CN112599746B - Preparation method and application of sulfur-doped tin disulfide/tin dioxide @ C/rGO material - Google Patents

Preparation method and application of sulfur-doped tin disulfide/tin dioxide @ C/rGO material Download PDF

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CN112599746B
CN112599746B CN202011482142.8A CN202011482142A CN112599746B CN 112599746 B CN112599746 B CN 112599746B CN 202011482142 A CN202011482142 A CN 202011482142A CN 112599746 B CN112599746 B CN 112599746B
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sulfur
sncl
washing
rgo
tin
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CN112599746A (en
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金双玲
古飞蛟
钱晨亮
贾培宇
韦家卿
孙学乾
韩奇
杭加旺
王晓瑞
金鸣林
张睿
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Shanghai Institute of 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
    • 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
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/387—Tin or alloys based on tin
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • 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
    • 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
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a preparation method of a sulfur-doped tin disulfide/tin dioxide @ C/rGO material and application of the sulfur-doped tin disulfide/tin dioxide @ C/rGO material in a lithium ion battery. The preparation method comprises the following steps: SnCl2Dissolving in concentrated HCl to form stable SnCl2A solution; SnCl2Mixing the solution, GO colloid, thiourea, L-ascorbic acid and the like, and stirring to form a uniform mixed solution; carrying out water bath negative pressure evaporation on the mixed solution, and then carrying out hydrothermal treatment to obtain a precursor; cooling the hydrothermal kettle to room temperature, centrifuging the precursor, and washing the obtained precipitate with water and alcohol in sequence; the precipitate was transferred again to the hydrothermal kettle and H was added2O2And (3) performing hydrothermal treatment again, after the sample in the kettle is cooled to room temperature, centrifuging, washing with water, washing with alcohol, and freeze-drying the obtained precipitate to obtain the sulfur-doped tin disulfide/tin dioxide @ C/rGO material. The method is simple to operate, environment-friendly and low in energy consumption, and the prepared nano composite electrode material has excellent electrochemical performance.

Description

Preparation method and application of sulfur-doped tin disulfide/tin dioxide @ C/rGO material
Technical Field
The invention relates to a sulfur-doped SnS2/SnO2A preparation method and application of a @ C/rGO electrode belong to the technical field of new energy materials.
Background
The lithium ion battery has the advantages of high energy density, long service life, low self-discharge and the like. These advantages have led to the widespread use of lithium ion batteries in portable electronic products. In recent years, with the development of society, environmental and energy problems are increasingly highlighted; this makes the application of lithium ion batteries more concentrated on electric vehicles and smart grids, which puts higher demands on their energy density and power density. However, the theoretical lithium storage capacity of the commercial anode material graphite is limited (372mAh/g), and the requirement of high energy and high power density is far from being met, so that the development of a high-capacity lithium ion battery anode material becomes a hot spot of current research.
SnO2As one of the candidates for the negative electrode material of the lithium ion battery, attention is paid due to its high theoretical capacity (783mAh/g), low intercalation potential (lower than graphite), and high storage abundance. However, SnO2Some inherent defects also limit the application of the lithium ion battery in the field of negative electrodes, such as low electron mobility, large volume expansion (250%), high irreversible capacity and the like. Recently SnS2Has received wide attention of researchers, on one hand, due to SnS2Low cost, safe use, large theoretical capacity and specific SnO2Higher conductivity of (B), on the other hand CdI2SnS of layered structure2The rapid de-intercalation of lithium ions is facilitated, and the advantages enable SnS2Specific SnO2Has better electrochemical performance. However, SnS2Do alone asIn the case of the negative electrode of a lithium ion battery, there is still a large volume expansion, which also leads to SnS2Powdering failure of the electrode. SnO2Has high capacity, and SnS2The development of tin and tin-based compounds is important to realize good cyclability while ensuring capacity. In recent years, the construction of a heterojunction has become a popular means for modifying materials, and the function of the heterojunction is to form an internal electric field between two phases and enable electrons to accumulate in a metal region, thereby further improving the conductivity and electrochemical reaction kinetics of the materials. Thus when SnS is used2And SnO2By complexing to SnS2/SnO2The electron transfer kinetics of the interface can be effectively improved during heterojunction, and the electrochemical performance of the electrode is further improved. The graphene is represented by a carbon atom in sp2Two-dimensional materials formed by hybridization have been widely studied for their excellent optical, electrical and thermal properties. When the graphene and SnS are mixed2/SnO2After heterojunction recombination, on one hand, electron migration of the composite material can be further improved due to excellent conductivity of graphite, and on the other hand, the specific surface area reported by graphene can effectively buffer SnS2/SnO2Volume expansion of the heterojunction during lithium deintercalation. Based on the advantages, the introduction of the graphene can effectively improve the electrochemical performance of the electrode.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: provides a sulfur-doped SnS with higher electrochemical performance2/SnO2@ C/rGO material.
In order to solve the technical problem, the invention provides a preparation method of a sulfur-doped tin disulfide/tin dioxide @ C/rGO material, which is characterized by comprising the following steps of:
step 1): SnCl2Dissolving in concentrated HCl to form stable SnCl2A solution;
step 2): SnCl2Mixing the solution, GO colloid, thiourea, L-ascorbic acid and distilled water, and stirring to form a uniform mixed solution;
step 3): carrying out water bath negative pressure evaporation on the mixed solution obtained in the step 2), and then transferring the mixed solution into a hydrothermal kettle for hydrothermal treatment to obtain a precursor;
step 4): cooling the hydrothermal kettle to room temperature, centrifuging the precursor, and washing the obtained precipitate with water and alcohol in sequence;
step 5): transferring the precipitate obtained in the step 4) to a hydrothermal kettle again, and adding H2O2And (3) performing hydrothermal treatment again, after the sample in the kettle is cooled to room temperature, centrifuging, washing with water and washing with alcohol according to the process same as the step 4), and freeze-drying the obtained precipitate to obtain the sulfur-doped tin disulfide/tin dioxide @ C/rGO material.
Preferably, SnCl is used in the step 1)2The mass concentration of the solution was 37%.
Preferably, SnCl in the step 2)2The mass ratio of GO colloid to thiourea to L-ascorbic acid to distilled water is 1:1.07:5: 78.6.
Preferably, the hydrothermal treatment in step 3) is carried out until the volume is reduced to 100 mL.
Preferably, ethanol is used for the alcohol washing in the step 4).
Preferably, the precipitation in step 5) is performed with H2O2The mass ratio of (A) to (B) is 6: 1.
The invention also provides application of the sulfur-doped tin disulfide/tin dioxide @ C/rGO material prepared by the preparation method of the sulfur-doped tin disulfide/tin dioxide @ C/rGO material in a lithium ion battery.
The invention utilizes a vulcanization-oxidation method to prepare the SnS doped with sulfur2/SnO2@ C/rGO nanocomposite electrode material in which SnS is present2And SnO2The close contact realizes the rapid transfer of electrons, and the introduction of the L-ascorbic acid not only promotes the SnS2And also forms a cross-linked carbon network while reducing GO and a heterojunction SnS2/SnO2Firmly anchored to the rGO sheet. In addition, the doping of sulfur in the GO sheet layer greatly increases the electron-withdrawing capability of the GO sheet layer, and further improves the electron transfer rate of the matrix GO. The SnS has the characteristics of composition and structure2/SnO2@ C/rGO shows excellent electrochemical performance at a current density of 0.1C (78.3mA/g)Lower SnS2/SnO2The specific discharge capacity of @ C/rGO for the first time is 1947.5mAh/g, the reversible discharge capacity of 1249mAh/g is still obtained after the capacitor is cycled to 120 times, and the discharge capacity of 1070mAh/g is still obtained after the capacitor is further cycled to 100 times under the current intensity of 0.5C (391.5mAh/g) of large current, which shows that the SnS doped with sulfur has the discharge capacity of 1070mAh/g2/SnO2The @ C/rGO nano composite electrode has excellent electrochemical performance.
Compared with the prior art, the invention has the beneficial effects that:
the invention uses SnCl2The sulfur-doped SnS is prepared by taking L-ascorbic acid, Graphene Oxide (GO) and thiourea as raw materials and adopting a negative pressure evaporation method and a two-step hydrothermal method2/SnO2@ C/rGO nanocomposites. Using SnS2/SnO2The conductivity of the electrode is effectively improved by the heterojunction and the sulfur-doped graphene, and the diffusion of Sn atoms is effectively inhibited by the crosslinked amorphous carbon, so that the electrode has more excellent cycle performance, and the flexible rGO sheet layer effectively buffers SnS2/SnO2Volume expansion of the heterojunction during lithium deintercalation. Thus, SnS2/SnO2The @ C/rGO nano-composite electrode shows excellent electrochemical performance.
Drawings
FIG. 1 shows the sulfur-doped SnS obtained in example 12/SnO2TEM of @ C/rGO material in different proportions;
FIG. 2 shows the sulfur-doped SnS obtained in example 12/SnO2XRD of @ C/rGO materials;
FIG. 3 shows the sulfur-doped SnS obtained in example 12/SnO2The peak separation fitting spectrum of XPS high-precision spectrum S2p of @ C/rGO material;
FIG. 4 shows sulfur-doped SnS prepared in example 12/SnO2The charge-discharge curve of @ C/rGO material at 0.1C (78.3mA/g) current density;
FIG. 5 shows the sulfur-doped SnS obtained in example 12/SnO2The cycling profile of the @ C/rGO material at a current density of 0.5C (391.5 mA/g).
Detailed Description
In order to make the invention more comprehensible, preferred embodiments are described in detail below with reference to the accompanying drawings.
Each raw material used in example 1 was a commercially available product.
Example 1
Sulfur-doped SnS2/SnO2The preparation method of the @ C/rGO nano composite material comprises the following specific steps:
(1) 0.5g SnCl was weighed2Dissolved in 0.4mL of concentrated HCl (the mass concentration is 37 percent) and stirred uniformly to form SnCl2Acid liquor;
(2) 0.4mL of SnCl2Adding acid solution into 343mL of distilled water, simultaneously adding 267.5mg of L-ascorbic acid, and magnetically stirring until the L-ascorbic acid is completely dissolved; finally, 107mL of GO colloid (with the concentration of 5mg/mL) and 50mL of thiourea solution (50mg/mL) are added into the solution, and the mixture is uniformly stirred to form a mixed solution A;
(3) putting the solution A obtained in the step (2) into a water bath kettle at the temperature of 80 ℃, carrying out negative pressure evaporation on the solution A under the pressure of-0.1 Pa, transferring the formed gel into a hydrothermal kettle to carry out evaporation at the temperature of 1 ℃ for min after the solution A is evaporated to 100mL-1The temperature rising rate of the reaction is at 180 ℃, the hydrothermal is carried out for 15 hours,
(4) when the hydrothermal kettle is cooled to room temperature, pouring the precursor in the polytetrafluoroethylene inner container into a centrifuge cup for sequentially centrifuging, washing with water and washing with ethanol;
(5) transferring the precursor precipitate obtained by centrifugation in the step 4 into a hydrothermal kettle again, and adding 40mL of H with the mass concentration of 0.375%2O2Solution, also at 1 ℃ min-1The temperature rising rate of (2) is at 180 ℃ and the hydrothermal is carried out for 12 hours. And after the sample in the kettle is cooled to room temperature, centrifuging and washing with water and ethanol for several times according to the same process as the step 4, and finally freeze-drying the obtained precipitate (the temperature of a cold trap is-59 ℃ and drying is carried out for 48 hours) to obtain the sulfur-doped SnS2/SnO2@ C/rGO nano-composite electrode material.
The samples prepared in this example were subjected to further characterization and analysis, the results of which are shown in FIGS. 1-5. SnS is visible in FIG. 12And SnO2Corresponding to the lattice fringes of the crystal planes. FIG. 2 further shows that the phase composition of the prepared samples is hexagonal SnS2(JCPSDS No.23-0677) and tetragonal SnO2(JCPSDS No. 41-1445). As can be seen in FIG. 3, a pair of fitted doublets appeared at 163.1eV and 163.9eV, which corresponds to the characteristic peak for C-S-C, indicating successful doping of S into rGO. As can be seen from FIG. 4, SnS2/SnO2The initial discharge specific capacity of @ C/rGO is 1947.5mAh/g, and the reversible discharge capacity of 1249mAh/g is still obtained after circulation is carried out for 120 times. As can be seen from FIG. 5, even at a large current density of 391.5mA/g, SnS2/SnO 2100 cycles of @ C/rGO still have reversible discharge capacities of 1070mAh/g, these results indicate that the sulfur-doped SnS2/SnO2The @ C/rGO nano composite material is successfully synthesized, and has excellent electrochemical performance.

Claims (7)

1. A preparation method of a sulfur-doped tin disulfide/tin dioxide @ C/rGO material is characterized by comprising the following steps:
step 1): SnCl2Dissolving in concentrated HCl to form stable SnCl2A solution;
step 2): SnCl2Mixing the solution, GO colloid, thiourea, L-ascorbic acid and distilled water, and stirring to form a uniform mixed solution;
step 3): carrying out water bath negative pressure evaporation on the mixed solution obtained in the step 2), and then transferring the mixed solution into a hydrothermal kettle for hydrothermal treatment to obtain a precursor;
step 4): cooling the hydrothermal kettle to room temperature, centrifuging the precursor, and washing the obtained precipitate with water and alcohol in sequence;
step 5): transferring the precipitate obtained in the step 4) to a hydrothermal kettle again, and adding H2O2And (3) performing hydrothermal treatment again, after the sample in the kettle is cooled to room temperature, centrifuging, washing with water and washing with alcohol according to the process same as the step 4), and freeze-drying the obtained precipitate to obtain the sulfur-doped tin disulfide/tin dioxide @ C/rGO material.
2. The method of claim 1, wherein the concentrated HCl concentration of step 1) is 37% by mass.
3. The method of claim 1, wherein the SnCl in step 2) is SnCl, and wherein the SnCl is a tin disulfide/tin dioxide @ C/rGO material2The mass ratio of GO colloid to thiourea to L-ascorbic acid to distilled water is 1:1.07:5:0.535: 686.
4. The method of claim 1, wherein the negative pressure evaporation in step 3) is reduced to a volume of 100 mL.
5. The method of claim 1, wherein ethanol is used for the alcohol washing in step 4).
6. The method of claim 1, wherein the step 5) comprises precipitating with H and forming a tin disulfide/tin dioxide @ C/rGO material2O2The mass ratio of (A) to (B) is 6: 1.
7. Use of the sulfur-doped tin disulfide/tin dioxide @ C/rGO material prepared by the process of any one of claims 1 to 6 in a lithium ion battery.
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CN113991084A (en) * 2021-10-27 2022-01-28 西安建筑科技大学 SnS-SnO2-GO @ C heterostructure composite material and preparation method and application thereof
CN114420926B (en) * 2022-01-19 2024-03-15 湖北亿纬动力有限公司 Positive electrode host material and preparation method and application thereof

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