CN112062158A - Transition metal sulfide/graphene composite material and preparation method and application thereof - Google Patents
Transition metal sulfide/graphene composite material and preparation method and application thereof Download PDFInfo
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 83
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 66
- 239000002131 composite material Substances 0.000 title claims abstract description 64
- -1 Transition metal sulfide Chemical class 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- CKFGINPQOCXMAZ-UHFFFAOYSA-N methanediol Chemical compound OCO CKFGINPQOCXMAZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 18
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- 238000004519 manufacturing process Methods 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
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- 230000001681 protective effect Effects 0.000 claims description 3
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- 239000010941 cobalt Substances 0.000 claims description 2
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- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 6
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
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- 229940082328 manganese acetate tetrahydrate Drugs 0.000 description 2
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 description 2
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- 239000012300 argon atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 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
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
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Abstract
The invention discloses a transition metal sulfide/graphene composite material and a preparation method and application thereof, wherein the preparation method of the transition metal sulfide/graphene composite material comprises the following steps: (1) dissolving transition metal salt in methanol, and performing solvothermal reaction to obtain hydroxymethyl hydroxide of the transition metal; (2) mixing hydroxymethyl hydroxide of transition metal with graphene oxide dispersion liquid to obtain a hydroxymethyl hydroxide/graphene composite material; (3) and vulcanizing the hydroxymethyl hydroxide/graphene composite material to obtain the transition metal sulfide/graphene composite material. The transition metal sulfide/graphene composite material has high specific capacitance, good cycle stability and high energy density.
Description
Technical Field
The invention belongs to the technical field of energy storage equipment materials, and particularly relates to a transition metal sulfide/graphene composite material as well as a preparation method and application thereof.
Background
The super capacitor draws wide attention by virtue of the characteristics of high power density, high charge-discharge rate, long service life and the like, is considered to be one of the most promising electrochemical energy storage devices, has the potential of supplementing or finally replacing battery energy storage application, and can be applied to wearable and portable electronic products, electric vehicles and hybrid vehicles.
Graphene is a two-dimensional carbon monolayer consisting of sp2The hybrid carbon composition has many excellent characteristics, such as light weight, high electrical and thermal conductivity, controllable surface area, strong mechanical strength, good chemical stability, and the like. These excellent properties allow graphene and graphene-based materials to find applications in high performance nanostructured composites, electronics, environmental protection, and energy devices (including energy generation and storage).
The electrochemical performance of the supercapacitor depends greatly on the kind, morphology and structure of the electrode material. Since sulfur has a lower electronegativity than oxygen, transition metal sulfides have a more flexible structure and higher electrical conductivity than transition metal oxides. In addition, the composite material composed of the graphene-based material and the transition metal sulfide shows excellent electrochemical performance, and becomes a hot spot of current research.
However, the existing sulfide electrode material has the problems of low capacity and poor stability due to the fact that the micro-morphology is inconvenient for ion and electron transfer, and therefore, the synthesis of the electrode material with high capacity and good stability is very important.
Disclosure of Invention
The present invention has been made to solve at least one of the technical problems occurring in the prior art, and therefore, a first object of the present invention is to provide a method for preparing a transition metal sulfide/graphene composite material, which exhibits high specific capacitance and good cycle stability when used as an electrode material.
The preparation method of the transition metal sulfide/graphene composite material provided by the invention comprises the following steps:
(1) dissolving transition metal salt in methanol, and performing solvothermal reaction to obtain hydroxymethyl hydroxide of the transition metal;
(2) mixing hydroxymethyl hydroxide of transition metal with graphene oxide dispersion liquid to obtain a hydroxymethyl hydroxide/graphene composite material;
(3) and vulcanizing the hydroxymethyl hydroxide/graphene composite material to obtain the transition metal sulfide/graphene composite material.
In the prior art, water is generally used as a solvent, a one-step hydrothermal method is adopted to react transition metal salt, graphene oxide and a sulfur source to obtain a composite material of transition metal sulfide and graphene, and the obtained composite material is to form transition metal sulfide nano particles on a graphene nano sheet. According to the invention, firstly, the transition metal salt and methanol are subjected to esterification reaction through solvothermal reaction to prepare the hydroxymethyl hydroxide with the ultrathin two-dimensional nanosheet shape, and then the hydroxymethyl hydroxide is sequentially mixed with graphene oxide and vulcanized to obtain the compound of the transition metal sulfide two-dimensional nanosheet and the graphene nanosheet, wherein transition metal sulfide nanoparticles do not exist. Compared with the existing transition metal sulfide nano-particles, the transition metal sulfide two-dimensional nano-sheet is more beneficial to electron and ion transfer, and the high conductivity of the graphene and the improvement effect of the graphene on the appearance of the transition metal sulfide two-dimensional nano-sheet are combined, so that the composite material has high specific capacitance, good circulation stability and high energy density.
In the step (1), the transition metal salt is at least one selected from the group consisting of a sulfate, an acetate and a chloride of a transition metal, preferably an acetate. The concentration of the transition metal salt dissolved in the organic solvent is 0.01-0.5 mol/L.
The transition metal is selected from at least one of manganese and cobalt.
In the step (1), the solvothermal reaction is carried out at the temperature of 100-200 ℃ for 6-60 hours.
In the step (2), the concentration of the graphene oxide dispersion liquid is 0.5-2.0 mg/mL, and the mass ratio of the transition metal hydroxymethyl hydroxide to the graphene oxide dispersion liquid is 4: 1-1: 4.
In the step (2), a morphology regulator is also added in the process of mixing the hydroxymethyl hydroxide of the transition metal and the graphene oxide dispersion liquid.
The morphology modifier is selected from Cetyl Trimethyl Ammonium Bromide (CTAB).
The cetyl trimethyl ammonium bromide can be added into a mixture formed by hydroxymethyl hydroxide and graphene oxide dispersion liquid in a solution form, the concentration of the cetyl trimethyl ammonium bromide solution is 0.1-0.5 mg/mL, and the weight ratio of the cetyl trimethyl ammonium bromide solution to the transition metal hydroxymethyl hydroxide is 1: 250-1: 50.
In the step (3), the vulcanization method comprises the following steps: and mixing the hydroxymethyl hydroxide/graphene composite material with sublimed sulfur, and calcining in a protective atmosphere. According to the invention, sublimed sulfur is used as a sulfur source, so that the vulcanization of the hydroxymethyl hydroxide of the transition metal can be realized, the two-dimensional nanosheet shape of the hydroxymethyl hydroxide of the transition metal can be maintained, and if other sulfur sources are used for vulcanization, the two-dimensional nanosheet shape is difficult to maintain, so that the electrochemical performance of the product is influenced.
The calcination temperature is 100-800 ℃, and the calcination time is 0.01-10 h.
The protective atmosphere is selected from any one of nitrogen atmosphere and argon atmosphere.
The second purpose of the invention is to provide the transition metal sulfide/graphene composite material obtained by the preparation method.
The transition metal sulfide/graphene composite material obtained by the preparation method has a nanosheet structure, wherein the width of the nanosheet is 0.5-5 microns, and the thickness of the nanosheet is 10-100 nm.
The third purpose of the invention is to provide the application of the transition metal sulfide/graphene composite material. Specifically, the invention provides an application of the transition metal sulfide/graphene composite material in the preparation of a super capacitor.
When a supercapacitor is manufactured, the transition metal sulfide/graphene composite material, a conductive material and a binder are mixed to prepare slurry, and then the slurry is coated on the surface of metal to manufacture an electrode for the supercapacitor.
The conductive material can adopt conductive carbon black, the binder can adopt polytetrafluoroethylene, and the mass ratio of the transition metal sulfide/graphene composite material to the conductive material to the binder can be 78-82: 3-7: 12-17.
Compared with the prior art, the invention has the following beneficial effects:
(1) the preparation method can obtain the composite material with a uniform two-dimensional nanosheet structure, and the morphology is uniform and controllable.
(2) The transition metal sulfide/graphene composite material has high specific capacitance, good cycle stability and high energy density.
Drawings
Fig. 1 is an SEM image of manganese sulfide/graphene composite (a, b) and manganese sulfide nanoplates (c, d);
fig. 2 is an XRD pattern of manganese sulfide/graphene composite (a) and manganese sulfide nanosheet (b);
FIG. 3 shows that the scanning speed of the manganese sulfide/graphene composite material in the supercapacitor is 5-100 mV · s-1Voltammetric cycling profiles of time;
FIG. 4 shows that the current density of the manganese sulfide/graphene composite material in the supercapacitor is 1-10 A.g-1Specific capacitance magnification graph;
FIG. 5 shows the stability test results of manganese sulfide/graphene composite;
FIG. 6 shows that the current density of manganese sulfide nanosheets in the supercapacitor is 1-10 A.g-1Specific capacitance magnification graph.
Detailed Description
The technical solution of the present invention is further described below with reference to specific examples.
Example 1
A transition metal sulfide/graphene composite material is prepared by the following steps:
(1) uniformly dissolving manganese acetate tetrahydrate in a methanol solvent according to the concentration of 0.2mol/L, sufficiently exhausting air, transferring the solution into a polytetrafluoroethylene inner liner, putting the inner liner into a hydrothermal outer kettle for fixing and sealing, carrying out solvothermal reaction for 48h at 180 ℃, carrying out centrifugal washing for three times by using ethanol, and carrying out vacuum drying for 12h at 80 ℃ to obtain hydroxymethyl manganese hydroxide Mn (OH) (OCH)3) (denoted as precursor (r)).
(2) Physically mixing 200g of precursor (i) with 50mL of graphene oxide aqueous solution (1 mg/mL) according to a mass ratio of 4:1, dropwise adding 8mL of CTAB aqueous solution (0.5mg/mL), centrifugally washing with water and ethanol for three times, and vacuum drying at 65 ℃ for 12 hours to obtain hydroxymethyl manganese hydroxide/graphene Mn (OH) (OCH)3) and/GO (denoted as precursor (C)).
(3) Placing 0.4g of sublimed sulfur and 0.2g of precursor II into a glass tube according to the mass ratio of 2:1, and calcining for 2 hours at 400 ℃ in a nitrogen atmosphere by using a tube furnace to obtain the manganese sulfide/graphene composite material (manganese sulfide/graphene composite nanosheet, marked as MnS/rGO).
And (3) morphology characterization:
the microscopic morphologies of the manganese sulfide/graphene composite material are shown in (a) and (b) of fig. 1. FIG. 1 shows that the manganese sulfide/graphene composite material has a uniform two-dimensional nanosheet microstructure, the nanosheet width is 0.5-5 μm, and the thickness is about 100 nm.
The XRD pattern of the manganese sulfide/graphene composite material is shown in (a) of fig. 2. The diffraction peaks of the manganese sulfide/graphene composite material correspond to JCPDS card NO.88-2223 cards of manganese sulfide one by one, and the successfully prepared manganese sulfide nanosheet can be illustrated by combining with figure 1.
And (3) electrochemical performance testing:
mixing the manganese sulfide/graphene composite material with conductive carbon black and polytetrafluoroethylene according to a mass ratio of 80:15:5 to prepare slurry, coating the slurry on the surface of foamed nickel, drying and tabletting to obtain the electrode for the supercapacitor. The electrode was used to fabricate a supercapacitor, and electrochemical performance tests were performed, with the results shown in fig. 3 and 4.
Wherein FIG. 3 shows that the scanning speed of the manganese sulfide/graphene composite material in the supercapacitor is 5-100 mV · s-1A voltammetric cyclic curve chart, and FIG. 4 shows that the current density of the manganese sulfide/graphene composite material in the supercapacitor is 1-10 A.g-1Specific capacitance magnification graph. According to the test results, the content of the manganese sulfide/graphene composite material is 1 A.g-1Has a discharge current density of 2024F · g-1High specific capacitance of (2). In addition, in order to investigate the stability of the manganese sulfide/graphene composite material, the stability was 5A · g -1, a cyclic charge and discharge test was performed at a discharge current density. Fig. 5 shows the test results, which still maintain 85.11% of specific capacity after 5000 cycles.
Comparative example 1
This comparative example provides a transition metal sulfide material without the addition of graphene oxide compared to example 1.
Specifically, the method for producing the transition metal sulfide material of the present comparative example includes the steps of:
(1) according to 0.2 mol.L-1The preparation method comprises the steps of uniformly dissolving manganese acetate tetrahydrate in a methanol solvent, transferring the solution into a polytetrafluoroethylene lining after air is fully exhausted, putting the lining into a hydrothermal outer kettle for fixing and sealing, carrying out hydrothermal reaction for 48 hours at 180 ℃, carrying out centrifugal washing for three times by using ethanol, and carrying out vacuum drying for 12 hours at 80 ℃ to obtain a precursor.
(2) And (2) placing the precursor and the sublimed sulfur in the step (1) into a glass tube according to the mass ratio of 1:1, and calcining for 3 hours at 400 ℃ in a nitrogen atmosphere by using a tube furnace to obtain the manganese sulfide nanosheet.
The morphologies of the manganese sulfide nanosheets are shown in fig. 1 (c) and (d), and the XRD is shown in fig. 2 (b). Fig. 1 and 2 reflect the successful preparation of manganese sulfide nanosheets in the comparative example, and it can be seen from fig. 1 that the thickness of the manganese sulfide nanosheets which are not compounded with graphene is greater than that of the manganese sulfide/graphene composite material, and the surface is rough.
Manganese sulfide nanosheets were formed into electrodes for supercapacitors according to the same method as in example 1, and subjected to electrochemical performanceThe results of the tests are shown in FIG. 6. FIG. 6 shows that when not complexed with graphene, manganese sulfide nanosheets are at 1A · g-1Has a specific capacitance of only 800 F.g at a discharge current density of-1Compared with a manganese sulfide/graphene composite material, the composite material is reduced by 60%. Therefore, the graphene and the manganese sulfide nanosheet are compounded, so that the microscopic morphology of the manganese sulfide nanosheet can be effectively improved, the manganese sulfide nanosheet is more beneficial to ion and electron transmission, and the specific capacitance of the manganese sulfide nanosheet is improved.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of a transition metal sulfide/graphene composite material is characterized by comprising the following steps: the method comprises the following steps:
(1) dissolving transition metal salt in methanol, and performing solvothermal reaction to obtain hydroxymethyl hydroxide of the transition metal;
(2) mixing hydroxymethyl hydroxide of transition metal with graphene oxide dispersion liquid to obtain a hydroxymethyl hydroxide/graphene composite material;
(3) and vulcanizing the hydroxymethyl hydroxide/graphene composite material to obtain the transition metal sulfide/graphene composite material.
2. The method for producing a transition metal sulfide/graphene composite material according to claim 1, characterized in that: in the step (1), the transition metal salt is at least one selected from the group consisting of a sulfate, an acetate and a chloride of a transition metal.
3. The method for producing a transition metal sulfide/graphene composite material according to claim 2, characterized in that: the transition metal is selected from at least one of manganese and cobalt.
4. The method for producing a transition metal sulfide/graphene composite material according to claim 1, characterized in that: in the step (1), the solvothermal reaction temperature is 100-200 ℃.
5. The method for producing a transition metal sulfide/graphene composite material according to claim 1, characterized in that: in the step (2), the concentration of the graphene oxide dispersion liquid is 0.5-2.0 mg/mL, and the mass ratio of the transition metal hydroxymethyl hydroxide to the graphene oxide dispersion liquid is 4: 1-1: 4.
6. The method for producing a transition metal sulfide/graphene composite material according to claim 1, characterized in that: in the step (3), the vulcanization method comprises the following steps: and mixing the hydroxymethyl hydroxide/graphene composite material with sublimed sulfur, and calcining in a protective atmosphere.
7. The method for producing a transition metal sulfide/graphene composite material according to claim 6, characterized in that: the calcination temperature is 100-800 ℃.
8. The transition metal sulfide/graphene composite material prepared by the preparation method of the transition metal sulfide/graphene composite material according to any one of claims 1 to 7.
9. The transition metal sulfide/graphene composite material according to claim 8, wherein: the transition metal sulfide/graphene composite material has a nanosheet structure.
10. Use of the transition metal sulfide/graphene composite material according to claim 8 or 9 in the manufacture of a supercapacitor.
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