CN113353970A - SnS-Fe1-xS double-sulfide heterojunction and synthesis method and application thereof - Google Patents
SnS-Fe1-xS double-sulfide heterojunction and synthesis method and application thereof Download PDFInfo
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- 239000002243 precursor Substances 0.000 claims abstract description 27
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- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011593 sulfur Substances 0.000 claims abstract description 18
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- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 5
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- C01G49/00—Compounds of iron
- C01G49/12—Sulfides
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- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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
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Abstract
The invention provides SnS-Fe1‑XThe synthesis method of the S double sulfide heterojunction comprises the following steps: construction of the precursor FeSnO (OH)5A nanoscale cube; heterojunction cell construction using dopamine pairs FeSnO (OH)5Coating the nano-scale cubic blocks; sulfurizing, namely, under the protection of inert gas, a sulfur source and a packageMixing and heating the coated precursor, pyrolyzing the sulfur source and carrying out a vulcanization reaction with the precursor to obtain a precursor FeSnO (OH)5Conversion to SnS-Fe in heterogeneous distribution1‑XS, converting dopamine coated on the outer layer into a carbon layer, and further synthesizing to obtain SnS-Fe1‑XAn S double sulfide heterojunction. The invention provides SnS-Fe1‑XThe prepared heterojunction can improve the conductivity and the ion/electron transmission efficiency of the SnS cathode material, and effectively relieve the volume expansion problem of the material in the energy storage process, so that the electrochemical properties of the SnS cathode material, such as the cyclicity, the stability and the like, can be improved. The invention also provides SnS-Fe1‑XAn S double sulfide heterojunction and applications thereof.
Description
Technical Field
The invention relates to the technical field of semiconductor materials, in particular to SnS-Fe1-XAn S double sulfide heterojunction and a synthesis method and application thereof.
Background
In the face of the continuous challenges brought by the fossil energy crisis and the ecological environmental protection problem, the research in the field of recyclable clean energy becomes the trend of future energy development, and among various methods, rechargeable batteries become one of the most important contents in the field of energy development. Among many rechargeable batteries, lithium ion batteries have been widely accepted due to their advantages of high energy density, long service life, etc., and have been put into commercial production, and have become an indispensable part of current social production in various fields such as civil use, medical treatment, aerospace, military and the like. Meanwhile, in order to solve the problems of uneven distribution and scarcity of lithium in the crust, sodium ion batteries and zinc ion batteries are developed accordingly. However, with the improvement of human technology, equipment has made higher requirements on an energy storage system, and the energy storage requirements of high energy density, good cycle safety and excellent charge and discharge performance are increasingly urgent. In order to solve the demand, the search for high-performance energy storage materials becomes one of important solutions, especially for negative electrode energy storage materials.
As a negative electrode material for commercial lithium ion batteries, carbon-based materials such as graphite have been used to date. However, the capacity of the graphite negative electrode material is low (the theoretical capacity is only 372mAh g)-1) The demand of the current development trend is far from being met. In addition, due to structural limitation and material factors, the application result of the graphite material in the field of sodium ion and zinc ion batteries is not ideal. Therefore, the development of a negative electrode material with high performance is one of the effective means for promoting the development of rechargeable batteries.
Among many negative electrode energy storage materials, SnS is considered one of the ideal negative electrode materials due to its layered structure characteristics and higher theoretical capacity. However, the SnS belongs to a semiconductor material, and the conductivity is poor, so that the transmission efficiency of electrons/ions in the charge and discharge process of the battery is influenced. On the other hand, the charge and discharge process of the battery operates by means of movement of ions (lithium ions, sodium ions, zinc ions, etc.) between the positive electrode and the negative electrode. During the charge and discharge process, ions are inserted and extracted back and forth between the two electrodes: during charging, ions are extracted from the positive electrode and are inserted into the negative electrode through the electrolyte, and the negative electrode is in an ion-rich state; the opposite is true during discharge. In the process, SnS can generate serious volume expansion, so that the damage of the material structure causes serious reduction of the capacity and the service life of the battery. Therefore, the practical application of SnS as a negative electrode material is seriously hindered.
In view of the above, the present invention aims to provide a new material to solve the above technical problems.
Disclosure of Invention
The invention aims to solve the technical problem of providing SnS-Fe1-XThe prepared heterojunction can improve the conductivity and the ion/electron transmission efficiency of the SnS cathode material, and effectively relieve the volume expansion problem of the material in the energy storage process, so that the electrochemical properties of the SnS cathode material, such as the cyclicity, the stability and the like, can be improved.
In order to solve the problems, the technical scheme of the invention is as follows:
SnS-Fe1-XThe synthesis method of the S double sulfide heterojunction comprises the following steps:
construction of the precursor FeSnO (OH)5A nanoscale cube;
heterojunction cell construction using dopamine pairs FeSnO (OH)5Nano-scale cubic block ofCoating;
sulfurizing, under the protection of inert gas, mixing and heating the sulfur source and the coated precursor, pyrolyzing the sulfur source and carrying out sulfurization reaction with the precursor to obtain a precursor FeSnO (OH)5Conversion to SnS-Fe in heterogeneous distribution1-XS, converting dopamine coated on the outer layer into a carbon layer, and further synthesizing to obtain SnS-Fe1-XAn S double sulfide heterojunction.
Further, the precursor construction process comprises the following steps: SnCl4·5H2O、C6H5Na3O7·2H2O、FeCl2·5H2Mixing O and water to prepare a mixed solution, adding a sodium hydroxide aqueous solution to perform coprecipitation, and filtering to obtain a precursor FeSnO (OH)5Nanoscale cubes.
Further, the precursor building process comprises the following steps:
SnCl4·5H2O、C6H5Na3O7·2H2O、FeCl2·5H2Mixing O with deionized water according to the molar ratio of 1:1:1 to prepare a mixed solution; and the molar concentration of each component in the mixed solution is 0.2M;
adding 0.4M sodium hydroxide aqueous solution into the mixed solution, carrying out coprecipitation, and carrying out suction filtration to obtain a precursor FeSnO (OH)5A nanoscale cube; wherein the volume ratio of the mixed solution to the sodium hydroxide aqueous solution is 0.5-0.8: 1.
Further, FeSnO (OH)5The mass ratio of the nano-scale cubic blocks to the dopamine is 1-3: 1.
Further, the sulfur source is excessive elemental sulfur or thiourea, and the excessive sulfur source forms a sulfur-doped structure on the carbon layer.
Furthermore, the heating temperature is 550-650 ℃, and the heating time is 3-5 h.
Further, the inert gas is argon or nitrogen.
Further, the inert gas is nitrogen, and a nitrogen-doped structure is formed on the carbon layer.
The invention also provides SnS-Fe1-XS double sulfide heterojunction prepared by the synthesis methodThus obtaining the product.
The invention also provides SnS-Fe1-XThe S double-sulfide heterojunction is applied to the negative energy storage material of a lithium ion battery, a lithium sulfur battery, a sodium ion battery or a zinc ion battery.
Compared with the prior art, the SnS-Fe provided by the invention1-XThe S double sulfide heterojunction and the synthesis method thereof have the beneficial effects that:
the invention provides SnS-Fe1-XS double sulfide heterojunction with SnS and Fe1-XS-bonding constructs heterostructures in which Fe1-XThe S has metal-grade conductivity, so that the conductivity of the negative electrode material can be improved, and the energy storage performance of the negative electrode material is improved; SnS-Fe1-XS is distributed in a heterogeneous mode, so that energy band difference among the components is caused, an internal field is further formed, the internal field can accelerate the migration of electrons and ions, and the energy storage performance of the cathode material is further improved; after the outer dopamine is converted into the carbon layer, the conductivity of the system can be well improved, and SnS and Fe are relieved simultaneously1-XS, the problem of volume expansion in the energy storage process; the doping of sulfur and nitrogen elements in the carbon layer provides a large number of active sites and defects, so that the transmission speed and the energy storage performance of electrons and ions are further enhanced. Therefore, the invention provides SnS-Fe1-XThe S double-sulfide heterojunction can effectively improve the cyclicity, stability and other electrochemical properties of the SnS cathode material.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 shows SnS-Fe of the present invention1-XXRD phase analysis pattern of S double sulfide heterojunction;
FIG. 2 shows SnS-Fe of the present invention1-XA projection electron microscope and mapping image of the S double-sulfide heterojunction;
FIG. 3 is SnS-Fe1-xS @ SC andapplying commercial SnS to an electrochemical performance comparison graph of a sodium-ion battery;
FIG. 4 is SnS-Fe1-xS @ SC and commercial SnS are applied to a diffusion performance characterization comparison graph of a sodium ion battery.
Detailed Description
The following description of the present invention is provided to enable those skilled in the art to better understand the technical solutions in the embodiments of the present invention and to make the above objects, features and advantages of the present invention more comprehensible.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual values, and between the individual values may be combined with each other to yield one or more new ranges of values, which ranges of values should be considered as specifically disclosed herein.
Example 1
SnS-Fe of the invention1-XThe S double sulfide heterogeneous synthesis method comprises the following steps:
step S1, constructing a precursor FeSnO (OH)5A nanoscale cube;
specifically, the method comprises the following steps:
step S11, adding SnCl4·5H2O、C6H5Na3O7·2H2O、FeCl2·5H2Mixing O with deionized water according to the molar ratio of 1:1:1 to prepare a mixed solution; and the molar concentration of each component in the mixed solution is 0.2M;
step S12, adding 0.4M sodium hydroxide aqueous solution into the mixed solution, carrying out coprecipitation, and obtaining a precursor FeSnO (OH) through suction filtration5A nanoscale cube; wherein the volume ratio of the mixed solution to the sodium hydroxide aqueous solution is 0.5-0.8:1, such as 0.5:1, 0.6:1, 0.7:1 or 0.8: 1.
Step S2, constructing heterojunction cell by using dopamine pair FeSnO (OH)5Nanoscale cube for packagingCovering;
in particular, FeSnO (OH)5The mass ratio of the nano-scale cubic blocks to the dopamine is 1-3:1, such as 1:1, 2:1 or 3: 1; dopamine coated FeSnO (OH)5The process of the nano-scale cube adopts a conventional dopamine coating process, the precursor and the dopamine in the proportion are added into 10mM Tris buffer solution, stirred for 4-12h, and centrifuged and dried. Dopamine pair FeSnO (OH)5The nano-scale cubic blocks are coated, so that the nano structure is maintained, independent units are constructed, and the dispersibility of the nano material is improved to prevent clustering.
Step S3, carrying out vulcanization treatment, mixing and heating a sulfur source and the coated precursor under the protection of inert gas, pyrolyzing the sulfur source and carrying out vulcanization reaction with the precursor to enable the precursor to be FeSnO (OH)5Conversion to SnS-Fe in heterogeneous distribution1-XS, converting dopamine coated on the outer layer into a carbon layer, and further synthesizing to obtain SnS-Fe1-XAn S double sulfide heterojunction.
Specifically, the inert gas is argon or nitrogen; the sulfur source is elemental sulfur or thiourea; the heating temperature is 550-650 ℃, and the heating time is 3-5 h; preferably, the heating temperature is 600 ℃ and the heating time is 4 h. The reaction principle is as follows:
SnS and Fe1-XThe reason why S shows heterogeneous distribution is that SnS2And different nucleation and crystallization rates among the components. When the sulfur source is pyrolyzed and reacts with the precursor to generate SnS2With Fe1-xS, at the same time, SnS2 is in liquid state due to high temperature, and Fe1-xSince S has a high melting point and is maintained in a solid state, solid-liquid separation may occur. SnS in liquid state as temperature decreases2A transition to the solid state SnS occurs. And the outer layer of dopamine is disulfated in the sealingThe system is converted into a carbon layer, and SnS-Fe with heterogeneous distribution is formed after the cooling process is finished1-xAn S heterojunction cell.
Preferably, the sulfur source is excessive elemental sulfur or thiourea, and the excessive sulfur source forms a sulfur-doped structure on the carbon layer; further preferably, the inert gas is nitrogen gas, so that a nitrogen-doped structure is formed in the carbon layer.
The doping of sulfur and nitrogen elements in the carbon layer provides a large number of active sites and defects, so that the transmission speed and the energy storage performance of electrons and ions are further enhanced.
The heterojunction structure according to the invention is denoted as SnS-Fe1-xS @ SC. The features and structure of the heterojunction of the present invention are shown in FIG. 1 and FIG. 2, wherein FIG. 1 is SnS-Fe of the present invention1-XXRD phase analysis pattern of S double sulfide heterojunction; FIG. 2 shows SnS-Fe of the present invention1-XProjection electron microscope and mapping image of S double sulfide heterojunction.
Example 2
The invention provides SnS-Fe1-XApplication example of S double sulfide heterojunction.
SnS-Fe prepared in example 11-XMixing the S double-sulfide heterojunction with a conductive agent (acetylene black) and a binding agent (PVDF) at a mixing ratio of 7:2:1 to prepare active substance slurry, coating the active substance slurry on a copper foil (the thickness is about 14 mu m), and drying (under the vacuum drying condition, the temperature is 90 ℃ and the time is 12 hours) to obtain a negative pole piece material;
punching the negative pole piece material, adopting a sodium metal sheet as a contraposition electrode, and completing the assembly of the button cell in a glove box by using a diaphragm, electrode liquid and a button cell packaging shell (CR 2016).
Comparative example 1
Corresponding to the application method of example 2, commercial SnS was used to prepare the electrode material and encapsulate the battery.
The electrochemical performance of the anode materials of example 2 and comparative example 1 was tested using a blue test system. The test method comprises the following steps:
(1)0.1mA g-1under the current density, different cathode materials are measured through 150 cycles of charge-dischargeSpecific discharge capacity of (a);
(2)2mA g-1measuring the discharge specific capacity of different cathode materials through 250 cycles of charge-discharge circulation under the current density;
(3)0.1,0.3,0.5,1.0mA g-1under the current density, measuring the rate performance of different cathode materials;
(4) diffusion coefficient characterization was performed according to the Gitt test model.
Please refer to FIG. 3, which shows SnS-Fe1-xS @ SC and commercial SnS are applied to the electrochemical performance comparison graph of the sodium-ion battery. Wherein FIG. 3a represents 0.1A g-1Discharge capacity at current density; FIG. 3b shows 2A g-1Discharging specific capacity under current density; figure 3c rate performance at different current densities. As can be seen from FIG. 3a, 0.1mA g-1Under the current density, after 150 cycles of charging and discharging, the SnS-Fe of the invention1-xS @ SC is applied to sodium ion battery and can maintain 610mAh g-1The discharge specific capacity and the charge-discharge efficiency are close to 100 percent; SnS is applied to sodium ion battery and only has 41mAh g-1Specific discharge capacity of (a); as can be seen from FIG. 3b, 2mA g-1Under the current density, after 250 cycles of charge and discharge, the SnS-Fe of the invention1-xS @ SC can maintain 403mAh g-1The discharge specific capacity and the charge-discharge efficiency are 99 percent; SnS is only 17mAh g-1Specific discharge capacity of (a); as can be seen from FIG. 3c, at 0.1,0.3,0.5,1.0mA g-1Under the current density, the SnS-Fe of the invention1-xS @ SC applied to sodium ion battery and having 611,552,530,491Ah g-1At a subsequent specific discharge capacity of 0.2,0.4,0.6,0.8A g-1Current density of 601,554,531,516mAh g-1Specific discharge capacity of (a); the commercial SnS is applied to the sodium ion battery and is controlled at 0.1,0.3,0.5 and 1.0mA g-1Only 358,181,139,87mAh g under the current density-1And only 116mAh g is maintained in the subsequent circulation-1Specific discharge capacity of (2).
Please refer to FIG. 4, which shows SnS-Fe1-xS @ SC and commercial SnS are applied to a diffusion performance characterization comparison graph of a sodium ion battery. As can be seen from FIG. 4, the SnS-Fe of the present invention1-xS @ SC responseThe sodium ion diffusion coefficient is higher than that of the commercial SnS material when the sodium ion battery is used for a sodium ion battery.
Thus, the SnS-Fe of the present invention1-XThe S double-sulfide heterojunction effectively improves the cyclicity, stability and other electrochemical properties of the SnS cathode material, fully exerts the application potential of the SnS in the aspect of energy storage materials, provides an effective solution for realizing the practicability and commercialization of the SnS cathode material, and provides a new method and power for the development of rechargeable batteries and energy storage materials.
SnS-Fe of the invention1-XThe S double-sulfide heterojunction can be applied to the negative energy storage materials of lithium ion batteries, lithium sulfur batteries or zinc ion batteries, and has good electrochemical performance.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the described embodiments. Various changes, modifications, substitutions and alterations to these embodiments will occur to those skilled in the art without departing from the spirit and scope of the present invention.
Claims (10)
1. SnS-Fe1-XThe synthesis method of the S double sulfide heterojunction is characterized by comprising the following steps:
construction of the precursor FeSnO (OH)5A nanoscale cube;
heterojunction cell construction using dopamine pairs FeSnO (OH)5Coating the nano-scale cubic blocks;
sulfurizing, under the protection of inert gas, mixing and heating the sulfur source and the coated precursor, pyrolyzing the sulfur source and carrying out sulfurization reaction with the precursor to obtain a precursor FeSnO (OH)5Conversion to SnS-Fe in heterogeneous distribution1-XS, converting dopamine coated on the outer layer into a carbon layer, and further synthesizing to obtain SnS-Fe1-XAn S double sulfide heterojunction.
2. The SnS-Fe of claim 11-XThe synthesis method of the S double-sulfide heterojunction is characterized in that the precursor construction process comprises the following steps: SnCl4·5H2O、C6H5Na3O7·2H2O、FeCl2·5H2Mixing O and deionized water to prepare a mixed solution, adding a sodium hydroxide aqueous solution to perform coprecipitation, and filtering to obtain a precursor FeSnO (OH)5Nanoscale cubes.
3. The SnS-Fe of claim 21-XThe synthesis method of the S double-sulfide heterojunction is characterized in that the precursor construction process comprises the following steps:
SnCl4·5H2O、C6H5Na3O7·2H2O、FeCl2·5H2Mixing O with deionized water according to the molar ratio of 1:1:1 to prepare a mixed solution; and the molar concentration of each component in the mixed solution is 0.2M;
adding 0.4M sodium hydroxide aqueous solution into the mixed solution, carrying out coprecipitation, and carrying out suction filtration to obtain a precursor FeSnO (OH)5A nanoscale cube; wherein the volume ratio of the mixed solution to the sodium hydroxide aqueous solution is 0.5-0.8: 1.
4. The SnS-Fe of claim 11-XThe synthesis method of the S double sulfide heterojunction is characterized in that the synthesis method is FeSnO (OH)5The mass ratio of the nano-scale cubic blocks to the dopamine is 1-3: 1.
5. The SnS-Fe of claim 11-XThe synthesis method of the S double-sulfide heterojunction is characterized in that the sulfur source is excessive elemental sulfur or thiourea, and the excessive sulfur source forms a sulfur-doped structure on the carbon layer.
6. SnS-Fe of claim 51-XThe synthesis method of the S double-sulfide heterojunction is characterized in that the heating temperature is 550-650 ℃, and the heating time is 3-5 h.
7. The SnS-Fe of claim 11-XThe synthesis method of the S double sulfide heterojunction is characterized in that inert gasThe body is argon or nitrogen.
8. The SnS-Fe of claim 71-XThe synthesis method of the S double-sulfide heterojunction is characterized in that the inert gas is nitrogen, and a nitrogen-doped structure is formed on the carbon layer.
9. SnS-Fe1-XAn S double sulfide heterojunction, characterized in that it is prepared by the synthesis method of any one of claims 1 to 8.
10. The SnS-Fe of claim 91-XThe S double-sulfide heterojunction is applied to the negative energy storage material of a lithium ion battery, a lithium sulfur battery, a sodium ion battery or a zinc ion battery.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111628155A (en) * | 2020-06-23 | 2020-09-04 | 广西师范大学 | Molybdenum-tin bimetallic sulfide as negative electrode material of lithium ion/sodium ion battery and preparation method thereof |
-
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111628155A (en) * | 2020-06-23 | 2020-09-04 | 广西师范大学 | Molybdenum-tin bimetallic sulfide as negative electrode material of lithium ion/sodium ion battery and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| FENGJUN ZHAO ET AL.: ""Synergistical coupling Janus SnS-Fe1-xS heterostructure cell and polydopamine-derived S doped carbon as high-rate anodes for sodium-ion batteries"", 《CHEMICAL ENGINEERING JOURNAL》 * |
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| CN114725343A (en) * | 2022-04-19 | 2022-07-08 | 西安航空学院 | Nitrogen and sulfur co-doped biochar/SnO2SnS/S composite material, preparation method and application |
| CN114725343B (en) * | 2022-04-19 | 2023-08-29 | 西安航空学院 | Nitrogen and sulfur co-doped biochar/SnO 2 SnS/S composite material, preparation method and application |
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