CN110190264B - Spherical nitrogen-doped crystallized carbon-coated iron sulfide prepared under supercritical condition and preparation method and application thereof - Google Patents

Spherical nitrogen-doped crystallized carbon-coated iron sulfide prepared under supercritical condition and preparation method and application thereof Download PDF

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CN110190264B
CN110190264B CN201910514602.1A CN201910514602A CN110190264B CN 110190264 B CN110190264 B CN 110190264B CN 201910514602 A CN201910514602 A CN 201910514602A CN 110190264 B CN110190264 B CN 110190264B
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coated iron
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iron sulfide
nitrogen
crystallized carbon
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CN110190264A (en
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曹丽云
王蓉
黄剑锋
李嘉胤
许占位
郭鹏辉
郭玲
罗晓敏
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Shaanxi University of Science and Technology
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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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • 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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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
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    • 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 spherical nitrogen-doped crystallized carbon-coated iron sulfide prepared under a supercritical condition, and a preparation method and application thereof, wherein the preparation method comprises the following steps: 1) mixing and grinding ferric ammonium oxalate, diphenyl carbodiimide and a carbon source to obtain a mixture A; 2) carrying out heat treatment on the mixture A in a low-temperature tubular furnace argon-hydrogen atmosphere to obtain nitrogen-doped crystallized carbon-coated iron carbide as a product B; 3) placing the product B in an ice water bath for ultrasonic dispersion to obtain a product C; 4) mixing and grinding the product C and a sulfur source to obtain a mixture D, adding deionized water, stirring and fully mixing, putting into a homogeneous reactor, reacting, and then performing centrifugal filtration to obtain a product; the nitrogen-doped crystallized carbon-coated iron sulfide structure prepared by the invention can provide a high-conductivity path with nitrogen-doped crystallized carbon during charging and discharging, simultaneously maintain the stability of the electrode microstructure, inhibit the charging and discharging expansion of the internal iron sulfide, maintain the high-performance long-cycle sodium storage performance, and has high charging and discharging capacity and good rate performance.

Description

Spherical nitrogen-doped crystallized carbon-coated iron sulfide prepared under supercritical condition and preparation method and application thereof
Technical Field
The invention belongs to the field of composite material synthesis, and particularly relates to spherical nitrogen-doped crystallized carbon-coated iron sulfide prepared under a supercritical condition, and a preparation method and application thereof.
Background
Because sodium element is widely distributed and abundant in the earth, in recent years, research and development of room-temperature sodium ion charge-discharge batteries are considered to be an effective way for replacing lithium ion batteries in the fields of large-scale energy storage, particularly smart power grids and the like so as to effectively solve the problems of low mineral reserve and high lithium source cost of the lithium ion batteries. Among the cathode material systems of sodium ion batteries, carbon, metal oxides or sulfides, and alloy materials such as Sn and Sb are the most interesting material systems of the scholars, and the details are shown in the document [1 ]. The metal sulfide has the advantages of high theoretical capacity, abundant resources, low toxicity, good conductivity and the like, and is a potential negative electrode material of the sodium-ion battery. The FeS is used as an electrode material of the sodium ion battery, is a stable, nontoxic and cheap material with simple preparation, but the defects of low conductivity, poor interface compatibility with organic electrolyte, large microscopic size of the electrode material and low utilization rate of effective charge and discharge active points greatly hinder the electrochemical sodium storage capacity of the FeS, and is described in a document [1 ]. Meanwhile, the FeS has larger resistivity, so that the voltage is reduced quickly during discharging, and particularly, serious polarization phenomenon can be generated during heavy-current discharging of the battery, so that the service life of the battery is greatly shortened. Therefore, the improvement of the cycle capacity and sustainability of FeS as a negative electrode material in sodium ion batteries is a direction to be studied in depth.
[1]L.Zhang,H.B.Wu,Y.Yan,X.Wang,X.W.Lou,Energy Environ.Sci.2014,7,3302.
[2]a)S.Y.Lee,Y.C.Kang,Chem.Eur.J.2016,22,2769；b)Y.J.Zhu,L.M.Suo,T.Gao,X.L.Fan,F.D.Han,C.S.Wang,Electrochem.Comm.2015,54,18.
Disclosure of Invention
The invention aims to provide spherical nitrogen-doped crystallized carbon-coated ferric sulfide prepared under a supercritical condition, a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
a method for preparing spherical nitrogen-doped crystallized carbon-coated iron sulfide under supercritical conditions comprises the following steps:
1) taking ferric ammonium oxalate, diphenyl carbodiimide and a carbon source according to the mass ratio of 1:1 (1-7), and mixing and grinding to obtain a mixture A;
2) carrying out heat treatment on the mixture A in a low-temperature tubular furnace in argon-hydrogen atmosphere, heating to 500-1200 ℃ at a heating rate of 2-20 ℃/min, keeping the temperature for 1-5 h, cooling, and taking out to obtain nitrogen-doped crystallized carbon-coated iron carbide serving as a product B;
3) placing the product B in an ice water bath for ultrasonic dispersion to obtain a product C;
4) taking the product C and a sulfur source according to the mass ratio of 1 (5-10), and mixing and grinding to obtain a mixture D;
5) adding the mixture D into a polytetrafluoroethylene lining, adding deionized water, and stirring to fully mix the sample in the solution;
6) the inner liner is put into a hydrothermal outer kettle for fixation and sealing, and then is put into a homogeneous reactor for reaction for 2 to 12 hours at the temperature of 100 to 250 ℃; and after the reaction is finished, carrying out centrifugal suction filtration to obtain the spherical nitrogen-doped crystallized carbon-coated iron sulfide.
Further, the carbon source is urea or dicyandiamide.
Further, the ultrasonic dispersion time in the step 3) is 30 min.
Further, the sulfur source is sublimed sulfur, thioacetamide, urea or trithiocyanuric acid.
Further, 20-50 ml of deionized water is added in the step 5), and the stirring time is 15 min.
Spherical nitrogen-doped crystallized carbon-coated ferric sulfide prepared under supercritical conditions is applied as a negative electrode material of a sodium ion battery.
Has the advantages that:
1) the invention can realize the nitrogen-doped crystallized carbon-coated iron carbide/iron nitride microstructure in one step, and then realize the transformation of the iron sulfide structure by supercritical synthesis; the prepared nitrogen-doped crystallized carbon-coated iron carbide/iron nitride composite structure is a precursor structure, the precursor structure can provide important crystallized phase transition sites for later supercritical synthesis of iron sulfide, and meanwhile, a nitrogen-doped crystallized carbon structure is constructed to protect the internal iron sulfide structure.
2) The nitrogen-doped crystallized carbon-coated iron sulfide structure prepared by the invention can provide a high-conductivity path with nitrogen-doped crystallized carbon during charging and discharging, simultaneously maintain the stability of the electrode microstructure, inhibit the charging and discharging expansion of the internal iron sulfide, maintain the high-performance long-cycle sodium storage performance, and has high charging and discharging capacity and good rate performance.
3) The iron sulfide prepared by the method is special in shape, and the conductivity and the structural stability of the material in the charging and discharging processes can be obviously improved.
4) The invention adopts a two-step synthesis method to prepare the spherical nitrogen-doped crystallized carbon-coated iron sulfide, the preparation method is simple and stable, the repeatability is strong, the price of the raw material is low, and the preparation cost of the material reported in the prior literature can be obviously reduced.
Drawings
FIG. 1 is an electron micrograph of a product prepared in example 1;
FIG. 2 is a transmission diagram of a product prepared in example 1;
FIG. 3 is a graph of the cycling performance of the product prepared in example 2 as a sodium ion battery negative electrode material;
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) taking 2g of ferric ammonium oxalate, 2g of diphenyl carbodiimide and 2g of urea, and mixing and grinding in a glass mortar to obtain a mixture, wherein the mixture is marked as A;
2) carrying out heat treatment on the mixture A in a low-temperature tubular furnace in argon-hydrogen atmosphere, cooling and taking out to obtain a product B, wherein the heating rate of the heat treatment is 2 ℃/min, the heat treatment temperature is 500 ℃, and the time is 5 h;
3) placing the product B in an ice water bath for ultrasonic dispersion for 30min to obtain a product C;
4) the product C1g was mixed with 5g of sublimed sulfur in a glass mortar and ground to give a mixture, which was designated as D;
5) adding the mixture D into a polytetrafluoroethylene lining, adding deionized water with the volume of 20ml, and stirring for 15min to fully mix the sample in the solution;
6) the inner liner is put into a hydrothermal outer kettle, fixed and sealed, and put into a homogeneous reactor, the reaction temperature range is 100 ℃, and the reaction time range is 12 hours; and after the reaction is finished, carrying out centrifugal suction filtration to obtain a product E.
When the sample is observed under a scanning electron microscope, the product is densely grown in spherical particles as can be seen from fig. 1. Fig. 2 is a transmission view of the sample, spherically structured and externally coated with a graphitized carbon layer.
Example 2:
1) taking 2g of ferric ammonium oxalate, 2g of diphenyl carbodiimide and 6g of dicyandiamide, and mixing and grinding in a glass mortar to obtain a mixture, wherein the mixture is marked as A;
2) carrying out heat treatment on the mixture A in a low-temperature tubular furnace in argon-hydrogen atmosphere, cooling and taking out to obtain a product B, wherein the heating rate of the heat treatment is 10 ℃/min, the heat treatment temperature is 800 ℃, and the time is 3 h;
3) placing the product B in an ice water bath for ultrasonic dispersion for 30min to obtain a product C;
4) the product C1g was mixed with 8g of thioacetamide in a glass mortar and ground to give a mixture, which was designated as D;
5) adding the mixture D into a polytetrafluoroethylene lining, adding deionized water with the volume of 30ml, and stirring for 15min to fully mix the sample in the solution;
6) the inner liner is put into a hydrothermal outer kettle, fixed and sealed, and put into a homogeneous reactor, the reaction temperature range is 200 ℃, and the reaction time range is 8 hours; and after the reaction is finished, carrying out centrifugal suction filtration to obtain a product E.
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, then 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, and testing the performance of the sodium ion cell cathode material, wherein a cycle performance diagram of the prepared spherical iron sulfide cathode material is shown in figure 3, and the specific capacities of the products are 550mAh g < -1 > respectively under the current densities of 0.5A respectively; and still stable after 300 cycles.
Example 3:
1) taking 2g of ferric ammonium oxalate, 2g of diphenyl carbodiimide and 10g of urea, and mixing and grinding in a glass mortar to obtain a mixture, wherein the mixture is marked as A;
2) carrying out heat treatment on the mixture A in a low-temperature tubular furnace in argon-hydrogen atmosphere, cooling and taking out to obtain a product B, wherein the heating rate of the heat treatment is 15 ℃/min, the heat treatment temperature is 1200 ℃, and the time is 1 h;
3) placing the product B in an ice water bath for ultrasonic dispersion for 30min to obtain a product C;
4) mixing and grinding the product C1g and 9g of trithiocyanuric acid in a glass mortar to obtain a mixture, wherein the mixture is marked as D;
5) adding the mixture D into a polytetrafluoroethylene lining, adding deionized water with the volume of 40ml, and stirring for 15min to fully mix the sample in the solution;
6) the inner liner is put into a hydrothermal outer kettle, fixed and sealed, and put into a homogeneous reactor, the reaction temperature range is 240 ℃, and the reaction time range is 2 hours; and after the reaction is finished, carrying out centrifugal suction filtration to obtain a product E.
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 (6)

1. A method for preparing spherical nitrogen-doped crystallized carbon-coated iron sulfide under supercritical conditions is characterized by comprising the following steps:
1) taking ferric ammonium oxalate, diphenyl carbodiimide and a carbon source according to the mass ratio of 1:1 (1-7), and mixing and grinding to obtain a mixture A;
2) carrying out heat treatment on the mixture A in a low-temperature tubular furnace in argon-hydrogen atmosphere, heating to 500-1200 ℃ at a heating rate of 2-20 ℃/min, keeping the temperature for 1-5 h, cooling, and taking out to obtain nitrogen-doped crystallized carbon-coated iron carbide serving as a product B; the carbon source is urea or dicyandiamide;
3) placing the product B in an ice water bath for ultrasonic dispersion to obtain a product C;
4) taking the product C and a sulfur source according to the mass ratio of 1 (5-10), and mixing and grinding to obtain a mixture D;
5) adding the mixture D into a polytetrafluoroethylene lining, adding deionized water, and stirring to fully mix the sample in the solution;
6) the inner liner is put into a hydrothermal outer kettle for fixation and sealing, and then is put into a homogeneous reactor for reaction for 2 to 12 hours at the temperature of 100 to 250 ℃; and after the reaction is finished, carrying out centrifugal suction filtration to obtain the spherical nitrogen-doped crystallized carbon-coated iron sulfide.
2. The method for preparing spherical nitrogen-doped crystallized carbon-coated iron sulfide according to claim 1 under supercritical conditions, wherein the method comprises the following steps: the ultrasonic dispersion time in the step 3) is 30 min.
3. The method for preparing spherical nitrogen-doped crystallized carbon-coated iron sulfide according to claim 1 under supercritical conditions, wherein the method comprises the following steps: the sulfur source is sublimed sulfur, thioacetamide or trithiocyanuric acid.
4. The method for preparing spherical nitrogen-doped crystallized carbon-coated iron sulfide according to claim 1 under supercritical conditions, wherein the method comprises the following steps: and 5) adding 20-50 ml of deionized water into the mixture, and stirring for 15 min.
5. A spherical nitrogen-doped crystallized carbon-coated iron sulfide prepared according to the method of any one of claims 1 to 4.
6. The application of the spherical nitrogen-doped crystallized carbon-coated iron sulfide prepared under the supercritical condition as the negative electrode material of the sodium-ion battery, as claimed in claim 5.
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