CN109286011B - Preparation method of tin disulfide/vertical graphene nanosheet array electrode - Google Patents

Preparation method of tin disulfide/vertical graphene nanosheet array electrode Download PDF

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CN109286011B
CN109286011B CN201811140062.7A CN201811140062A CN109286011B CN 109286011 B CN109286011 B CN 109286011B CN 201811140062 A CN201811140062 A CN 201811140062A CN 109286011 B CN109286011 B CN 109286011B
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vertical graphene
tin disulfide
array electrode
nanosheet array
graphene nanosheet
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CN109286011A (en
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陈明华
张家伟
陈庆国
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Harbin University of Science and Technology
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Harbin University of Science and Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • 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
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • 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

A preparation method of a tin disulfide/vertical graphene nanosheet array electrode belongs to a preparation method of a flexible electrode. According to the method, vertical graphene grows on carbon cloth by using a plasma enhanced chemical vapor deposition method, and after the reaction is finished, the vertical graphene is cooled to room temperature for later use; dissolving tin tetrachloride pentahydrate in n-butanol under the condition of stirring, then adding thioacetamide, and stirring to obtain a carrier solution for later use; and immersing the prepared vertical graphene substrate into the prepared carrier solution for hydrothermal reaction, taking out the obtained product after the reaction, cleaning and drying to obtain the tin disulfide/vertical graphene nanosheet array electrode. The vertical graphene prepared by the plasma enhanced chemical vapor deposition method has the characteristic of high conductivity of the carbon-based material, and has a porous grid structure. The vertical graphene has good conductivity, high porosity, low density, large specific surface area and excellent electrochemical performance.

Description

Preparation method of tin disulfide/vertical graphene nanosheet array electrode
Technical Field
The invention belongs to a preparation method of an ion battery electrode, and particularly relates to a preparation method of a tin disulfide/vertical graphene nanosheet array electrode.
Background
With the increasing demand of electronic devices, some disadvantages of lithium ion batteries, such as resource shortage and high cost, are gradually exposed, and researchers are gradually looking at sodium ion batteries. The electrode material plays a vital role in the performance of the sodium-ion battery, and particularly, the cathode material is used, so that the research and preparation of the cathode material suitable for the sodium-ion battery are particularly important.
The transition metal sulfide has high theoretical specific capacity and is a good candidate for a sodium ion battery cathode material, but the low conductivity enables the metal sulfide to have poor cycle performance and rate capability, and meanwhile, the transition metal sulfide electrode material has the defect of large volume expansion which is not negligible in the charging and discharging process of the sodium ion battery. In order to solve the above problems, a metal sulfide is often compounded with a carbon-based material to improve the conductivity of the active material, and a porous array structure is prepared to effectively increase the buffer space of the active material to suppress the volume expansion of the active material during charge and discharge. The selection of carbon-based materials becomes a key point, and the carbon-based materials commonly used at present mainly include carbon nanotubes, redox graphene, carbon nanospheres and the like, but none of the carbon materials can meet the requirement of porosity.
Disclosure of Invention
The invention aims to provide a preparation method of a tin disulfide/vertical graphene nanosheet array electrode.
The invention is realized by the following technical scheme:
a preparation method of a tin disulfide/vertical graphene nanosheet array electrode comprises the following steps:
step 1, preparing a vertical graphene electrode, growing vertical graphene on carbon cloth by using a plasma enhanced chemical vapor deposition method, and cooling to room temperature after the reaction is finished for later use;
step 2, preparing a carrier solution, dissolving tin tetrachloride pentahydrate in n-butanol under the condition of stirring, then adding thioacetamide, and stirring to obtain the carrier solution for later use;
and 3, preparing a tin disulfide/vertical graphene nanosheet array electrode, immersing the vertical graphene electrode prepared in the step 1 into the carrier solution prepared in the step 2 for hydrothermal reaction, taking out after the hydrothermal reaction, cleaning, and drying to prepare the tin disulfide/vertical graphene nanosheet array electrode.
According to the preparation method of the tin disulfide/vertical graphene nanosheet array electrode, carbon cloth in step 1 is that carbon fibers in the carbon cloth are 8-10 microns in diameter, and the surface is smooth and free of holes.
According to the preparation method of the tin disulfide/vertical graphene nanosheet array electrode, in the step 1, the step of growing the vertical graphene on the carbon cloth through chemical vapor deposition is that when the pressure of a cabin reaches 10mTorr, the carbon cloth is placed into the cabin, then when the temperature is raised to 400 ℃, hydrogen and methane are introduced, and the flow rate ratio of the hydrogen to the methane is 3: 2, the plasma generator power is 550W, and the reaction time is 2 h.
According to the preparation method of the tin disulfide/vertical graphene nanosheet array electrode, in the step 1, in the process of growing vertical graphene on carbon cloth through chemical vapor deposition, the hydrogen flow is 90sccm, and the methane flow is 60 sccm.
The invention relates to a preparation method of a tin disulfide/vertical graphene nanosheet array electrode, wherein in the step 2, the mass ratio of tin tetrachloride pentahydrate to n-butyl alcohol to thioacetamide is 2-3: 140-150: 1.5 to 2.
The invention relates to a preparation method of a tin disulfide/vertical graphene nanosheet array electrode, wherein in the step 2, the mass ratio of tin tetrachloride pentahydrate to n-butanol to thioacetamide is 2.16: 148.18: 1.84.
the preparation method of the tin disulfide/vertical graphene nanosheet array electrode, disclosed by the invention, has the advantage that the stirring time in the step 2 is 15-30 min.
According to the preparation method of the tin disulfide/vertical graphene nanosheet array electrode, in the step 3, the vertical graphene electrode is immersed in a carrier solution.
According to the preparation method of the tin disulfide/vertical graphene nanosheet array electrode, in the step 3, hydrothermal reaction is carried out for 24 hours under the condition of 180 ℃.
According to the preparation method of the tin disulfide/vertical graphene nanosheet array electrode, in the step 3, deionized water is used for cleaning for 3-5 times, then absolute ethyl alcohol is used for cleaning for 3-5 times, and the drying temperature after cleaning is 60 ℃.
According to the preparation method of the tin disulfide/vertical graphene nanosheet array electrode, the prepared tin disulfide nanosheets uniformly cover the vertical graphene substrate, are uniform and stable in appearance, do not contain substances with other structural appearances, and vertically grow on the top of the vertical graphene; the thickness of the tin disulfide nanosheets is about 128nm, the length of the tin disulfide nanosheets is about 1 μm, and meanwhile, the tin disulfide nanosheets are mutually connected to form a grid-shaped structure; ultrathin tin disulfide nanosheets in the prepared tin disulfide/vertical graphene nanosheet array electrode are mutually connected.
According to the preparation method of the tin disulfide/vertical graphene nanosheet array electrode, the tin disulfide/vertical graphene nanosheet array electrode prepared by the preparation method of the tin disulfide/vertical graphene nanosheet array electrode is assembled into a button cell, the assembling process is carried out in a glove box, and the assembling sequence is as follows: the lithium ion battery comprises a positive electrode shell, an electrode material, electrolyte, a diaphragm, electrolyte, a sodium sheet, foamed nickel, electrolyte and a negative electrode shell. Then packaging with packaging machine to complete the assembly of the battery, and performing cycle performance test with current density of 100mAg-1The first-circle discharge specific capacity can be up to 1160mAhg-1(ii) a When the current density is 1Ag-1Specific discharge capacity of 897mAhg-1(ii) a When the current density is as high as 5Ag-1In this case, 727mAhg of electrode can be maintained-1The capacity of (c). The current density returns to the low current of 1Ag again-1The discharge specific capacity is recovered to 879mAhg-1The discharge specific capacity is substantially restored to the capacity before rapid charge and discharge.
According to the preparation method of the tin disulfide/vertical graphene nanosheet array electrode, the vertical graphene prepared by a Plasma Enhanced Chemical Vapor Deposition (PECVD) method has the characteristic of high conductivity of a carbon-based material, and the vertical graphene has a porous grid structure. The vertical graphene has good conductivity, high porosity, low density and large specific surface area, and the prepared tin disulfide/vertical graphene nanosheet array electrode has excellent performance.
Drawings
FIG. 1 is an SEM image of carbon fibers in a carbon cloth used in a method according to an embodiment at 1000 times magnification;
fig. 2 is an SEM image of a vertical graphene electrode prepared by a method according to an embodiment, at 2000 times magnification;
fig. 3 is an SEM image of a vertical graphene electrode prepared by a method according to an embodiment, at 5000 x magnification;
fig. 4 is an SEM image of a tin disulfide/vertical graphene nanoplate array electrode prepared by a method according to an embodiment at 3000 times magnification;
fig. 5 is an SEM image of 13000 times larger than the tin disulfide/vertical graphene nanoplate array electrode prepared by the method according to the first embodiment;
fig. 6 is an SEM image of 40000 times magnification of a tin disulfide/vertical graphene nanoplatelet array electrode prepared by a method according to an embodiment;
FIG. 7 is a TEM image of 10000 times enlargement of tin disulfide nanosheets on a tin disulfide/vertical graphene nanosheet array electrode prepared by a method according to one embodiment;
fig. 8 is a TEM image of 20000 times magnified tin disulfide nanoplatelets on a tin disulfide/vertical graphene nanoplatelet array electrode prepared by a method according to an embodiment;
FIG. 9 is a HRTEM image of 400000 times magnification of tin disulfide nanoplatelets on a tin disulfide/vertical graphene nanoplatelet array electrode prepared by a method according to an embodiment;
fig. 10 is an electron diffraction pattern of tin disulfide nanoplatelets on a tin disulfide/vertical graphene nanoplatelet array electrode prepared by a method according to an embodiment;
fig. 11 is an XRD test curve of the array electrode of tin disulfide/vertical graphene nanoplatelets prepared by the method of the embodiment;
fig. 12 is a raman spectrum of a tin disulfide/vertical graphene nanoplate array electrode prepared by a method of an embodiment;
fig. 13 is a cyclic voltammetry curve of a tin disulfide/vertical graphene nanoplate array electrode prepared by a method according to an embodiment;
fig. 14 is a cycle number charge-discharge capacity curve of a tin disulfide/vertical graphene nanosheet array electrode prepared by a method according to an embodiment;
fig. 15 is an ac impedance contrast plot of a tin disulfide/vertical graphene nanoplate array electrode prepared by a method of an embodiment with pure tin disulfide powder;
fig. 16 is an alternating current impedance simulation circuit diagram of the tin disulfide/vertical graphene nanosheet array electrode and pure tin disulfide powder prepared by the method of the first embodiment.
Detailed Description
The first embodiment is as follows:
a preparation method of a tin disulfide/vertical graphene nanosheet array electrode comprises the following steps:
step 1, preparing a vertical graphene electrode, growing vertical graphene on carbon cloth by using a chemical vapor deposition method, and cooling to room temperature after reaction is finished for later use;
step 2, preparing a carrier solution, dissolving tin tetrachloride pentahydrate in n-butanol under the condition of stirring, then adding thioacetamide, and stirring to obtain the carrier solution for later use;
and 3, preparing a tin disulfide/vertical graphene nanosheet array electrode, immersing the vertical graphene electrode prepared in the step 1 into the carrier solution prepared in the step 2 for hydrothermal reaction, taking out after the hydrothermal reaction, cleaning, and drying to prepare the tin disulfide/vertical graphene nanosheet array electrode.
In the preparation method of the tin disulfide/vertical graphene nanosheet array electrode according to the embodiment, in the step 1, the carbon cloth is characterized in that carbon fibers in the carbon cloth have diameters of 8-10 μm, and the surface is smooth and has no pores.
In the preparation method of a tin disulfide/vertical graphene nanosheet array electrode according to the embodiment, in the step 1, the step of growing vertical graphene on carbon cloth through chemical vapor deposition is that when the cabin pressure reaches 10mTorr, the carbon cloth is placed into a cabin, then when the temperature is raised to 400 ℃, hydrogen and methane are introduced, and the flow rate ratio of the hydrogen to the methane is 3: 2, the plasma generator power is 550W, and the reaction time is 2 h.
In the method for preparing a tin disulfide/vertical graphene nanosheet array electrode according to the embodiment, in the step 1, the hydrogen flow rate is 90sccm and the methane flow rate is 60sccm in the process of growing vertical graphene on carbon cloth by chemical vapor deposition.
In the preparation method of the tin disulfide/vertical graphene nanosheet array electrode according to the embodiment, in the step 2, the mass ratio of tin tetrachloride pentahydrate, n-butanol and thioacetamide is 2.16: 148.18: 1.84.
in the preparation method of the tin disulfide/vertical graphene nanosheet array electrode according to the embodiment, the stirring time in the step 2 is 15-30 min.
In the method for preparing a tin disulfide/vertical graphene nanosheet array electrode according to the embodiment, the vertical graphene electrode is immersed in a carrier solution in step 3.
In the preparation method of the tin disulfide/vertical graphene nanosheet array electrode according to the embodiment, in the step 3, the hydrothermal reaction condition is 180 ℃ and the reaction is carried out for 24 hours.
In the preparation method of the tin disulfide/vertical graphene nanosheet array electrode according to the embodiment, in the step 3, the cleaning is performed 3-5 times by using deionized water, then the cleaning is performed 3-5 times by using absolute ethyl alcohol, and the drying temperature after the cleaning is 60 ℃.
An SEM image of carbon fibers in carbon cloth used in the preparation method of a tin disulfide/vertical graphene nanosheet array electrode in the present embodiment, which is magnified 1000 times, is shown in fig. 1, and it can be seen from fig. 1 that carbon fibers of carbon cloth used for preparing a tin disulfide/vertical graphene nanosheet array electrode in the present embodiment have smooth surfaces and no pores.
In the preparation method of the tin disulfide/vertical graphene nanosheet array electrode according to the embodiment, the SEM image of the vertical graphene electrode prepared by the method is enlarged by 2000 times is shown in fig. 2, and the SEM image of the vertical graphene electrode prepared by 5000 times is shown in fig. 3, the vertical graphene is formed by vertically growing graphene sheets on carbon fibers, the graphene sheets are mutually connected to form a porous latticed structure, and the thickness of the graphene sheets is about 96 nm.
An SEM image of the tin disulfide/vertical graphene nanosheet array electrode prepared by the method for preparing the tin disulfide/vertical graphene nanosheet array electrode according to the embodiment, which is magnified 3000 times, is shown in fig. 4, an SEM image of the tin disulfide/vertical graphene nanosheet array electrode magnified 13000 times is shown in fig. 5, and an SEM image of the tin disulfide/vertical graphene nanosheet array electrode magnified 40000 times is shown in fig. 6: as can be seen from fig. 4 and 5, the tin disulfide nanosheets uniformly cover the vertical graphene substrate, are uniform and stable in morphology, do not have substances with other structural morphologies, and vertically grow on the surface of the vertical graphene. As can be seen from fig. 6, in the tin disulfide/vertical graphene nanosheet array electrode according to this embodiment, the thickness of the tin disulfide nanosheets is about 128nm, the length of the tin disulfide nanosheets is about 1 μm, and it can be seen that the tin disulfide nanosheets are connected with each other to form a grid-like structure.
A TEM image of the tin disulfide/vertical graphene nanosheet array electrode prepared by the method for preparing a tin disulfide/vertical graphene nanosheet array electrode according to the embodiment, which is magnified 10000 times, is shown in fig. 7, and a TEM image magnified 20000 times is shown in fig. 8: as can be seen from fig. 7 and 8, in the tin disulfide/vertical graphene nanosheet array electrode prepared by the first method in the embodiment, the ultrathin SnS is provided2The nanoplatelets are interconnected to each other.
An HRTEM of 400000 times magnification of the tin disulfide/vertical graphene nanosheet array electrode prepared by the preparation method of the tin disulfide/vertical graphene nanosheet array electrode in the embodiment is shown in fig. 9, and as can be seen from fig. 9, the distances between the lattice planes of adjacent edges are respectively 0.18nm and 0.59nm through lattice analysis, and correspond to the (001) and (200) crystal planes of the tin disulfide nanosheets.
An electron diffraction pattern of the tin disulfide/vertical graphene nanosheet array electrode prepared by the preparation method of the tin disulfide/vertical graphene nanosheet array electrode in the embodiment is shown in fig. 10, and it can be confirmed again from fig. 10 that (200) and (100) crystal faces exist in the tin disulfide nanosheet in the tin disulfide/vertical graphene nanosheet array electrode.
An XRD test curve of the tin disulfide/vertical graphene nanosheet array electrode prepared by the preparation method of the tin disulfide/vertical graphene nanosheet array electrode in the present embodiment is shown in fig. 11, and as can be seen from fig. 11, diffraction peaks of the tin disulfide/vertical graphene nanosheet array electrode array respectively appear at 15.0, 28.2, 32.1, 41.9, 50.0, 52.5, 55.0 and 60.6 °, respectively correspond to crystal planes (001), (100), (101), (102), (110), (111), (103) and (201), and can be known as hexagonal tin disulfide by contrasting a standard spectrogram (JCPDF 42-1467).
A raman spectrum of the tin disulfide/vertical graphene nanosheet array electrode prepared by the method for preparing the tin disulfide/vertical graphene nanosheet array electrode according to the embodiment is shown in fig. 12, and can be seen from fig. 12 that the raman spectrum is 200cm-1And 2000cm-1370cm in between-1The Raman peak which appears corresponds to the Raman characteristic peak of the tin disulfide and is positioned at 1323cm-1And 1589cm-1Raman spectrum analysis proves that the tin disulfide/vertical graphene nanosheet array electrode contains tin disulfide and vertical graphene.
The tin disulfide/vertical graphene nanosheet array electrode prepared by the preparation method of the tin disulfide/vertical graphene nanosheet array electrode according to the embodiment is assembled into a button cell, the assembling process is carried out in a glove box, and the assembling sequence is as follows: the lithium ion battery comprises a positive electrode shell, an electrode material, electrolyte, a diaphragm, electrolyte, a sodium sheet, foamed nickel, electrolyte and a negative electrode shell. Then, the battery assembly can be completed after the battery is packaged by a packaging machine, the cyclic voltammetry test curve is shown in figure 13, and the cycle number charge-discharge capacity curve is shown in figure 14: fig. 13 shows that a reversible redox reaction occurs during charging and discharging of a tin disulfide/vertical graphene nanosheet array electrode; the test current densities of fig. 14 are: 0.1, 0.2, 0.3, 0.5, 1, 2, 3 and 5Ag-1As can be seen from FIG. 14, the current density was 100mAg-1The first-circle discharge specific capacity can be up to 1160mAhg-1(ii) a When the current density is 1Ag-1Specific discharge capacity of 897mAhg-1(ii) a When the current density is as high as 5Ag-1In this case, 727mAhg of electrode can be maintained-1The capacity of (c). The current density returns to the low current of 1Ag again-1The discharge specific capacity is recovered to 879mAhg-1The discharge specific capacity is substantially restored to the capacity before rapid charge and discharge. The tin disulfide/vertical graphene nanosheet array electrode prepared by the method has excellent electrochemical performance.
The tin disulfide/vertical graphene nanosheet array electrode prepared by the preparation method of the tin disulfide/vertical graphene nanosheet array electrode according to the embodiment is assembled into a button cell, an alternating current impedance comparison graph of pure tin disulfide powder prepared by the same method is shown in fig. 15, and an alternating current impedance simulation circuit schematic diagram is shown in fig. 16: as can be seen from fig. 15, the impedance of the tin disulfide/vertical graphene nanosheet array electrode prepared by the preparation method of the tin disulfide/vertical graphene nanosheet array electrode is much lower than the impedance of the pure tin disulfide nanosheet prepared by the same method. Table 1 shows the impedance comparison values of the ac impedance analog circuit shown in table 1:
TABLE 1 AC-IMPEDANCE ANALOG CIRCUIT IMPEDANCE COMPARATIVE VALUES
Figure BDF0000013604620000061
From table 1, specific resistance values can be seen, and by comparing the resistance values of the tin disulfide/vertical graphene nanosheet array electrode and the pure tin disulfide nanosheet electrode, the R of the tin disulfide/vertical graphene nanosheet array electrodebIs 2.543 omega, R1Is 1.947 omega, R2The tin disulfide/vertical graphene nanosheet array electrode is 3.961 ohms, and has a smaller resistance value, namely, more excellent conductivity performance.
The second embodiment is as follows:
a preparation method of a tin disulfide/vertical graphene nanosheet array electrode comprises the following steps:
step 1, preparing a vertical graphene electrode, growing vertical graphene on carbon cloth by using a chemical vapor deposition method, and cooling to room temperature after reaction is finished for later use;
step 2, preparing a carrier solution, dissolving tin tetrachloride pentahydrate in n-butanol under the condition of stirring, then adding thioacetamide, and stirring to obtain the carrier solution for later use;
and 3, preparing a tin disulfide/vertical graphene nanosheet array electrode, immersing the vertical graphene electrode prepared in the step 1 into the carrier solution prepared in the step 2 for hydrothermal reaction, taking out after the hydrothermal reaction, cleaning, and drying to prepare the tin disulfide/vertical graphene nanosheet array electrode.
According to the preparation method of the tin disulfide/vertical graphene nanosheet array electrode, the prepared tin disulfide nanosheets uniformly cover the vertical graphene substrate, are uniform and stable in shape and do not contain substances with other structural shapes, and vertically grow on the top of the vertical graphene; the thickness of the tin disulfide nanosheets is about 128nm, the length of the tin disulfide nanosheets is about 1 μm, and meanwhile, the tin disulfide nanosheets are mutually connected to form a grid-shaped structure; ultrathin tin disulfide nanosheets in the prepared tin disulfide/vertical graphene nanosheet array electrode are mutually connected.
In the preparation method of the tin disulfide/vertical graphene nanosheet array electrode according to the embodiment, the tin disulfide/vertical graphene nanosheet array electrode prepared by the preparation method of the tin disulfide/vertical graphene nanosheet array electrode is assembled into a button cell, the assembling process is performed in a glove box, and the assembling sequence is as follows: the lithium ion battery comprises a positive electrode shell, an electrode material, electrolyte, a diaphragm, electrolyte, a sodium sheet, foamed nickel, electrolyte and a negative electrode shell. Then packaging with packaging machine to complete the assembly of the battery, and performing cycle performance test with current density of 100mAg-1The first-circle discharge specific capacity can be up to 1160mAhg-1(ii) a When the current density is 1Ag-1Specific discharge capacity of 897mAhg-1(ii) a When the current density is as high as 5Ag-1In this case, 727mAhg of electrode can be maintained-1The capacity of (c). The current density returns to the low current of 1Ag again-1The discharge specific capacity is recovered to 879mAhg-1The discharge specific capacity is substantially restored to the capacity before rapid charge and discharge.
In the preparation method of the tin disulfide/vertical graphene nanosheet array electrode according to the embodiment, the vertical graphene prepared by the Plasma Enhanced Chemical Vapor Deposition (PECVD) method has the characteristic of high electrical conductivity of the carbon-based material, and the vertical graphene has a porous grid structure. The vertical graphene has good conductivity, high porosity, low density and large specific surface area, and the prepared tin disulfide/vertical graphene nanosheet array electrode has excellent performance.
The third concrete implementation mode:
according to the second specific embodiment, in the step 1, the carbon cloth is carbon fibers with diameters of 8-10 μm, and the surface of the carbon cloth is smooth and has no pores.
The fourth concrete implementation mode:
according to the second specific embodiment, in the step 1 of growing the vertical graphene on the carbon cloth by chemical vapor deposition, when the cabin pressure reaches 10mTorr, the carbon cloth is placed in the cabin, then when the temperature is raised to 400 ℃, hydrogen and methane are introduced, and the flow rate ratio of the hydrogen to the methane is 3: 2, the plasma generator power is 550W, and the reaction time is 2 h.
The fifth concrete implementation mode:
according to the second specific embodiment, in the step 1, the hydrogen flow rate is 90sccm and the methane flow rate is 60sccm in the process of growing the vertical graphene on the carbon cloth by chemical vapor deposition.
The sixth specific implementation mode:
according to the second specific embodiment, in the step 2, the mass ratio of tin tetrachloride pentahydrate, n-butanol and thioacetamide is 2-3: 140-150: 1.5 to 2.
The seventh embodiment:
according to the second specific embodiment, in the step 2, the mass ratio of tin tetrachloride pentahydrate, n-butanol and thioacetamide is 2.16: 148.18: 1.84.
the specific implementation mode is eight:
according to the preparation method of the tin disulfide/vertical graphene nanosheet array electrode, stirring time in the step 2 is 15-30 min.
The specific implementation method nine:
according to the second specific embodiment, in the step 3, the vertical graphene electrode is immersed in the carrier solution.
The detailed implementation mode is ten:
according to the preparation method of the tin disulfide/vertical graphene nanosheet array electrode described in the second specific embodiment, the hydrothermal reaction condition in the step 3 is 180 ℃ for 24 hours.
The concrete implementation mode eleven:
according to the second specific embodiment, in the step 3, the cleaning is performed 3-5 times by using deionized water, and then is performed 3-5 times by using absolute ethyl alcohol, and the drying temperature after cleaning is 60 ℃.

Claims (3)

1. A preparation method of a tin disulfide/vertical graphene nanosheet array electrode is characterized by comprising the following steps: the method comprises the following steps:
step 1, preparing a vertical graphene electrode, growing vertical graphene on carbon cloth by using a plasma enhanced chemical vapor deposition method, and cooling to room temperature after the reaction is finished for later use;
the step of growing the vertical graphene on the carbon cloth by chemical vapor deposition in the step 1 is that when the pressure of the cabin reaches 10mTorr, the carbon cloth is put into the cabin, then when the temperature is raised to 400 ℃, hydrogen and methane are introduced, and the flow rate ratio of the hydrogen to the methane is 3: 2, the power of the plasma generator is 550W, the reaction time is 2h, the hydrogen flow is 90sccm, and the methane flow is 60 sccm;
the diameter of the carbon fiber in the carbon cloth in the step 1 is 8-10 mu m;
step 2, preparing a carrier solution, dissolving tin tetrachloride pentahydrate in n-butanol under the condition of stirring, then adding thioacetamide, and stirring to obtain the carrier solution for later use;
in the step 2, the mass ratio of the tin tetrachloride pentahydrate to the n-butanol to the thioacetamide is 2.16: 148.18: 1.84;
step 3, preparing a tin disulfide/vertical graphene nanosheet array electrode, immersing the vertical graphene electrode prepared in the step 1 into the carrier solution prepared in the step 2 for hydrothermal reaction, taking out after the hydrothermal reaction, cleaning and drying to prepare the tin disulfide/vertical graphene nanosheet array electrode;
in the step 3, the hydrothermal reaction is carried out for 24 hours under the condition of 180 ℃;
the tin disulfide/vertical graphene nanosheet array electrode is used for a sodium ion battery, and when the current density is 100mAg-1The specific discharge capacity of the first circle can reach 1160mAhg-1(ii) a When the current density is 1Ag-1Specific discharge capacity of 897mAhg-1(ii) a When the current density is as high as 5Ag-1In this case, 727mAhg of electrode can be maintained-1The capacity of (c).
2. The preparation method of the tin disulfide/vertical graphene nanosheet array electrode according to claim 1, wherein: and 2, stirring for 15-30 min.
3. The preparation method of the tin disulfide/vertical graphene nanosheet array electrode according to claim 1, wherein: and in the step 3, the cleaning is carried out for 3-5 times by using deionized water, and then is carried out for 3-5 times by using absolute ethyl alcohol, and the drying temperature after cleaning is 60 ℃.
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Publication number Priority date Publication date Assignee Title
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