CN113200565A - Flaky tin disulfide and preparation method and application thereof - Google Patents

Flaky tin disulfide and preparation method and application thereof Download PDF

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CN113200565A
CN113200565A CN202110499597.9A CN202110499597A CN113200565A CN 113200565 A CN113200565 A CN 113200565A CN 202110499597 A CN202110499597 A CN 202110499597A CN 113200565 A CN113200565 A CN 113200565A
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tin disulfide
sns
flaky
mixed solution
reaction kettle
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张睿智
肖新宇
尹岚
黄靖栋
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Hunan Institute of Technology
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G19/00—Compounds of tin
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • 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
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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
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
    • C01P2004/24—Nanoplates, i.e. plate-like particles with a thickness from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
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    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

A flaky tin disulfide and a preparation method and application thereof relate to the technical field of battery electrode materials, and the preparation method comprises the following steps: taking a proper amount of stannous chloride dihydrate and thioacetamide, mixing, adding a proper amount of deionized water, and stirring to fully mix to obtain a mixed solution; adding a proper amount of ammonia water into the mixed solution to adjust the pH value of the mixed solution to 8-9; transferring the mixed solution after the pH value is adjusted to a reaction kettle, sealing the reaction kettle, performing hydrothermal treatment at the temperature of 110-130 ℃ until the reaction is finished, and taking out the reaction kettle after the reaction kettle is cooled to room temperature to obtain a product after the reaction; and washing and drying the product to obtain yellow powdery flaky tin disulfide. When the flaky tin disulfide prepared by the invention is applied to the negative electrode of a lithium ion or sodium ion battery, the stability and the rate capability of the battery can be improved.

Description

Flaky tin disulfide and preparation method and application thereof
Technical Field
The invention relates to the technical field of battery electrode materials, in particular to flaky tin disulfide and a preparation method and application thereof.
Background
With the rapid development of modern society, the energy crisis gradually becomes a significant problem that attracts global attention. As a main energy storage device, a rechargeable lithium ion battery has outstanding characteristics of high energy density, small self-discharge, no memory effect, long cycle life and the like, so that the rechargeable lithium ion battery becomes the most widely applied battery in modern digital products such as mobile phones, notebook computers and the like, and is rapidly advancing from electronic devices to electric vehicles, renewable energy sources and a plurality of new industries at present. The theoretical capacity of the industrialized graphite cathode material is lower, generally 372 mAh g-1The high energy density required for large-sized electric vehicles (EV/PHEV) and large-scale energy storage systems (EES) cannot be satisfied. However, the market share of lithium ion batteries to be occupied by the two application fields is not small and varies, so that the development of new lithium ion battery negative electrode materials is very urgent.
SnS, a typical layered metal sulfide2CdI having octahedron of tin atom and sulfur atom by Van der Waals' force2Crystalline structure of type (III) and having a high reversible specific capacity. However, most existing SnS2When the material is used as a base material of a lithium ion battery or a sodium ion battery, the cycling stability and the rate capability are poor. Nanostructured SnS compared to micron and submicron scale materials2The material (such as nano wire, nano sheet and the like) is more favorable in electrochemical application, so that SnS is optimized in nano scale2The structure to improve the electrochemical performance of the lithium ion and sodium ion storage will be a big trend in the future.
Disclosure of Invention
The invention aims to provide a preparation method of nano-grade flaky tin disulfide, which is applied to a lithium ion or sodium ion battery cathode to improve the stability and rate capability of the battery.
In order to solve the technical problems, the invention adopts the following technical scheme: a preparation method of flaky tin disulfide comprises the following steps:
(1) taking a proper amount of stannous chloride dihydrate and thioacetamide, mixing, adding a proper amount of deionized water, and stirring to fully mix to obtain a mixed solution.
(2) And adding a proper amount of ammonia water into the mixed solution to adjust the pH value of the mixed solution to 8-9.
(3) And transferring the mixed solution after the pH value is adjusted to a reaction kettle, sealing the reaction kettle, performing hydrothermal treatment at the temperature of 110-130 ℃ until the reaction is finished, and taking out the reaction kettle after the reaction kettle is cooled to room temperature to obtain a product after the reaction.
(4) And washing and drying the product to obtain yellow powdery flaky tin disulfide.
Wherein the mass ratio of the stannous chloride dihydrate to the thioacetamide is 1: 5.
more preferably, the stirring time in the step (1) is 20 to 40 minutes.
More preferably, the hydrothermal time in step (3) is about 5-8 h.
More preferably, in step (4), the product is centrifugally washed 2-4 times with anhydrous ethanol, and then centrifugally washed 2-4 times with deionized water.
More preferably, the drying manner in the step (4) is to perform sufficient drying in a drying oven at 70 to 90 ℃.
In addition, the invention also provides flaky tin disulfide which is prepared by the preparation method.
Meanwhile, the invention also relates to application of the flaky tin disulfide in a lithium ion battery negative electrode material or a sodium ion battery negative electrode material.
The invention has the beneficial effects that: the invention can prepare the flaky SnS under the hydrothermal condition of about 120 ℃ in a shorter hydrothermal time2Compared with the prior SnS2Compared with the preparation method, the preparation method has the advantages of lower energy consumption in the reaction process, higher production efficiency and more contribution to industrial production and application. In addition, the crystallinity of the flaky tin disulfide prepared by the simple hydrothermal method is highBetter, larger crystal grains, more regular particle arrangement in the crystal structure, and nano-scale flaky SnS therein2Extremely thin and nearly transparent, which makes the sheet-like SnS2The material has larger specific surface area, thereby improving and enhancing the electrochemical performance of the material and having better application value as an electrode material.
Moreover, when the prepared flaky tin disulfide is used as a negative electrode material of a lithium ion battery or a sodium ion battery, the nano-sized part in the flaky tin disulfide can shorten the diffusion path of lithium ions or sodium ions to a certain extent, so that the corresponding electrode has high reversibility in the charge-discharge cycle process, and the battery has better stability. Through cyclic voltammetry tests and rate performance tests, the batteries with the flaky tin disulfide negative electrode material can still maintain higher coulombic efficiency under the change of current density, so that the corresponding batteries can obtain higher rate performance.
Drawings
FIG. 1 is a schematic view of a preparation process in an embodiment of the present invention;
FIG. 2 shows SnS2(PDF #23-0677) phase and SnS obtained in this example2Schematic diagram of X-ray powder diffraction pattern comparison between samples;
FIG. 3 shows a sheet-like SnS in the example2After XPS test, obtaining a full spectrogram (a) in the range of 0-1200eV, a Sn 3d spectrogram (b) obtained by peak shape fitting of Sn and S elements and an S2 p spectrogram (c) obtained by peak shape fitting of Sn and S elements;
FIG. 4 shows an example of SnS2FESEM images, (c) TEM images, (d) HRTEM images, (e) elemental distribution diagram of S, Sn, and (f) EDX spectra of the materials;
FIG. 5 shows an example of SnS2When the electrode is used as the negative electrode material of the lithium ion battery, (a) a Cyclic Voltammetry (CV) curve, (b) a constant current charging and discharging curve, and (c) a current density of 0.1Ag−1Cyclic stability in time, (d) rate capability, (e) current density of 1Ag−1Cyclic stability of time;
FIG. 6 shows SnS in the example2When the electrode is used as a negative electrode material of a sodium ion battery, (a) constant current charge-discharge curve, (b) rate performance, and (c) current density of 0.1Ag−1Cyclic stability in time (d) current density of 1Ag−1Cycling stability of time.
Detailed Description
In order to facilitate understanding of those skilled in the art, the present invention will be further described with reference to the following examples and drawings, which are not intended to limit the present invention. It should be noted that the following examples are carried out in the laboratory, and it should be understood by those skilled in the art that the amounts of the components given in the examples are merely representative of the proportioning relationship between the components, and are not specifically limited.
Firstly, preparing flake tin disulfide.
As shown in fig. 1, the preparation process comprises the following steps:
(1) 0.3949g of stannous chloride dihydrate (SnCl) were weighed out2·2H2O) and 1.9722g of thioacetamide (CH)3CSNH2) Placed in a clean beaker, then 35ml of deionized water was added and stirred for about 30 minutes to mix well to obtain a mixed solution.
(2) And adding a proper amount of ammonia water into the mixed solution to adjust the pH value of the mixed solution to 8-9.
(3) And transferring the mixed solution after the pH value is adjusted to a high-pressure reaction kettle with the volume of 50ml, sealing, putting the sealed mixed solution in a drying oven with the temperature of 120 ℃ for hydrothermal for about 6 hours until the reaction is finished, and taking out the mixed solution after the high-pressure reaction kettle is cooled to the room temperature to obtain a product after the reaction.
(4) Centrifuging and washing the product for 3 times by using absolute ethyl alcohol, centrifuging and washing the product for 3 times by using deionized water to obtain a washed product, placing the washed product in a drying box for fully drying, wherein the temperature condition in the drying box is about 80 ℃, and collecting the obtained yellow powder after drying, namely the flaky tin disulfide (SnS)2) A material.
Second, the SnS prepared in this example2And carrying out appearance and structure characterization.
First, the flaky SnS obtained in this example2Extracting certain SnS from the material2Sample, determination of SnS by X-ray powder diffraction technique (XRD)2The crystal structure and phase purity of the sample, and the obtained map result are shown in the lower half of figure 2, and the upper half of figure 2 is SnS2(PDF #23-0677) phase standard map PDF card, and by comparing the two maps, diffraction peaks in the two maps are very consistent, wherein SnS2Peaks of the sample at 15.03 °, 28.20 °, 30.26 °, 32.12 °, 41.89 °, 46.12 °, 49.96 °, 52.45 °, 54.96 ° and 58.35 ° were compared with SnS, respectively2(PDF #23-0677) phase crystal planes (001), (100), (002), (101), (102), (003), (110), (111), (103) and (200) are completely coincident. The peak intensity of the corresponding (001) plane at 15.03 ℃ is extremely high, the intensity of the peaks at other positions is relatively weak, but the peak shape is sharp, and SnS2The overall peak in the sample map is sharp and no peak broadening appears, which can indicate that the flaky SnS prepared by the embodiment2Better crystallinity, larger crystal grains and more regular arrangement of mass points in the crystal structure. Furthermore, SnS2No other miscellaneous peak is observed in the diffraction pattern of the sample, and the XRD data result shows that the high-purity flaky SnS is successfully prepared2。
Further, the flaky SnS was measured by X-ray photoelectron spectroscopy (XPS)2The chemical components of (a) were detected, and the detection results are shown in FIGS. 3 (a) to 3 (c). Wherein, FIG. 3 (a) shows a sheet-like SnS2From the full spectrum in the range of 0-1200eV after XPS test, it can be seen that only the weaker O peak in the range of 500-600eV is detected, which may be due to the long-term exposure to air without dry storage of the sample. In which several strong peaks of Sn and S elements were mainly detected, and peaks of other elements were hardly observed. This further indicates that Sn and S are obviously present in the synthesized material, and also indicates that no other impurity elements are finally introduced after the synthesis of the material.
After peak shape fitting is carried out on the Sn and the S, high-resolution scanning maps shown in FIGS. 3 (b) and 3 (c) are obtained, wherein the map shown in FIG. 3 (b) is a Sn 3d spectrogram, and the bonding energies 494.8 eV and 486.4 eV shown in the map correspond to the Sn 3d respectively3/2、Sn 3d5/2Description of SnS2Middle Sn4+Is actually present. While the spectrum shown in FIG. 3 (c) is an S2 p spectrum in which the XPS peaks are S2 p at binding energies of 161.8 eV and 163.2 eV, respectively3/2And S2 p1/2May correspond to S2-Ions. The combination energy and SnS respectively corresponding to the Sn element and the S element in the detection result2The binding energy of the two elements is generally identical. Final observations with existing SnS2The Raman characteristic peaks are consistent, and the SnS in the prepared material is proved2And the valence of the Sn element and S element.
Because the flaky tin disulfide synthesized by one step by a hydrothermal method is not subjected to high-temperature sintering treatment, the phenomenon of crystal grain agglomeration can be avoided to a certain extent, and in order to verify the characteristics, SnS is revealed by SEM and TEM images2Morphology and microstructure of. Specifically, FIGS. 4 (a-d) are SnS2SEM and TEM images of the Material, as can be seen from FIGS. 4 (a, b), SnS2Is a substantially irregular sheet-like structure and is overlapped with each other in an irregular manner, and the surface is very smooth as a whole. Individual flakes SnS can be observed in these differently overlapped sheets2A nearly hexagonal morphology, as presented in fig. 4 (b). These flaky SnS2The size of the middle most part is in micron order, about 2-5 μm, and the thickness is about 200 nm. Some SnS in nano-scale2Nano-scale flaky SnS scattered on the large micron-scale sheets2Extremely thin and nearly transparent, and can increase the prepared flaky SnS2The specific surface area of the material, which is a characteristic of the material, can improve and enhance the final electrochemical performance of the material to a certain extent.
FIG. 4 (c) shows SnS2Transmission electron microscope image (TEM) of material, in which SnS2Is around 2-5 μm, which is consistent with SEM image results. The sheet-shaped morphology shown in the figure is close to hexagonal and presents a semitransparent state, so that other nano-scale sheet-shaped SnS can be further illustrated2The transparency should be higher, which is also consistent with the results shown in SEM images. FIG. 4 (d) shows SnS2High Resolution TEM (HRTEM) images of the lamellar material with sharp and continuous portions having lattice fringe spacings of about 0.20 nm and 0.29 nm, respectively close to the hexagonal phase SnS2(110) And the value of the interplanar spacing d of the (002) plane.
The EDX test results in FIG. 4(e, f) show flaky SnS2The Sn element and the S element are uniformly distributed in the material, and other impurity elements do not appear. Again proves that the one-step hydrothermal method successfully synthesizes the high-purity flaky SnS2A material.
Third, the SnS prepared in this example2Testing on lithium storage performance.
Specifically, the sheet-shaped SnS prepared in the embodiment2Preparing a wafer electrode with the diameter of 12mm, assembling the wafer electrode into a button half cell and a button full cell, and detecting SnS by using methods such as cyclic voltammetry, rate performance test and the like2The electrode has electrochemical performance when being used as a negative electrode material of a lithium ion battery.
First, SnS is detected by cyclic voltammetry2The lithium storage mechanism of the electrode as the negative electrode material of the lithium ion battery. In the voltage range of 0.01-3V and the scanning rate of 0.1mV s-1The Cyclic Voltammogram (CV) of the material is obtained as shown in FIG. 5 (a) (the curves of the three circles are shown as 1st-3rd in the figure) after three cycles in total. Two sharp reduction peaks at about 1.75v and 1.2v appear during the first cathodic scan (reduction reaction). During the second and third cycles, the peaks at these two locations gradually disappeared and finally merged into a peak around 1.3 v. This indicates that the reaction which occurs in this process is irreversible. This overall irreversible process may correspond to several irreversible reactions: lithium ion intercalation of SnS2Interlaminar, tin disulfide conversion and alloying reactions, and solid electrolyte interfacesFilm (SEI) generation.
It is known to those skilled in the art that an SEI film is an interfacial film formed by an electrolyte solution that undergoes a redox reaction during a first charge process of a lithium ion battery to be decomposed and then deposited on the surface of an electrode material. The film is the key for determining the compatibility of the negative electrode/electrolyte, and the ion conduction effect and the electronic insulation property of the SEI film ensure that the lithium ion battery can stably work for a long time. Therefore, the lithium ion battery plays a very critical role in the performance of the battery, including capacity, rate, cycle, safety performance and the like.
In the first anode scanning process (oxidation reaction), oxidation peaks occur at about 0.6v, 0.8v and 2.3v, which are attributable to the fact that lithium ions are separated from SnS2De-intercalation, de-alloying and reconversion between layers to produce SnS2The process of (1). Wherein the insertion/extraction of lithium ions is a partially reversible process. It is noted that the oxidation peaks at 0.6v, 0.8v were not attenuated during the latter two cycles. The oxidation peak even at 0.6v is divided by one peak into two small peaks. This is the result of activation through the first charge-discharge cycle. The cyclic curves in the second and third circles of the CV curve are substantially coincident with each other from the peak position or the height of the peak, thereby proving that SnS2The electrodes are highly reversible during charge and discharge cycles.
And then SnS is subjected to rate capability test2The electrochemical properties of (2) were further investigated, and specifically, the current density was set to 0.1Ag-1、0.3Ag-1、0.5Ag-1、1Ag-1Finally returning to 0.1Ag-1And respectively performing charge-discharge cycles for 10 circles under each current density. As can be seen in fig. 5 (d): under the condition of gradient current density, the test result shows that SnS2Has excellent rate capability because the current density is 0.1A g-1After 10 times of charge-discharge circulation, the specific discharge capacity is maintained at 846.8 mAh g-1. The reversible specific capacity can be stably maintained at 835.5mAh g-1Around, the corresponding coulombic efficiency was 98.66%. The current density is increased to 0.3 Ag-1Has 657.8 mAh g after-1Its reversible specific capacity is 651.9 mAh g-1The coulombic efficiency was 98.82%. Further increasing the current density to 0.5A g-1The corresponding reversible specific capacity is about 605.8mAh g-1And the specific discharge capacity is 614.5 mAh g-1The coulombic efficiency was 98.58%. Finally 1Ag-1The discharge specific capacity of the current density can reach 544.8 mAh g-1The reversible specific capacity is kept at 536.7 mAh g-1The coulombic efficiency was 98.52%. When the current density is restored to 0.1A g-1When, SnS2The electrode still reaches about 768.3 mAh g-1Reversible specific capacity of about, and 793.6 mAh g-1The corresponding coulombic efficiency was 96.81%.
It should be noted that, under the condition of gradient current density test, the corresponding specific discharge capacity and reversible specific capacity are reduced to some extent as the current density is increased. This is because, in the process of increasing the current density, a large amount of electrolyte ions are adsorbed on the electrode electrolyte interface, so that the concentration of the electrolyte ions at the interface is rapidly reduced, the concentration polarization is inevitably increased, a higher excitation voltage is inevitably required under the condition that a high current density is required to be maintained, but the number of interface charges is not increased, so that the capacity is reduced with the increase of the current density. That is, the greater the current density, the more severe the degree of polarization of the electrode. The current density is a microscopic unit of magnification, and the capacity loss caused by the polarization of the battery under high magnification is a very normal phenomenon. The coulombic efficiency is maintained to be about 96-98% without the first circle, and the overall change is small. The higher capacity and coulombic efficiency can be maintained after the low current density is recovered, which shows that the flaky SnS prepared in the embodiment2Has excellent rate performance.
And for flaky SnS2The cycle stability of the material can adopt a voltage window of 0.01-3V and 0.1A g-1And 1A g-1The current density of the lithium-ion half cell was tested. FIG. 5 (c) shows that at a current density of 0.1 Ag-1SnS corresponding in time2The charge-discharge cycle curve of the electrode is shown at 0.1A g-1At a current density of (S), SnS2The first discharge specific capacity of the electrode can reach 1670.7mAh g-1The coulombic efficiency was 58.67%.
It should be further noted that coulombic efficiency, i.e. discharge efficiency, refers to the ratio of the battery discharge capacity to the charge capacity during the same cycle, i.e. the percentage of the discharge capacity to the charge capacity. As for the negative electrode material, the ratio of the lithium removal capacity to the lithium insertion capacity, i.e., the discharge capacity/charge capacity. The factors influencing the coulombic efficiency of the lithium ion battery include the following factors:
1. and (3) temperature. The influence of temperature on diffusion is obvious, and generally, the temperature rise is beneficial to lithium ion diffusion, namely, the migration resistance is reduced, so that the migration rate of lithium ions is increased, and the first coulombic efficiency is likely to be higher. 2. And (5) forming an SEI film. The SEI film consumes a part of charged lithium ions during the generation process, and the negative electrode reaction process is a process of lithium ion intercalation and deintercalation in the interlayer structure of carbon, so the formation of the SEI film reduces the first cycle efficiency of the negative electrode. 3. Decomposition of the electrolyte. The redox reaction of the electrolyte causes a great deal of lithium ion loss, and the quantity of lithium ions in the charge-discharge cycle process is reduced, so that the first coulombic efficiency of the material is reduced. 4. Poor reversibility: electrode materials with poor reversibility can lead to an increased amount of deactivation of lithium ions, thereby reducing coulombic efficiency.
But the reversible specific capacity is kept at 522.7 mAh g after 100 cycles-1About 535.7 mAh g as specific discharge capacity-1Coulombic efficiency was maintained at 97.56%. The irreversible capacity loss at this current density is about 67.9%. And when the current density increased to 1A g-1The specific discharge capacity of the first circle is 1297.4 mAh g-1After 100 cycles, the reversible specific capacity is maintained at 326.7 mAh g-1About, the specific discharge capacity is kept at 336.2 mAh g-1. Coulombic efficiency was maintained at 97.20% and the irreversible capacity loss at this current density was about 74%. The first irreversible capacity is generated due to SnS2And (3) a conversion reaction in the lithiation process, decomposition of the electrolyte after an oxidation-reduction reaction and formation of an SEI film.
To further explore the reactions during the long cycles, 0.1A g was added separately-1Current densities of (a) and (b) in fig. 5 (b), the constant current charge and discharge curves of circles 5, 50 and 80 are compared. It can be seen from the figure that the charge and discharge plateau is consistent with the cyclic voltammogram. Compared with the constant-current charging and discharging curve of the 5 th circle, the curves of the 50 th circle and the 80 th circle have larger changes, and the difference value between the discharging specific capacity and the charging specific capacity is gradually reduced. The constant current charging and discharging curves of the 50 th circle and the 80 th circle are basically consistent, and overlapped parts can be seen in the graphs, which shows that the charging and discharging capacity change is small in the following charging and discharging cycle process.
Fourth, SnS prepared in this example2Testing on sodium storage performance.
Those skilled in the art will appreciate that the size of sodium ions is 34% larger than that of lithium ions, and therefore it is very challenging to develop an excellent negative electrode material for sodium ion batteries. However, due to the advantages of high specific capacity, large interlayer spacing and the like, the tin disulfide becomes a potential sodium ion battery cathode material.
To confirm the synthesized SnS2The material was used for energy storage, and this example further assembled a sodium ion battery to evaluate its sodium storage capacity. Specifically, the product prepared in the embodiment can be made into a wafer electrode and assembled into a button half cell, and similarly, the SnS can be detected by a method similar to a lithium ion battery by utilizing a cycle stability test and a rate capability test2The electrochemical performance of the electrode as the negative electrode material of the sodium-ion battery is shown in the test result of fig. 6.
FIG. 6 (a) shows SnS2The electrode was at 100mA g-1The 1st, 30 th and 66 th cycles after constant current charging and discharging at a low current. As can be seen from the figure, the specific discharge capacity and the specific charge capacity of the first circle of the electrode are 1146.8mAhg respectively-1And 540.8 mAhg-1. The specific charge-discharge capacity of the 30 th circle is lower than 300mAhg-1. Loop 66 ofThe specific capacity is about 300mAhg < -1 >, the capacity is increased to a certain extent in comparison with the capacity of the 30 th circle, but the overall difference is not large, the specific capacity is increased at the later stage of charge-discharge cycle, and then is reduced and is recovered to the initial specific capacity value, and the phenomenon is probably caused by the side reaction of the electrode in the charge-discharge process, so that the capacity is increased.
As can be seen from FIG. 6 (c), g is 100mA-1The capacity of the capacitor is not greatly improved in the process of charging and discharging 100 circles in a low-current density circulating manner. The charging and discharging specific capacity is maintained at 258.7mAhg after 100 cycles-1And 262.8mAhg-1. There is a certain capacity fading before the 20 th cycle, and the specific charge-discharge capacity is lower than 300mAhg from the 30 th cycle-1This form of capacity fade is similar to existing sodium ion batteries and is within an industry-accepted range.
SnS as shown in FIG. 6 (b)2And (3) the rate performance test result of the electrode as the negative electrode material of the sodium-ion battery. Firstly, 100mA g is selected-1Was subjected to activation for 3 charge-discharge cycles at a small current, and then each was charged at 100mA g-1、300mA g-1、500mA g-1And 1A g-1The charge-discharge cycle is carried out under the current density gradient, and 10 cycles are respectively carried out under each current density. Wherein, 100mA g-1The charging specific capacity after circulating for 10 circles under the current density is 263.3 mAhg-1The specific discharge capacity is 283.8mAhg-1. The current density is increased to 300mAg-1The corresponding charge-discharge specific capacities are respectively 202.7 mAhg-1And 208.5mAhg-1. The current density continued to increase to 500mAg-1The post-charging and discharging specific capacity is maintained to be 175.6 mAhg-1And 178.6 mAhg-1. Finally when the current density is 1Ag-1The charging and discharging specific capacities after 10 cycles are respectively 144.3 mAhg-1And 146.0 mAhg-1. And when the current density returns to 0.1mA g-1The specific charge-discharge capacity is 202.0mAhg-1And 208.3mAhg < -1 >, the coulombic efficiency in the first cycle is low, and the test result under the subsequent current density gradient shows that the coulombic efficiency is about 90 percent.
To SnS2The cycling stability of the electrode as a negative electrode material for sodium ion batteries was further investigated. FIG. 6 (d) shows 1A g-1The current density of the electrode. It can be observed from the figure that when 1Ag is used-1When the current density is subjected to constant-current charge-discharge circulation, the charge-discharge specific capacity of the first circle is extremely low, and the charge-discharge specific capacity is increased to 464.6mAhg after the second circle of circulation-1And 955.6mAhg-1Presumably, the capacity is increased only at the second turn, since the electrode is not fully activated at the first turn. After the 8 th circulation, the charging and discharging specific capacity is reduced to 200mAhg-1The following. After 100 cycles, SnS2The charging and discharging specific capacity of the electrode is maintained at 124.5mAhg-1And 125.1mAhg-1On the left and right, the coulombic efficiencies from the 10 th charge-discharge cycle are all greater than 98%, compared with the existing sodium ion battery, the SnS provided by the embodiment2Has obvious advantage of high coulomb efficiency on the sodium storage performance.
The test results above show that:
flake-like SnS2When the material is used as a negative electrode material of a lithium ion battery, the content of the Ag is 0.1Ag-1At a current density of (S), SnS2The electrode maintains a relatively high 1670.7mAhg-1Initial discharge capacity of (1) and maintained at 522.7 mAhg after 100 cycles of charge and discharge-1The reversible capacity of (a). Current density of 1Ag-1After circulating for 100 circles, the reversible specific capacity is 326.7 mAhg-1；
(di) sheet-like SnS2When the material is used as a negative electrode material of a sodium ion battery, the content of the Ag is 0.1Ag-1Has a current density of 1146.8mAhg-1The initial discharge capacity of (1) is maintained at 262.8mAhg after 100 charge-discharge cycles-1Specific discharge capacity of (2). When the current density is increased to 1Ag-1The specific discharge capacity is maintained at 125.1mAhg after 100 charge-discharge cycles-1。
Therefore, when the flaky tin disulfide material prepared by the simple hydrothermal method is applied to a lithium ion battery cathode material or a sodium ion battery cathode material, the flaky tin disulfide material can have a certain capacityLoss due to SnS2In the process of lithium/sodium desorption of the electrode material, the volume of the electrode material expands, so that the structure of the material is cracked to a certain degree, and the electrode material falls off from a current collector, so that the reversible specific capacity is reduced, and the action principle of the electrode is a common condition in a recyclable battery. However, the lithium ion/sodium ion battery using the electrode material has high reversibility in the charge-discharge cycle process, so that the battery has better stability, and the batteries can still maintain higher coulombic efficiency under the change of current density, so that the flaky tin disulfide has excellent rate performance.
The technical personnel in the field should know that the capacity loss is always a common characteristic in the field of energy storage, the capacity of the recyclable battery is gradually reduced after the recyclable battery is used for a long time, and the capacity reduction condition generated by the flaky tin disulfide material provided by the invention in application belongs to the range acceptable in the industry, but the flaky tin disulfide material is obviously superior to the existing lithium ion battery and sodium ion battery in stability and rate capability, so that the flaky tin disulfide prepared by the preparation method provided by the invention can generate a very large application value in the energy storage industry, can make a contribution to solving the energy crisis problem in the future, and meanwhile, the preparation method provided by the invention is relatively more than the existing SnS2The preparation method also has the advantages of lower energy consumption in the reaction process, higher production efficiency and more contribution to industrial production and application.
The above embodiments are preferred implementations of the present invention, and the present invention can be implemented in other ways without departing from the spirit of the present invention.
Some of the drawings and descriptions of the present invention have been simplified to facilitate the understanding of the improvements over the prior art by those skilled in the art, and some other elements have been omitted from this document for the sake of clarity, and it should be appreciated by those skilled in the art that such omitted elements may also constitute the subject matter of the present invention.

Claims (8)

1. The preparation method of the flaky tin disulfide is characterized by comprising the following steps of:
(1) taking a proper amount of stannous chloride dihydrate and thioacetamide, mixing, adding a proper amount of deionized water, and stirring to fully mix to obtain a mixed solution;
(2) adding a proper amount of ammonia water into the mixed solution to adjust the pH value of the mixed solution to 8-9;
(3) transferring the mixed solution after the pH value is adjusted to a reaction kettle, sealing the reaction kettle, performing hydrothermal treatment at the temperature of 110-130 ℃ until the reaction is finished, and taking out the reaction kettle after the reaction kettle is cooled to room temperature to obtain a product after the reaction;
(4) and washing and drying the product to obtain yellow powdery flaky tin disulfide.
2. The method for preparing the flaky tin disulfide according to claim 1, wherein: the mass ratio of the stannous chloride dihydrate to the thioacetamide is 1: 5.
3. the method for preparing the flaky tin disulfide according to claim 1, wherein: the stirring time in the step (1) is 20-40 minutes.
4. The method for preparing the flaky tin disulfide according to claim 1, wherein: the hydrothermal time in the step (3) is about 5-8 h.
5. The method for preparing the flaky tin disulfide according to claim 1, wherein: in the step (4), the drying is fully carried out at the temperature of 70-90 ℃.
6. A flaky tin disulfide prepared by the preparation method of any one of claims 1 to 5.
7. The use of the tin disulfide flakes of claim 6 in a negative electrode material for a lithium ion battery.
8. The use of the tin disulfide flakes of claim 6 in a negative electrode material for a sodium ion battery.
CN202110499597.9A 2021-05-08 2021-05-08 Flaky tin disulfide and preparation method and application thereof Pending CN113200565A (en)

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