CN110853931A - Synthesis method of cobalt-molybdenum bimetallic sulfide for supercapacitor electrode material - Google Patents
Synthesis method of cobalt-molybdenum bimetallic sulfide for supercapacitor electrode material Download PDFInfo
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- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims abstract description 55
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000007772 electrode material Substances 0.000 title claims abstract description 43
- 238000001308 synthesis method Methods 0.000 title claims abstract description 16
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- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000002156 mixing Methods 0.000 claims abstract description 22
- CXVCSRUYMINUSF-UHFFFAOYSA-N tetrathiomolybdate(2-) Chemical compound [S-][Mo]([S-])(=S)=S CXVCSRUYMINUSF-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000005406 washing Methods 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 12
- 150000001868 cobalt Chemical class 0.000 claims abstract description 11
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- 238000000034 method Methods 0.000 claims description 29
- 230000002194 synthesizing effect Effects 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000001291 vacuum drying Methods 0.000 claims description 11
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 6
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 4
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- 229940044175 cobalt sulfate Drugs 0.000 claims description 4
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 4
- BZRRQSJJPUGBAA-UHFFFAOYSA-L cobalt(ii) bromide Chemical compound Br[Co]Br BZRRQSJJPUGBAA-UHFFFAOYSA-L 0.000 claims description 4
- ZKKLPDLKUGTPME-UHFFFAOYSA-N diazanium;bis(sulfanylidene)molybdenum;sulfanide Chemical compound [NH4+].[NH4+].[SH-].[SH-].S=[Mo]=S ZKKLPDLKUGTPME-UHFFFAOYSA-N 0.000 claims description 4
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 4
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 4
- 229960004011 methenamine Drugs 0.000 claims description 4
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 2
- 239000003990 capacitor Substances 0.000 abstract description 16
- 239000003792 electrolyte Substances 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 abstract description 3
- 239000002105 nanoparticle Substances 0.000 abstract description 3
- 238000009792 diffusion process Methods 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 description 12
- 238000000840 electrochemical analysis Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 229910052976 metal sulfide Inorganic materials 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910002483 Cu Ka Inorganic materials 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- -1 Transition metal sulfides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical group [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910000474 mercury oxide Inorganic materials 0.000 description 1
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- 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
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention provides a synthesis method of a cobalt-molybdenum bimetallic sulfide for a supercapacitor electrode material, which comprises the steps of mixing and dissolving cobalt salt and deionized water to obtain a solution A, mixing and dissolving a morphology regulator, tetrathiomolybdate and deionized water to obtain a solution B, mixing the solution A and the solution B in equal volume, carrying out hydrothermal reaction, cooling after the reaction is finished, and washing and drying to obtain the cobalt-molybdenum bimetallic sulfide. According to the synthesis method of the cobalt-molybdenum bimetallic sulfide, the cobalt-molybdenum bimetallic sulfide prepared by combining cobalt salt and tetrathiomolybdate is used as the electrode material of the super capacitor, so that the super capacitor has high reversibility and excellent circulation stability, and meanwhile, the prepared cobalt-molybdenum bimetallic sulfide is a loose porous structure formed by accumulating nano particles, so that the diffusion of electrolyte ions is facilitated, the specific capacitance value of a capacitor can be greatly improved, and the super capacitor has good electrochemical performance.
Description
Technical Field
The invention relates to the technical field of preparation of capacitor electrode materials, in particular to a synthesis method of a cobalt-molybdenum bimetallic sulfide for a super capacitor electrode material.
Background
The super capacitor as a novel energy storage device has the advantages of high power density, long charging and discharging time and the like, and as a main evaluation standard of the super capacitor, the selection of electrode materials of the super capacitor is particularly important. Transition metal sulfides have higher specific capacitance and conductivity than the corresponding oxides, so more and more people are beginning to look at metal sulfides. Many monometallic sulfides, including NiS/Ni3S2CoS and MoS2And the like, have been widely applied to supercapacitor electrode materials and exhibit good capacitance properties.
At present, Tang et al synthesized CoS by solvothermal method2The specific capacitance value of the/rGO nano composite material as the electrode material of the super capacitor can reach 331F/g [ Tang J, et al. ceramics International,2014,40(10):15411-](ii) a Zhu et al synthesized octahedral-structured CoS by hydrothermal method without using any surfactant and template2The specific capacity of the crystal at 1A/g reaches 236.5F/g [ Xing J C, et al. journal of Materials Chemistry,2012,22:15750-]. However, the electrode materials prepared by the two methods are still not ideal when applied to a super capacitor, so that a new preparation process of the metal sulfide is needed to be developed to obtain the electrode material of the super capacitor with better performance.
Disclosure of Invention
In view of the above, the present invention is directed to a method for synthesizing cobalt-molybdenum bimetallic sulfide used as an electrode material of a supercapacitor, so as to obtain a metal sulfide for preparing an electrode material with a high specific capacitance value.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a method for synthesizing cobalt molybdenum bimetallic sulfide used for supercapacitor electrode materials is characterized by comprising the following steps: the synthesis method comprises the following steps:
s1, mixing and dissolving cobalt salt and deionized water to obtain a solution A;
s2, mixing and dissolving the morphology regulator, tetrathiomolybdate and deionized water to obtain a solution B;
s3, mixing the solution A and the solution B in equal volume, carrying out hydrothermal reaction, cooling after the reaction is finished, and washing and drying to obtain the cobalt-molybdenum bimetallic sulfide.
Further, in step s1, the mass ratio of the cobalt salt to the deionized water is (0.002-0.005): 1.
further, in step s2, the ratio of the amount of the materials among the morphology regulator, molybdate and deionized water is (0.001-0.002): (0.002-0.005): 1.
further, in step s3, the reaction temperature of the hydrothermal reaction is 100-160 ℃, the reaction time is 6-12 hours, and in step s3, the cobalt molybdenum bimetallic sulfide is obtained by centrifugal washing and vacuum drying.
Further, the centrifugal washing comprises three times of washing respectively by deionized water and ethanol.
Further, the vacuum drying is carried out for 10 hours under the conditions that the vacuum degree is 0.8KPa and the temperature is 60 ℃.
Further, the cobalt salt is one of cobalt chloride hexahydrate, cobalt nitrate, cobalt bromide and cobalt sulfate.
Further, the tetrathiomolybdate is one of sodium tetrathiomolybdate, potassium tetrathiomolybdate, ammonium tetrathiomolybdate and barium tetrathiomolybdate.
Further, the morphology regulator is one of ammonium fluoride, sodium dodecyl sulfate, cetyl trimethyl ammonium bromide and hexamethylene tetramine.
Further, the specific capacitance value of the cobalt molybdenum bimetal sulfide obtained in the step s3 at the current density of 0.5A/g is between 450 and 3000F/g
Compared with the prior art, the invention has the following advantages:
the synthesis method of the cobalt-molybdenum bimetallic sulfide firstly introduces Co ions to change the conductivity of an electrode material on the basis of applying a wider Mo sulfide material, secondly utilizes a morphology regulator to regulate the surface morphology of the electrode material, improves the specific surface area of the electrode material, can utilize surface modification to increase reaction active sites, and finally synthesizes a product which is a loose porous structure formed by stacking nano-scale nano-particles and is beneficial to the diffusion of electrolyte ions.
Therefore, the synthesis method can synthesize the bimetallic sulfide electrode material with better conductivity, lower crystallinity and more pore structures, has high reversibility and excellent cycling stability, can greatly improve the specific capacitance value of the super capacitor, and has good electrochemical performance.
In addition, the synthesis method has the advantages of simple process, low raw material cost and wide application potential.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate an embodiment of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 is an XRD pattern of a cobalt molybdenum bimetallic sulfide prepared according to preparation example 1 of the present invention;
FIG. 2 is an SEM image of a cobalt molybdenum bimetallic sulfide prepared by the preparation example 1 of the present invention;
FIG. 3 is a graph of specific capacitance data of cobalt molybdenum bimetallic sulfide prepared in preparation example 4 of the present invention as an electrode material.
Detailed Description
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
The embodiment relates to a synthesis method of cobalt-molybdenum bimetallic sulfide used as an electrode material of a super capacitor.
The method for synthesizing the cobalt-molybdenum bimetallic sulfide specifically comprises the steps of mixing and dissolving cobalt salt and deionized water to obtain a solution A, mixing and dissolving a morphology regulator, molybdate and deionized water to obtain a solution B, mixing the solution A and the solution B in equal volume, carrying out hydrothermal reaction, cooling after the reaction is finished, and washing and drying to obtain the cobalt-molybdenum bimetallic sulfide.
Wherein, in the synthesis method, the mass ratio of the cobalt salt to the deionized water is (0.002-0.005): 1, and it may be, for example, 0.002: 1. 0.003: 1. 0.004:1 or 0.005: 1. the quantity ratio of substances among the morphology regulator, molybdate and deionized water is (0.001-0.002): (0.002-0.005): specific examples of 1 include 0.001: 0.002: 1. 0.001: 0.003: 1. 0.001: 0.004: 1. 0.001: 0.005:1 or 0.002: 0.002: 1. 0.002: 0.003: 1. 0.002: 0.004: 1. 0.002: 0.005: 1.
the reaction temperature of the hydrothermal reaction may be specifically 100-160 deg.C, such as 100 deg.C, 105 deg.C, 120 deg.C, 125 deg.C, 130 deg.C, 140 deg.C or 145 deg.C, 150 deg.C, 160 deg.C, and the reaction time may be 6-12 hours, such as 6 hours, 6.5 hours, 7 hours, 8 hours or 9 hours, 10 hours, 10.5 hours, 11 hours, 12 hours. In addition, in the above synthesis method, the cobalt-molybdenum bimetallic sulfide is obtained by centrifugal washing and vacuum drying.
Specifically, the centrifugal washing includes three times of washing with deionized water and ethanol, respectively, for the centrifugal washing, and drying under vacuum at 0.8KPa and 60 deg.C for 10 hr for the vacuum drying.
In the synthesis method of the present embodiment, the cobalt salt may be specifically cobalt chloride hexahydrate (CoCl)2·6H2O), cobalt nitrate (Co (NO)3)2) Cobalt bromide (CoBr)2) And cobalt sulfate (CoSO)4) One of (1); the tetrathiomolybdate can be sodium tetrathiomolybdate (Na)2MoS4) Potassium tetrathiomolybdate (K)2MoS4) Ammonium tetrathiomolybdate ((NH)4)2MoS4) Barium tetrathiomolybdate (BaMoS)4) One of (1); the morphology regulator can be one of ammonium fluoride, sodium dodecyl sulfate, hexadecyl trimethyl ammonium bromide and hexamethylene tetramine.
The cobalt-molybdenum bimetallic sulfide synthesis method can synthesize a loose porous structure formed by stacking nano-scale nanoparticles, can prepare a bimetallic sulfide electrode material with good conductivity, low crystallinity and more pore structures, can enable a super capacitor applying the bimetallic sulfide electrode material to have high reversibility and excellent circulation stability, and can greatly improve the specific capacitance value of the super capacitor.
The method for synthesizing cobalt molybdenum bimetallic sulfide of this embodiment is further illustrated in the following specific preparation examples.
Preparation of example 1
In the method for synthesizing cobalt molybdenum bimetallic sulfide for supercapacitor electrode material of the present example, first, cobalt chloride hexahydrate (CoCl)2·6H2O) and deionized water according to the mass ratio of 0.002:1 to obtain a solution A, and then ammonium fluoride and sodium tetrathiomolybdate (Na) serving as morphology regulators are mixed and dissolved2MoS4) And deionized water in a mass ratio of 0.001: mixing and dissolving 0.002:1 to obtain a solution B. And then mixing the solution A and the solution B in equal volume, carrying out hydrothermal reaction at 100 ℃ for 6 hours, cooling after the reaction is finished, respectively centrifugally washing the mixture for three times by deionized water and ethanol, and finally carrying out vacuum drying for 10 hours under the conditions that the vacuum degree is 0.8KPa and the temperature is 60 ℃ to obtain the cobalt-molybdenum bimetallic sulfide.
The XRD patterns of the cobalt molybdenum bimetallic sulfide synthesized in the preparation examples are shown in FIG. 1 (under the test conditions that a Bruker D8 and BDX3300 type X-ray diffractometer is used for XRD test, an excitation source is a Cu-Ka light source, the X-ray wavelength is 1.54A, the tube voltage is 30kV, and the tube current is 30 mA). Meanwhile, the scanning electron micrograph of the cobalt molybdenum bimetallic sulfide synthesized in the example is shown in fig. 2.
In addition, the electrochemical test is carried out on the electrode material of the cobalt-molybdenum bimetallic sulfide synthesized by the embodiment, and the specific test conditions comprise that a three-electrode working system is adopted, wherein the three-electrode working system mainly comprises three electrodes, namely a working electrode, a reference electrode and an auxiliary electrode, an electrolyte and a diaphragm, and a Lujin capillary tube and a salt bridge which are used for eliminating a liquid connection potential and reducing the resistance of a solution are also arranged.
The working electrode used in electrochemical test is prepared electricityThe polar materials, and in particular the conductive agent (carbon black), the binder (PTFE emulsion), ethanol, were mixed in a mass ratio of about 75:15:10:10, and the paste mixture was uniformly coated on a current collector (nickel foam, 1 x 1 cm)2) And vacuum drying, and pressing into electrode plate under about 6MPa pressure. The reference electrode is mercury/mercury oxide (Hg/HgO), the platinum mesh (Pt mesh) is used as an auxiliary electrode, the electrolyte is potassium hydroxide solution, and the diaphragm is a cellulose membrane.
Through the electrochemical tests, the specific capacitance value of the electrode material of the cobalt-molybdenum bimetallic sulfide synthesized by the method reaches 453F/g at the current density of 0.5A/g.
Preparation of example 2
In the method for synthesizing cobalt molybdenum bimetallic sulfide for supercapacitor electrode material of the present example, first, cobalt nitrate (Co (NO) is added3)2) Mixing with deionized water at a mass ratio of 0.003:1 to obtain solution A, and adding morphology regulator such as sodium dodecyl sulfate and potassium tetrathiomolybdate (K)2MoS4) And deionized water in a mass ratio of 0.001: mixing and dissolving the mixture at a ratio of 0.003:1 to obtain a solution B. And then mixing the solution A and the solution B in equal volume, carrying out hydrothermal reaction at 120 ℃ for 8 hours, cooling after the reaction is finished, respectively centrifugally washing the mixture for three times by deionized water and ethanol, and finally carrying out vacuum drying for 10 hours under the conditions that the vacuum degree is 0.8KPa and the temperature is 60 ℃ to obtain the cobalt-molybdenum bimetallic sulfide.
The electrode material of cobalt molybdenum bimetallic sulfide synthesized by the example is subjected to the same electrochemical test as that in the example 1, and the specific capacitance value of the electrode material reaches 800F/g under the current density of 0.5A/g.
Preparation of example 3
In the method for synthesizing cobalt molybdenum bimetallic sulfide for supercapacitor electrode material of the present example, first, cobalt bromide (CoBr)2) Mixing and dissolving the solution A and deionized water according to the mass ratio of 0.003:1 to obtain a solution A, and then adding morphology regulators of cetyl trimethyl ammonium bromide and ammonium tetrathiomolybdate ((NH)4)2MoS4) And deionized water in a mass ratio of 0.002: 0.004:1 mixingAnd dissolving to obtain solution B. And then mixing the solution A and the solution B in equal volume, carrying out hydrothermal reaction at 140 ℃ for 10 hours, cooling after the reaction is finished, respectively centrifugally washing the mixture for three times by deionized water and ethanol, and finally carrying out vacuum drying for 10 hours under the conditions that the vacuum degree is 0.8KPa and the temperature is 60 ℃ to obtain the cobalt-molybdenum bimetallic sulfide.
The same electrochemical test as in example 1 was carried out on the electrode material of cobalt molybdenum bimetallic sulfide synthesized by this example, and the specific capacitance value of the electrode material reaches 1400F/g under the current density of 0.5A/g.
Preparation of example 4
In the method for synthesizing cobalt molybdenum bimetallic sulfide for supercapacitor electrode material of the present example, first, cobalt sulfate (CoSO) was added4) Mixing with deionized water at a mass ratio of 0.005:1 to obtain solution A, and adding morphology regulator hexamethylenetetramine and barium tetrathiomolybdate (BaMoS)4) And deionized water in a mass ratio of 0.002: mixing and dissolving at a ratio of 0.005:1 to obtain a solution B. And then mixing the solution A and the solution B in equal volume, carrying out hydrothermal reaction at 160 ℃ for 12 hours, cooling after the reaction is finished, respectively centrifugally washing the mixture for three times by deionized water and ethanol, and finally carrying out vacuum drying for 10 hours under the conditions that the vacuum degree is 0.8KPa and the temperature is 60 ℃ to obtain the cobalt-molybdenum bimetallic sulfide.
The same electrochemical test method as in example 1 was used to test the data graph of specific capacitance values in this example as shown in fig. 3, which shows that the specific capacitance value reached 2656F/g at a current density of 0.5A/g as shown in fig. 3.
As can be seen from the above preparation examples, the specific capacitance value of the cobalt-molybdenum bimetallic sulfide electrode material obtained by the synthesis method of the embodiment at a current density of 0.5A/g is between 450F/g and 3000F/g, which greatly improves the specific capacitance value compared with the existing metal sulfide electrode, and can well improve the performance of the supercapacitor.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A method for synthesizing cobalt molybdenum bimetallic sulfide used for supercapacitor electrode materials is characterized by comprising the following steps: the synthesis method comprises the following steps:
s1, mixing and dissolving cobalt salt and deionized water to obtain a solution A;
s2, mixing and dissolving the morphology regulator, tetrathiomolybdate and deionized water to obtain a solution B;
s3, mixing the solution A and the solution B in equal volume, carrying out hydrothermal reaction, cooling after the reaction is finished, and washing and drying to obtain the cobalt-molybdenum bimetallic sulfide.
2. The method for synthesizing the cobalt molybdenum bimetallic sulfide for the electrode material of the supercapacitor according to claim 1, wherein the method comprises the following steps: in step s1, the mass ratio of the cobalt salt to the deionized water is (0.002-0.005): 1.
3. the method for synthesizing the cobalt molybdenum bimetallic sulfide for the electrode material of the supercapacitor according to claim 2, characterized in that: in step s2, the quantity ratio of the substances among the morphology regulator, molybdate and deionized water is (0.001-0.002): (0.002-0.005): 1.
4. the method for synthesizing the cobalt molybdenum bimetallic sulfide for the electrode material of the supercapacitor according to claim 3, wherein the method comprises the following steps: in step s3, the reaction temperature of the hydrothermal reaction is 100-160 ℃, the reaction time is 6-12 hours, and in step s3, the cobalt molybdenum bimetallic sulfide is obtained by centrifugal washing and vacuum drying.
5. The method for synthesizing the cobalt molybdenum bimetallic sulfide for the electrode material of the supercapacitor according to claim 4, wherein the method comprises the following steps: the centrifugal washing comprises three separate washes with deionized water and ethanol.
6. The method for synthesizing the cobalt molybdenum bimetallic sulfide for the electrode material of the supercapacitor according to claim 4, wherein the method comprises the following steps: the vacuum drying is drying for 10 hours under the conditions that the vacuum degree is 0.8KPa and the temperature is 60 ℃.
7. The method for synthesizing cobalt molybdenum bimetallic sulfide for supercapacitor electrode materials according to any one of claims 1 to 6, characterized in that: the cobalt salt is one of cobalt chloride hexahydrate, cobalt nitrate, cobalt bromide and cobalt sulfate.
8. The method for synthesizing the cobalt molybdenum bimetallic sulfide for the electrode material of the supercapacitor according to claim 7, wherein the method comprises the following steps: the tetrathiomolybdate is one of sodium tetrathiomolybdate, potassium tetrathiomolybdate, ammonium tetrathiomolybdate and barium tetrathiomolybdate.
9. The method for synthesizing the cobalt molybdenum bimetallic sulfide for the electrode material of the supercapacitor according to claim 8, wherein the method comprises the following steps: the morphology regulator is one of ammonium fluoride, sodium dodecyl sulfate, hexadecyl trimethyl ammonium bromide and hexamethylene tetramine.
10. The method for synthesizing the cobalt molybdenum bimetallic sulfide for the electrode material of the supercapacitor according to claim 9, wherein the method comprises the following steps: the specific capacitance value of the cobalt molybdenum bimetal sulfide obtained in the step s3 at the current density of 0.5A/g is 450F/g-3000F/g.
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| CN113161558A (en) * | 2021-04-14 | 2021-07-23 | 天津大学 | Cobalt-molybdenum binary amorphous sulfide compound ultrathin nano film with self-spin state regulation |
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