CN112786858A - SnS2Preparation method of nano-sheet loaded graphene-based nano composite material - Google Patents

SnS2Preparation method of nano-sheet loaded graphene-based nano composite material Download PDF

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CN112786858A
CN112786858A CN202110071425.1A CN202110071425A CN112786858A CN 112786858 A CN112786858 A CN 112786858A CN 202110071425 A CN202110071425 A CN 202110071425A CN 112786858 A CN112786858 A CN 112786858A
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graphene
nano
sns
graphene oxide
composite material
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宋品
赵峰
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Anhui Guangte New Material Technology Co ltd
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Anhui Guangte New Material Technology Co ltd
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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
    • 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
    • H01M10/054—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
    • H01M4/58—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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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 SnS2The preparation method of the nano-sheet loaded graphene-based nano composite material comprises the following steps: step 1: dispersing graphene oxide nanosheets in deionized water to prepare a graphene oxide solution; step 2: dissolving tin tetrachloride in deionized water, and adding thiourea as a sulfur source and a reducing agent; and step 3: adding the graphene oxide solution obtained in the step 1 into the solution obtained in the step 2, and performing mixing treatment by ultrasonic waves; transferring the mixture of the two solutions after ultrasonic treatment into a hydrothermal reaction kettle for reactionObtaining a precipitate; and 4, step 4: and (4) centrifuging, washing, drying and grinding the precipitate obtained in the step (3) to obtain the graphene nanosheet/tin disulfide composite nanomaterial. The graphene nanosheet/tin disulfide composite nanomaterial prepared by the method has high capacity and stability when used as a sodium storage electrode material.

Description

SnS2Preparation method of nano-sheet loaded graphene-based nano composite material
Technical Field
The invention relates to the technical field of energy storage and conversion, in particular to SnS2A preparation method of a nano-sheet loaded graphene-based nano composite material.
Background
With the development of modern new energy automobiles and smart grids, novel chemical power sources play an important role in human development. Conventional secondary batteries, such as lead-acid batteries, have limited applications because they contain a harmful metallic element, Pb. The lithium ion battery has excellent performances of high specific energy, no memory effect, environmental friendliness and the like, but because the safety of the lithium ion battery is not well solved all the time and the lithium resource is limited, the wide application of the lithium ion battery still has a lot of work to be done.
With the development of new energy automobiles and the large-scale application of energy storage batteries, a secondary battery with high capacity, low price and environmental friendliness is urgently needed to be found. Because of the small radius of sodium ions, some compounds are easily intercalated and deintercalated into a layered structure. Meanwhile, sodium has the advantages of low price, high specific energy, environmental friendliness and the like. Therefore, sodium ion batteries are being more and more extensively explored. However, there are still many problems to date as an electrode material for electrochemical sodium storage with high performance, and the performance of the electrode material needs to be improved and improved.
The two-dimensional nano material has unique appearance and excellent characteristics, and the graphene serving as the most typical two-dimensional material has unique two-dimensional structure and numerous excellent characteristics, so that the graphene has important scientific research significance and wide application prospect. The graphene has high specific surface area, high conductivity, high heat conductivity, excellent mechanical properties and the like, and the characteristics enable the graphene to have wide application prospects in the fields of electronic devices, catalyst materials, electrochemical energy storage and energy sources.
Tin disulfide has a structure similar to graphene, with covalent bonds within the layers, and weak van der waals forces between the layers. The weaker interlayer forces and larger interlayer spacings of tin disulfide allow the introduction of foreign atoms between its layers by intercalation reactions. This advantage encourages the tin disulfide material to act as the host material for the intercalation reaction. Thus, tin disulfide is a promising electrode material for electrochemical sodium storage. However, the electrochemical sodium storage capacity of the common tin disulfide nano material is low, and the practical application cannot be met.
Two-dimensional nanomaterials have many excellent properties, which have attracted researchers' extensive attention, such as single or few layers of transition metal disulfides. For the transition metal disulfide of a layered structure, as the number of layers thereof is reduced, the band structure or electronic properties thereof are significantly changed, thereby causing it to exhibit physical or chemical characteristics different from those of the corresponding bulk material. Research shows that the tin disulfide with a few layers has better electrochemical sodium storage performance.
Because the tin disulfide and the graphene have similar two-dimensional nanosheet structures, the tin disulfide and the graphene have good similarity in microscopic morphology. The graphene and the tin disulfide nanosheet are compounded, so that the high conductivity of the graphene can improve the conductivity of the composite material, enhance the electron transfer in the reaction process of the sodium storage electrode and improve the electrochemical sodium storage performance of the composite material.
Disclosure of Invention
The invention aims to provide SnS2The graphene nanosheet/tin disulfide composite nanomaterial prepared by the method has high capacity and stability when used as a sodium storage electrode material, and is used for solving the technical problems in the background technology.
The invention adopts the technical scheme that the SnS2The preparation method of the nano-sheet loaded graphene-based nano composite material comprises the following steps:
step 1: dispersing graphene oxide nanosheets in deionized water to prepare a graphene oxide solution;
step 2: dissolving tin tetrachloride in deionized water, and adding thiourea as a sulfur source and a reducing agent;
and step 3: adding the graphene oxide solution obtained in the step 1 into the solution obtained in the step 2, and performing mixing treatment by ultrasonic waves; transferring the mixture of the two solutions subjected to ultrasonic treatment into a hydrothermal reaction kettle for reaction to obtain a precipitate;
and 4, step 4: and (4) centrifuging, washing, drying and grinding the precipitate obtained in the step (3) to obtain the graphene nanosheet/tin disulfide composite nanomaterial.
In a preferred embodiment, the concentration of the graphene oxide in the step 1 is 5-10 mg/ml.
In a preferred embodiment, the mass ratio of the tin tetrachloride to the thiourea in the step 2 is 1 to 2.
In a preferred embodiment, the time of the ultrasonic treatment in the step 3 is 1-2h, the reaction temperature in the hydrothermal reaction kettle is 200-220 ℃, and the reaction time is 24-36 h.
The technical scheme of the invention has the beneficial effects that:
1. the preparation method is simple, common raw material reagents are low in cost, simple and easy to implement, and good in stability, the sodium storage composite electrode material with uniform loading capacity is successfully prepared by using a one-step hydrothermal method, the heating temperature adopted by experimental hydrothermal is safe and easy to realize, and the method is suitable for large-scale production.
2. The graphene nanosheet/tin disulfide composite nanomaterial prepared by the method has high activity and large specific surface area, has a folded sheet structure similar to graphene oxide, and is high in stability because tin disulfide is uniformly dispersed on a folded thin graphene sheet layer.
Drawings
FIG. 1 shows an SnS of the present invention2Scanning electron micrographs of/Graphene samples,
FIG. 2 shows an SnS of the present invention2、SnS2X-ray diffraction pattern (XRD) of the/Graphene sample,
FIG. 3 shows an SnS of the present invention2Scanning energy spectrum mapping graph of/Graphene sample,
FIG. 4 shows an embodiment of the present invention SnS2、SnS2Charge and discharge curves for the/Graphene sample.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments. The embodiments of the present invention have been presented for purposes of illustration and description, and are not intended to be exhaustive or limited to the invention in the form disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art. The embodiment was chosen and described in order to best explain the principles of the invention and the practical application, and to enable others of ordinary skill in the art to understand the invention for various embodiments with various modifications as are suited to the particular use contemplated.
The invention adopts the technical scheme that the SnS2The preparation method of the nano-sheet loaded graphene-based nano composite material comprises the following steps:
step 1: dispersing graphene oxide nanosheets in deionized water to prepare a graphene oxide solution;
step 2: dissolving tin tetrachloride in deionized water, and adding thiourea as a sulfur source and a reducing agent;
and step 3: adding the graphene oxide solution obtained in the step 1 into the solution obtained in the step 2, and performing mixing treatment by ultrasonic waves; transferring the mixture of the two solutions subjected to ultrasonic treatment into a hydrothermal reaction kettle for reaction to obtain a precipitate;
and 4, step 4: and (4) centrifuging, washing, drying and grinding the precipitate obtained in the step (3) to obtain the graphene nanosheet/tin disulfide composite nanomaterial.
The concentration of the graphene oxide in the step 1 is 5-10 mg/ml. The mass ratio of the tin tetrachloride to the thiourea in the step 2 is 1-2. The usage amount of the deionized water in the step 1 and the step 2 is not particularly limited, and the graphene oxide and the tin tetrachloride can be dissolved.
The ultrasonic treatment time in the step 3 is 1-2h, and the purpose of the ultrasonic treatment is to fully disperse the graphene oxide in the tin disulfide solution. The reaction temperature in the hydrothermal reaction kettle is 200-220 ℃, and the reaction time is 24-36 h.
The graphene nanosheet/tin disulfide composite nanomaterial prepared by the method has a chemical expression of SnS2Graphene) as an electrode material, and the obtained battery has better performance. The graphene is used as a conductive substrate, so that the electron transfer in the sodium storage electrode reaction process can be enhanced, and the improvement of the battery performance is promoted.
The graphene nanosheet/tin disulfide composite nanomaterial (SnS) prepared by the method is combined with comparative example through experimental data and attached drawings2/Graphene) for further elucidation.
Comparative example a tin disulfide nanomaterial was prepared as follows:
1. dissolving 1 g of stannic chloride in 30 ml of deionized water, and adding 1.8 g of thiourea as a sulfur source and a reducing agent;
2. carrying out ultrasonic treatment on the solution in the step 1 for 1-2h, transferring the mixture into a hydrothermal reaction kettle, and reacting for 24-36h at the temperature of 200-220 ℃;
3. and centrifuging, washing, drying and grinding the precipitate obtained by the reaction of the step 2 to obtain the tin disulfide nano material.
The analytical results were as follows: the appearance of the sample is shown by an SEM characterization method, and the result is shown in figure 1, namely tin disulfide (SnS)2) The nano-sheets are uniformly loaded on the graphene substrate. The prepared sample was examined by XRD, and the result is shown in fig. 2, which shows the same characteristic peak, i.e., the same structure. SnS by mapping spectrum2The characterization of the/Graphene sample shows that the result is shown in fig. 3, the sample contains carbon, oxygen, tin and sulfur elements, the atomic ratio of the elements is analyzed, the atomic ratio of tin to sulfur is 1:2, and the result is shown in the following table 1:
element(s) Atomic percent (%)
C 71.09
O 3.53
S 17.18
Sn 8.20
Total amount of 100
TABLE 1
From the charge-discharge curve of the sample, fig. 4 shows that: SnS2the/Graphene has higher capacity and cycling stability when being used as an electrochemical sodium storage composite electrode material.
According to the preparation method and the comparative example, the SnS2 nanosheet loaded graphene-based nanocomposite material prepared by the method has high capacity and cycling stability when being used as an electrochemical sodium storage composite electrode material.
It is to be understood that the described embodiments are merely a few embodiments of the invention, and not all embodiments. All other embodiments, which can be derived by one of ordinary skill in the art and related arts based on the embodiments of the present invention without any creative effort, shall fall within the protection scope of the present invention. Structures, devices, and methods of operation not specifically described or illustrated herein are generally practiced in the art without specific recitation or limitation.

Claims (4)

1. SnS2The preparation method of the nano-sheet loaded graphene-based nano composite material is characterized by comprising the following steps:
step 1: dispersing graphene oxide nanosheets in deionized water to prepare a graphene oxide solution;
step 2: dissolving tin tetrachloride in deionized water, and adding thiourea as a sulfur source and a reducing agent;
and step 3: adding the graphene oxide solution obtained in the step 1 into the solution obtained in the step 2, and performing mixing treatment by ultrasonic waves; transferring the mixture of the two solutions subjected to ultrasonic treatment into a hydrothermal reaction kettle for reaction to obtain a precipitate;
and 4, step 4: and (4) centrifuging, washing, drying and grinding the precipitate obtained in the step (3) to obtain the graphene nanosheet/tin disulfide composite nanomaterial.
2. The SnS of claim 12The preparation method of the nano-sheet loaded graphene-based nano composite material is characterized in that the concentration of the graphene oxide in the step 1 is 5-10 mg/ml.
3. The SnS of claim 12The preparation method of the nano-sheet loaded graphene-based nano composite material is characterized in that the mass ratio of the tin tetrachloride to the thiourea in the step 2 is 1-2.
4. The SnS of claim 12The preparation method of the nano-sheet loaded graphene-based nano composite material is characterized in that the ultrasonic treatment time in the step 3 is 1-2h, the reaction temperature in the hydrothermal reaction kettle is 200-220 ℃, and the reaction time is 24-36 h.
CN202110071425.1A 2021-01-19 2021-01-19 SnS2Preparation method of nano-sheet loaded graphene-based nano composite material Pending CN112786858A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113772718A (en) * 2021-09-09 2021-12-10 西安建筑科技大学 SnS-SnS2@ GO heterostructure composite material and preparation method and application thereof
CN115425204A (en) * 2022-09-21 2022-12-02 陕西科技大学 Biomass pine derived carbon PDC/SnS 2 @ rGO material and preparation method and application thereof

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CN106654192A (en) * 2016-08-13 2017-05-10 华南理工大学 Tin sulfide/graphene sodium ion battery composite cathode material and preparation method thereof
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113772718A (en) * 2021-09-09 2021-12-10 西安建筑科技大学 SnS-SnS2@ GO heterostructure composite material and preparation method and application thereof
CN113772718B (en) * 2021-09-09 2022-11-22 西安建筑科技大学 SnS-SnS 2 @ GO heterostructure composite material and preparation method and application thereof
CN115425204A (en) * 2022-09-21 2022-12-02 陕西科技大学 Biomass pine derived carbon PDC/SnS 2 @ rGO material and preparation method and application thereof
CN115425204B (en) * 2022-09-21 2024-03-29 陕西科技大学 Biomass pine derived carbon PDC/SnS 2 @rGO material and preparation method and application thereof

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