperature of the tubular furnace at 150 ℃ (the temperature rise rate is 2 ℃/min) for 15 minutes under the hydrogen sulfide atmosphere, and naturally cooling the tubular furnace to room temperature after the reaction is finished to obtain the FeS with the three-dimensional porous structure2The nano-chain, SEM image and TEM image are shown in FIG. 1a and FIG. 1 b.
Example 2: mixing Fe (CO)5(0.25M) and acetone at a volume ratio of 1:35, stirring for 50 minutes under magnetic stirring (1800 revolutions) to form a yellow transparent solution; and then adding the prepared precursor solution into 2 spray barrels for ultrasonic spraying to carry out atomization spraying. Ultrasonic spray frequency is 1.7MHz, nozzle caliber is 1.2mm, included angle between nozzle and horizontal plane is adjusted to 90 degrees, 25kV direct current voltage is applied, curing distance is 8cm, temperature is 30 ℃, relative humidity is 60 percent, and Fe (CO) generated by ultrasonic spray5The droplets, which had a diameter of about 5 μm and were carried out by compressed air (gas flow rate of 800sccm), were sprayed onto a hot plate having a surface temperature of 160 ℃ to generate a large amount of carbon monoxide gas and Fe nanoparticles. Putting the Fe nano-particles prepared by ultrasonic spraying into a tubular furnace to carry out heat treatment in the atmosphere of air (gas flow rate of 800sccm), wherein the reaction temperature is 500 ℃ (the heating rate is 8 ℃/min), the reaction time is 40 minutes, and after the reaction is finished, the Fe nano-particles are naturally cooled to room temperature in the atmosphere of air to obtain Fe with a three-dimensional porous structure2O3And (4) nano-chains. Finally, introducing hydrogen sulfide gas (the gas flow rate is 10-1000sccm), keeping the temperature of 350 ℃ (the heating rate is 80 ℃/min) for 40 minutes under the hydrogen sulfide atmosphere, and naturally cooling the tubular furnace to room temperature after the reaction is finished to obtain the FeS with the three-dimensional porous structure2The XRD, Raman and XPS patterns of the nanochain are shown in figures 2 a-2 d.
Example 3: FeCl is added2(10 wt%) and S (35 wt%) were dissolved in ethanolamine (55 wt%) and stirred for 30 minutes with magnetic stirring (500 revolutions) to form a homogeneous tan solution. Firstly, putting the prepared solution into a 100ml polytetrafluoroethylene inner container; then placing the inner container into a reaction kettle and screwing down the reaction kettle; and finally, placing the reaction kettle in a program temperature control box type furnace, keeping the temperature at 150 ℃, reacting for 4h, and raising the temperature at the rate of 2 ℃/min. After the reaction is finished and the reaction kettle is naturally cooled to room temperature, carrying out suction filtration by using an organic filter membrane (the diameter of the filter membrane is 13mm, and the aperture is 0.22um) to obtain a gel sample; repeatedly washing the sample with ethanol and deionized water, freezing the cleaned sample in a refrigerating chamber (-6 deg.C) for 4h, and freeze-drying in a freeze-drying machine (15 h); finally, the dried sample is placed in a vacuum drying oven to be insulated for 26 hours at the temperature of 80 ℃ to obtain FeS with a three-dimensional structure2The nano petals are shown in SEM images of figures 3a-3 b.
Example 4: FeCl is added2(15 wt%) and S (45 wt%) were dissolved in ethanolamine (45 wt%) and stirred for 20 hours with magnetic stirring (1500 rpm) to form a homogeneous tan solution. Firstly, putting the prepared solution into a 100ml polytetrafluoroethylene inner container; then placing the inner container into a reaction kettle and screwing down the reaction kettle; and finally, placing the reaction kettle in a program temperature control box type furnace, keeping the temperature at 250 ℃, reacting for 8h, and raising the temperature at 8 ℃/min. After the reaction is finished and the reaction kettle is naturally cooled to room temperature, carrying out suction filtration by using an organic filter membrane (the diameter of the filter membrane is 13mm, and the aperture is 0.22um) to obtain a gel sample; repeatedly washing the sample with ethanol and deionized water, freezing the cleaned sample in a refrigerating chamber (-8 deg.C) for 20h, and freeze-drying in a freeze-drying machine (40 h); finally, putting the dried sample into a vacuum drying oven, and preserving the heat for 45 hours at 180 ℃ to obtain the FeS with the three-dimensional structure2The XRD pattern and Raman pattern of the nano petals are shown in figures 4 a-4 b.
Example 5: mixing Fe (CO)5(0.08M) and acetone at a volume ratio of 1:35, stirring for 30 minutes under magnetic stirring (200 revolutions) to form a yellow transparent solution; and then adding the prepared precursor solution into 2 spray barrels for ultrasonic spraying to carry out atomization spraying. The ultrasonic spray frequency is2.0MHz, the caliber of the nozzle is 0.6mm, the included angle between the nozzle and the horizontal plane is adjusted to be 100 degrees, 10kV direct current voltage is applied, the curing distance is 8cm, the temperature is 10 ℃, the relative humidity is 10 percent, and Fe (CO) generated by ultrasonic spraying is generated5The droplets, which had a diameter of about 5 μm and were carried out by compressed air (gas flow rate 50sccm), were sprayed onto a hot plate having a surface temperature of 80 ℃ to generate a large amount of carbon monoxide gas and Fe nanoparticles. Putting the Fe nano-particles prepared by ultrasonic spraying into a tubular furnace to carry out heat treatment in the atmosphere of air (the gas flow rate is 80sccm), wherein the reaction temperature is 300 ℃ (the heating rate is 5 ℃/min), the reaction time is 20 minutes, and after the reaction is finished, the Fe nano-particles are naturally cooled to room temperature in the atmosphere of air to obtain Fe with a three-dimensional porous structure2O3And (4) nano-chains. Finally, introducing hydrogen sulfide gas (the gas flow rate is 30sccm), keeping the temperature of the tubular furnace at 200 ℃ (the temperature rise rate is 5 ℃/min) for 20 minutes under the hydrogen sulfide atmosphere, and naturally cooling the tubular furnace to room temperature after the reaction is finished to obtain the FeS with the three-dimensional porous structure2The electrochemical performance of the nano-chain is shown in fig. 5 a-5 d.
Finally, it should also be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.

Claims (2)

1. FeS with three-dimensional structure2The preparation method of the nano material is characterized by comprising the following steps:
dissolving an iron source in a volatile organic solvent to form a precursor solution, and spraying the precursor solution onto a carrier with the surface temperature of 50-180 ℃ in an ultrasonic spraying manner to form Fe nanoparticles, wherein the adopted ultrasonic spraying conditions comprise: the ultrasonic spraying frequency is 1.5-2.5 MHz, the caliber of the nozzle is 0.3-1.4 mm, the included angle between the nozzle and the horizontal plane is 60-120 degrees, the applied direct current voltage is 7-30 kV, the curing distance is 5-10 cm, the temperature is 0-35 ℃, the relative humidity is 10-70%, and the flow rate of carrier gas is 10-1000 sccm;
placing the Fe nano particles in an air atmosphere, heating to 200-600 ℃ at a heating rate of 1-10 ℃/min, carrying out constant-temperature heat treatment for 10-50 mim, and then naturally cooling to room temperature to form Fe with a three-dimensional porous structure2O3A nanochain; and, adding said Fe2O3Placing the nanochain in hydrogen sulfide atmosphere, heating to 100-400 ℃ at a heating rate of 1-10 ℃/min, carrying out constant-temperature heat treatment for 10-50 mim, and then naturally cooling to room temperature to form FeS with a three-dimensional porous structure2A nanochain;
the FeS2The size of the nano chain is 30-50 nm, the aperture of the contained hole is 20-300 nm, the porosity is 10-30%, and the specific surface area is 30-40 m2g-1And said FeS2FeS in nano material2The content of (A) is more than 95%.
2. The method of claim 1, wherein: the concentration of an iron source contained in the precursor solution is 0.1-0.5M, wherein the adopted iron source is selected from carbonyl iron or iron acetate, and the adopted organic solvent comprises acetone.
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CN108899526A (en) * 2018-07-11 2018-11-27 中国科学院宁波材料技术与工程研究所 A kind of transient metal sulfide electrode material and preparation method thereof and solid lithium battery
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