CN114937561B - Tungsten nitride/molybdenum nitride composite material with layered staggered structure and preparation method and application thereof - Google Patents
Tungsten nitride/molybdenum nitride composite material with layered staggered structure and preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 80
- GPBUGPUPKAGMDK-UHFFFAOYSA-N azanylidynemolybdenum Chemical compound [Mo]#N GPBUGPUPKAGMDK-UHFFFAOYSA-N 0.000 title claims abstract description 58
- -1 Tungsten nitride Chemical class 0.000 title claims abstract description 17
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 16
- 239000010937 tungsten Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title abstract description 21
- 150000003839 salts Chemical class 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000002135 nanosheet Substances 0.000 claims abstract description 20
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims abstract description 15
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000007772 electrode material Substances 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 239000011259 mixed solution Substances 0.000 claims description 13
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 12
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 12
- 239000011609 ammonium molybdate Substances 0.000 claims description 12
- 229940010552 ammonium molybdate Drugs 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 11
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 8
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- 238000003756 stirring Methods 0.000 claims description 7
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 239000013067 intermediate product Substances 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
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- 238000001816 cooling Methods 0.000 claims description 3
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- 239000011684 sodium molybdate Substances 0.000 claims description 3
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 3
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
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- 239000013078 crystal Substances 0.000 description 3
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- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004176 ammonification Methods 0.000 description 1
- IVHJCRXBQPGLOV-UHFFFAOYSA-N azanylidynetungsten Chemical compound [W]#N IVHJCRXBQPGLOV-UHFFFAOYSA-N 0.000 description 1
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Classifications
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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
- H01G11/30—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
- H01G11/22—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
- H01G11/84—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
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- 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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- 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
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
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- Manufacturing & Machinery (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention relates to a tungsten nitride/molybdenum nitride composite material with a layered staggered structure, and a preparation method and application thereof. The material is a composite of WN and MoN, has a three-dimensional staggered layered composite structure, and is a three-dimensional structure formed by mutually inserting ultrathin WN nano sheets and MoN nano sheets; in the preparation method, a salt template synthesis method is adopted, and the WN/MoN composite material with a layered staggered structure is prepared by controlling the conditions of mass ratio of template salt and tungsten/molybdate in the reactant, the dosage of molybdate in the reactant, the calcining temperature, the calcining time and the like. When the WN/MoN composite material synthesized by the method is used as an electrode material of a supercapacitor, the composite material has excellent electrochemical energy storage property. The preparation method of the composite material has the advantages of simple operation, controllable composite phase components, mild preparation conditions, low cost and the like.
Description
Technical Field
The technical scheme of the invention relates to a tungsten nitride (WN)/molybdenum nitride (MoN) composite material for a supercapacitor electrode and a preparation method thereof, in particular to a WN/MoN composite material with a layered staggered structure and a salt template synthesis method thereof.
Background
Supercapacitors (SC), also known as electrochemical capacitors, are a new type of electrochemical energy storage device. Compared with electrochemical energy storage devices such as lithium ion batteries, SCs have the advantages of high power density, rapid charge and discharge, large discharge current, wide use temperature window, good cycle stability and the like (Nat. Mater.4 (2005)) and are widely applied to the fields of electric automobiles, distributed communication equipment, clean energy storage, high-cold communication, industrial control and the like, and form a market (APL Mater.7 (2019) 100901) exceeding trillion dollars. However, the energy density of SC is about one order of magnitude lower than that of the secondary battery, and a key factor affecting the SC performance is an electrode material.
Transition group metal nitrides (TMNs) have the advantages of high conductivity, high pseudocapacitance capacity, good stability, large voltage window and the like, and are considered to be a relatively ideal supercapacitor electrode material (nat.rev.mater.2 (2017) 16098; ceram.int.45 (2019) 21062-21076), but the study of controllable synthesis of the microstructure of the material is still quite lacking. Currently, the preparation methods of TMNs mainly include precursor ammoniation, chemical vapor deposition, solvothermal, solid-state displacement, molecular precursor cleavage, and salt template methods (Frontiers in Chemistry,9 (2021) 638216). The precursor ammoniation method generally takes corresponding transition group metal oxide or carbide as raw material, and uses ammonia (NH) 3 ) TMNs are prepared by an ammonification reaction under an atmosphere. This process generally requires higher synthesis temperatures and product morphology is not controllable. The chemical vapor deposition method uses transition group metal halide as raw material, and uses N 2 Or NH 3 And depositing and growing TMNs on the substrate under the atmosphere. This method requires precise control of the synthesis process, and the reaction raw materials are costly and toxic. The solvothermal method is used for preparing TMNs by taking azide as a reaction raw material and carrying out high-pressure reaction, and the method requires harsh preparation conditions and dangerous reaction process. The salt template method utilizes lattice matching between the surface of the salt template and a target crystal to prepare TMNs, and is an efficient and extensible method for preparing transition group metal nitrides. Xu et al prepared ultra-thin, electrochemically excellent MoN nanoplatelets (ACS Nano,11 (2017) 2180-2186) using salt templating. The salt template method has the advantages of high yield, controllable product structure, cyclic use of template salt and the like.
The Mo-N and W-N binary phase diagrams are complex and contain phases with different stoichiometric ratios. Thus, the preparation conditions, such as reaction temperature, precursor composition, ammonia flow size, etc., have a significant impact on the phase composition, microcosmic morphology and electrochemical energy storage properties of the final product. Lv et al prepared a nitrogen-doped carbon cloth load by a simple nitridation processMon electrode and flexible spiral super capacitor prepared therefrom, the super capacitor has super long cycle life and 467.6mF/cm 2 High area specific capacitance (ACS Applied Materials)&Interfaces,13 (2021) 29780-29787). Dubal et al grow MoN nanoparticles with high ion affinity and thermodynamic stability on phosphorus doped carbon cloth, and the nanocomposite improves surface redox kinetics, and pseudocapacitance reaches 400mF/cm at a rapid charge and discharge rate 2 (2 times higher than the MoN based electrode) (Iscience, 16 (2019) 50-62). Salman et al prepared a reduced graphene oxide fiber (rGOF) composite electrode coated with WN at 0.05A/cm -3 The volume specific capacity of the super capacitor prepared by the electrode is 16.29F/cm 3 The energy density can reach 1.448mWh/cm 3 (nanoscales 12 (2020) 20239-20249). In general, although several MoN and WN-based composite electrodes are reported in the current research, high performance, microstructure-controlled WN/MoN composite electrodes have not been reported.
Disclosure of Invention
Aiming at the defects of the electrode material of the current super capacitor, the invention provides a tungsten nitride/molybdenum nitride composite material with a layered staggered structure, and a preparation method and application thereof. The material is a WN/MoN nano composite material and has a three-dimensional layered staggered structure; in the preparation method, a salt template synthesis method is adopted, and the WN/MoN composite material with a layered staggered structure is prepared by controlling the conditions of mass ratio of template salt and tungsten/molybdate in the reactant, the dosage of molybdate in the reactant, the calcining temperature, the calcining time and the like. The WN/MoN composite material synthesized by the method has excellent electrochemical energy storage property, and the preparation method of the composite material has the advantages of simplicity in operation, controllable composite phase components, mild preparation conditions, low cost and the like.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the tungsten nitride/molybdenum nitride composite material with the layered staggered structure is a composite of WN and MoN, wherein the molar ratio of WN to MoN=90%:10% -96:4%;
wherein, the material is a three-dimensional staggered lamellar composite structure, a three-dimensional structure is formed by the mutual interpenetration of ultrathin WN nano-sheets and MoN nano-sheets, the thickness of the two nano-sheets is 2-10 nm, and the width is 200-600 nm.
The preparation method of the WN/MoN nanocomposite with the layered staggered structure comprises the following steps:
(1) Adding tungstate and molybdate into the mixed solution, and stirring to obtain a mixed solution of tungstate and molybdate; heating the solution to 40-90 ℃, adding KCl powder into the mixed solution for 2-10 times, wherein the interval between two adjacent times is 5-15 min, continuously stirring at 40-90 ℃ for 2-6 hours after the KCl powder is added, and drying after stirring is finished to obtain a mixed salt/KCl intermediate product;
wherein the mole ratio of W/Mo in tungstate and molybdate is 90 percent, 10 percent to 80 percent, 20 percent; the mixed solution consists of deionized water and ethanol, and the volume ratio of the deionized water to the ethanol is 4:1-1:2; the mass ratio of KCl to (tungstate+molybdate) is 100:1-1000:1; the concentration of the sum of the tungstate radical and the molybdate radical ions in the mixed solution is 1-10 mmol/L;
the tungstate is ammonium tungstate ((NH) 4 ) 6 W 7 O 24 ·6H 2 O), sodium tungstate (Na 2 WO 4 ·2H 2 O), ammonium paratungstate ((NH) 4 ) 10 W 12 O 41 ·5H 2 O)；
The molybdate is ammonium paramolybdate ((NH) 4 ) 6 Mo 7 O 24 ·4H 2 O), sodium molybdate (Na 2 MoO 4 ·2H 2 O), ammonium molybdate ((NH) 4 ) 2 MoO 4 )；
(2) Placing the mixed salt/KCl intermediate product obtained in the step (1) into ammonia gas flow, heating to 500-800 ℃ for reaction for 1-10 h, and then cooling to room temperature in ammonia gas atmosphere to obtain a reaction product; washing the reaction product with deionized water and ethanol, and drying at 40-90 ℃ to obtain WN/MoN nano-sheets, namely the tungsten nitride/molybdenum nitride composite material with the layered staggered structure;
in the step (2), the temperature rising rate is 1-20 ℃/min.
The application of the tungsten nitride/molybdenum nitride composite material with the layered staggered structure is used as an electrode material of the super capacitor.
The beneficial effects of the invention are as follows:
1. the WN/MoN composite electrode with the three-dimensional layered staggered structure has high mass specific capacity, good cycle stability and rate capability, and is a super capacitor electrode material with excellent performance. FIG. 1 is an X-ray diffraction (XRD) pattern of a WN/MoN composite electrode prepared with a mixed salt of ammonium tungstate and ammonium molybdate in a molar ratio of 85% to 15% as reactants. The main phase of the composite material is WN with a hexagonal crystal structure, and the second phase is MoN with a cubic crystal structure. For convenience of description, this composite is referred to herein as WM-85. Quantitative analysis by inductively coupled plasma mass spectrometry (ICP-MS) can determine that the molar ratio of WN/MoN in the WM-85 composite product is 93.5 percent to 6.5 percent. Excess Mo source and related products are washed away during the preparation process. FIG. 2 is a Scanning Electron Microscope (SEM) picture of the microscopic morphology of the WM-85 composite. Fig. 3 is a Transmission Electron Microscope (TEM) image and lattice fringe phase of the microstructure of the composite material described above. The WM-85 composite material has a three-dimensional layered staggered structure, namely, WN and MoN sheets with the thickness of 2-10 nm are staggered and stacked, and the structure enables the composite material to expose more surface active sites and is beneficial to the diffusion and migration of ions in electrolyte solution. FIG. 4 shows a three electrode test system at 0.5. 0.5M H 2 SO 4 And in the electrolyte solution, testing the obtained Cyclic Voltammetry (CV) curve, constant current charge and discharge (GCD) curve, mass specific capacity under different current densities and Electrochemical Impedance Spectroscopy (EIS) of the WM-85 composite electrode. Under the test current density of 0.5A/g, the discharge time of the WM-85 composite electrode is up to 5000s, and the calculated mass specific capacity is 3125F/g which is far higher than the specific capacities of a pure WN electrode (158F/g) and a pure MoN electrode (294F/g). Even if the current density is increased to 5A/g, the mass specific capacity of the composite electrode can still reach 2300F/g. As shown in fig. 4 (d), the WM-85 composite electrode has lower internal resistance than the WN electrode and the MoN electrode. FIG. 5 shows a three electrode test system at 0.5. 0.5M K 2 SO 4 The solution is electrolyte, and WM-85 complex is measuredThe CV curve and the GCD curve of the combined electrode. At a current density of 0.5A/g, the discharge time of the WM-85 composite electrode was 1370s, and the calculated mass specific capacity was 1625F/g. Therefore, such WN/MoN electrodes exhibit excellent electrochemical energy storage properties in both acidic and neutral electrolytes. As shown in FIG. 6, the specific capacity retention of the electrode was still as high as 90.3% after 3000 cycles at a test current density of 20A/g. The above results indicate that the WN/MoN nanocomposite material with a three-dimensional layered staggered structure is an electrode material for super capacitors with excellent performance.
2. The salt template method used by the invention is a simple, efficient and low-cost WN/MoN composite material preparation method. The method utilizes the lattice mismatch characteristic between the Mon of the cubic structure, the WN of the hexagonal structure and the KCl fused salt of the cubic structure to realize the different oriented growth of the Mon and the WN nano-sheets, and forms a three-dimensional structure formed by interlacing ultrathin Mon and WN nano-sheets. This structure not only effectively prevents the stacking of the nanoplates, but also exposes more active sites, and provides more ion transport channels. The preparation method needs simple equipment, the product structure is controllable, and KCl template salt can be recycled, so that the method is an efficient WN/MoN composite material preparation method.
Drawings
The invention is further described below with reference to the drawings and the detailed description.
FIG. 1 is an X-ray diffraction pattern of a WM-85 composite material prepared by the salt template method of example 1. In the preparation process of the composite material, the mol ratio of ammonium tungstate to ammonium molybdate in the reactant is 85 percent to 15 percent.
FIG. 2 SEM pictures of the microstructure of the WM-85 composite synthesized in example 1; wherein FIG. 2 (a) is an SEM image at a magnification of 10,000, FIG. 2 (b) is an SEM image at a magnification of 30,000,
FIG. 3 TEM image of the microstructure and lattice fringe phase of the WM-85 composite synthesized in example 1; among them, fig. 3 (a) is a lattice fringe phase of WN nanoplatelets, fig. 3 (b) is a lattice fringe phase of MoN nanoplatelets, fig. 3 (c) is a low-resolution TEM image of WN/MoN composite material, and fig. 3 (d) is a high-resolution TEM image of WN/MoN composite material.
FIG. 4 is a graph of H at 0.5M 2 SO 4 The aqueous solution was the electrolyte and electrochemical energy storage performance characterization of the WM-85 composite material obtained in example 1 was measured in a three electrode system. Fig. 4 (a) is a cyclic voltammogram, fig. 4 (b) is a constant current charge-discharge curve, fig. 4 (c) is a change curve of mass specific capacity with measured current density, and fig. 4 (d) is an ac impedance curve.
The working electrode is prepared by uniformly dripping the prepared composite material on a glassy carbon electrode, wherein a graphite rod electrode is used as a counter electrode, and an Ag/AgCl electrode is used as a reference electrode.
FIG. 5K at 0.5M 2 SO 4 The aqueous solution is electrolyte, and the WM-85 composite electrode obtained by measurement in a three-electrode system is characterized in that (a) is a cyclic voltammogram and (b) is a constant-current charge-discharge curve.
FIG. 6 stability test of specific capacity of WN/MoN composite electrode prepared in example 1 over 3000 cycles at a current density of 20A/g.
FIG. 7 is a SEM photograph of the microstructure of a WN/MoN composite of different compositions; among them, fig. 7 (a) is an SEM picture of a WN/MoN composite material (hereinafter, denoted by WM-95) prepared by using a mixed salt of ammonium tungstate and ammonium molybdate in a molar ratio of 95% to 5% as a reaction raw material, and fig. 7 (b) is an SEM picture of a WN/MoN composite material (hereinafter, denoted by WM-75) prepared by using a mixed salt of ammonium tungstate and ammonium molybdate in a molar ratio of 75% to 25% as a reaction raw material.
FIG. 8 electrochemical energy storage behavior characterization of WN/MoN composites of different chemical compositions; fig. 8 (a) shows CV curves of different electrodes, and fig. 8 (b) shows GCD curves of different electrodes. Electrolyte for test 0.5. 0.5M H 2 SO 4 An aqueous solution.
Detailed Description
Example 1
(1) 0.170mmol (0.321 g) (NH) 4 ) 6 W 7 O 24 ·6H 2 O and 0.030mmol (0.037 g) (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O is dispersed in a mixed solution composed of 20mL deionized water and 10mL ethanol, and heatedStir 2h to 60 ℃ until the solution is clear. 107.4g KCl powder was added to the transparent colorless precursor solution in 6 portions, 10min was allowed to elapse between the two additions, and stirring was continued at 60℃for 4h after the KCl powder addition was completed, and drying was performed.
(2) Placing the mixed powder dried in the step (1) into a horizontal tube furnace, introducing ammonia gas flow, heating to 700 ℃ at a speed of 1 ℃/min for reaction for 5 hours, and then cooling to room temperature under an ammonia gas atmosphere to obtain a reaction product; and cleaning the reaction product by deionized water and ethanol in sequence, and drying at 60 ℃ to obtain the WM-85 composite electrode material.
FIG. 1 is an X-ray diffraction pattern of a WM-85 composite. From the figure, X-ray diffraction peaks belonging to WN and MoN were observed, and XRD peaks belonging to the remaining impurities were not observed, indicating that WN/MoN composite materials were obtained. The WN/MoN molar ratio in the WM-85 composite was 93.5% to 6.5% by inductively coupled plasma mass spectrometry (ICP-MS) quantitative analysis. This means that ammonium molybdate in the reaction feed did not fully form MoN nanoplatelets. FIG. 2 is a scanning electron microscope picture of the microstructure of the WM-85 composite. The MoN nano-sheets and the WN nano-sheets are subjected to oriented growth in different directions, so that a three-dimensional structure formed by staggered ultrathin nano-sheets is formed, and the nano-sheets are effectively prevented from being stacked. The thickness of WN and MoN nano-sheets is about 2-10 nm, and the width is about 200-600 nm. The three-dimensional staggered structure has higher active surface area, can provide more channels for electrolyte diffusion, and therefore has more excellent energy storage performance. Combining these effects, the WM-85 composite prepared has excellent electrochemical energy storage properties, as shown in FIGS. 4 and 5. The electrochemical energy storage performance of the WM-85 electrode is tested by adopting a three-electrode system, a graphite rod electrode is used as a counter electrode, an Ag/AgCl electrode is used as a reference electrode, and 0.5M H is used as a reference electrode 2 SO 4 The aqueous solution is an electrolyte. 5mg of WM-85 composite material is dispersed in a mixed solution of ethanol (950 mu L) and naphthol (50 mu L), the mixed solution is subjected to ultrasonic dispersion, then 2 mu L of suspension liquid is dripped on the surface of a clean glassy carbon electrode, and the working electrode is obtained after drying. The WM-85 composite electrode mass specific capacity reaches 3125F/g at a test current density of 0.5A/g. As shown in FIG. 4 (c), the specific capacity of the composite electrode increased from 0.5A/g to 5A/gStill up to 2300F/g. In FIG. 6, the specific capacity retention of the electrode was as high as 90.3% after 3000 cycles at a test current density of 20A/g. Therefore, the WM-85 composite electrode also has good cycling stability.
Examples 2, 3 and 4
The other steps were the same as in example 1 except that the calcination temperatures in step (2) were changed to 500, 600 and 800℃to obtain the same product as in example 1.
Examples 5 and 6
The other steps were the same as in example 1 except that the calcination time in step (2) was changed to 1h and 10h, to obtain the same product as in example 1.
Examples 7, 8 and 9
Other steps were the same as in example 1 except that the heating rate in step (2) was changed to 5℃per minute, 10℃per minute and 20℃per minute, to obtain the same product as in example 1.
Examples 10 and 11
The other steps were the same as in example 1 except that the KCl amount used in step (1) was changed to 35.8 and 358g to obtain the same product as in example 1.
Example 12
Other steps were the same as in example 1 except that the amounts of deionized water and ethanol in step (1) were changed to 20mL and 5mL to obtain the same product as in example 1.
Example 13
Other steps were the same as in example 1 except that the amounts of deionized water and ethanol in step (1) were changed to 10mL and 20mL to obtain the same product as in example 1.
Example 14
Other steps were the same as in example 1 except that the contents of deionized water and ethanol prepared in step (1) were changed to 133.3mL and 66.7mL, to obtain the same product as in example 1.
Example 15
Other steps were the same as in example 1 except that the contents of deionized water and ethanol prepared in step (1) were changed to 13.3mL and 6.7mL, to obtain the same product as in example 1.
Examples 16, 17, 18, 19
The other steps were the same as in example 1 except that the drying temperature in step (1) was changed to 40, 50, 70 and 90℃to obtain the same product as in example 1.
Example 20
Other steps are the same as in example 1 except that the ammonium tungstate in step (1) was changed to sodium tungstate (Na 2 WO 4 ·2H 2 O), ammonium molybdate is changed into sodium molybdate (Na 2 MoO 4 ·2H 2 O), and weighed Na 2 WO 4 ·2H 2 O、Na 2 MoO 4 ·2H 2 The masses of O and KCl were 0.056g, 0.007g and 18.9g, respectively, to give the same product as in example 1.
Example 21
Other steps are the same as in example 1 except that ammonium tungstate ((NH) in step (1) 4 ) 6 W 7 O 24 ·6H 2 O) and ammonium molybdate ((NH) 4 ) 6 Mo 7 O 24 ·4H 2 The amount of O) was adjusted to 0.180 and 0.020mmol, respectively, i.e., 0.340 and 0.025g, respectively; the amount of KCl salt was adjusted to 109.4g to give the same product as in example 1. Other synthesis processes are the same as those of example 1, the molar ratio of WN/MoN in the product is 96% to 4% measured by ICP-MS, and the electrochemical energy storage performance of the composite electrode is obtained by testing, so that the product is the same as that of example 1.
Example 22
Other steps are the same as in example 1 except that ammonium tungstate ((NH) in step (1) 4 ) 6 W 7 O 24 ·6H 2 O) and ammonium molybdate ((NH) 4 ) 6 Mo 7 O 24 ·4H 2 The amount of O) was adjusted to 0.160 and 0.040mmol, respectively, i.e. 0.302 and 0.049g, respectively; the KCl salt was adjusted to a dose of 105.4g. Other synthesis processes are the same as those of example 1, the molar ratio of WN/MoN in the composite material prepared by ICP-MS measurement is 90 percent to 10 percent, and the electrochemical energy storage performance of the composite electrode is obtained by testing, so that the product is the same as that of example 1.
Comparative example 1
Other steps are the same as in example 1 except that the mixture in step (1) is dispersedAmmonium tungstate ((NH) in liquid 4 ) 6 W 7 O 24 ·6H 2 O) and ammonium molybdate ((NH) 4 ) 6 Mo 7 O 24 ·4H 2 The amount of O) was adjusted to 0.190 and 0.010mmol, respectively, i.e., 0.359 and 0.012g, respectively, and the KCl amount was changed to 111.4g. As shown in FIG. 7 (a), the WM-95 composite material prepared had a flaky agglomerate structure. As shown in FIG. 8, the electrochemical energy storage performance of the electrode is drastically reduced, and the mass specific capacity thereof is 769F/g.
Comparative example 2
The other steps are the same as in example 1, except that ammonium tungstate ((NH) is added to the mixed dispersion in step (1) 4 ) 6 W 7 O 24 ·6H 2 O) and ammonium molybdate ((NH) 4 ) 6 Mo 7 O 24 ·4H 2 The amount of O) was adjusted to 0.150 and 0.050mmol, respectively, i.e., 0.283 and 0.062g, respectively, and the KCl amount was changed to 103.5g. As shown in FIG. 7 (b), a WM-75 composite material was prepared having a layered microstructure. The mass specific capacity of this composite electrode was calculated to be 1812F/g according to FIG. 8 (b).
Comparative example 3
The other steps are the same as in example 1, except that the calcination temperature in step (2) is adjusted to 450 ℃, and the interface bonding of the obtained composite product is not tight, and the mass specific capacity is 500F/g, which is only slightly higher than WN (158F/g).
Comparative example 4
The other steps were the same as in example 1, except that the calcination temperature in step (5) was adjusted to 850℃respectively, and WN and MoN reacted, so that WN/MoN composite material could not be obtained.
As can be seen from the above examples and comparative examples, the inventors of the present invention have found through extensive studies that the molar ratio of tungstate and molybdate in the raw materials and the calcination temperature must be strictly controlled in the preparation, otherwise the final product will not have a three-dimensional structure formed by interlacing ultra-thin nano-sheets, and excellent energy storage properties due to the structure. Thus, it is demonstrated that a suitable process is critical for preparing ultra-thin nanosheet structured WN/MoN composites.
The invention is not a matter of the known technology.
Claims (5)
1. A tungsten nitride/molybdenum nitride composite material with a layered staggered structure is characterized in that the material is a composite of WN and MoN, wherein the molar ratio of WN to MoN=90%:10% -96:4%;
the material is of a three-dimensional staggered layered composite structure, a three-dimensional structure is formed by mutually staggering ultrathin WN nano sheets and MoN nano sheets, the thickness of the two nano sheets is 2-10 nm, and the width of the two nano sheets is 200-600 nm.
2. The method for preparing the tungsten nitride/molybdenum nitride composite material with the layered staggered structure as claimed in claim 1, which is characterized by comprising the following steps:
(1) Adding tungstate and molybdate into the mixed solution, and stirring to obtain a mixed solution of tungstate and molybdate; heating the solution to 40-90 DEG o C, adding KCl powder into the mixed solution for 2-10 times, wherein the interval between two adjacent adding steps is 5-15 min, and continuing to add the KCl powder for 40-90 min after the adding of the KCl powder is completed o C, stirring for 2-6 hours, and drying after stirring is finished to obtain a mixed salt/KCl intermediate product;
wherein the mole ratio of W/Mo in tungstate and molybdate is 90 percent, 10 percent to 80 percent, 20 percent; the mixed solution comprises deionized water and ethanol, wherein the volume ratio of the deionized water to the ethanol is 4:1-1:2; the mass ratio of KCl to salt is 100:1-1000:1, and the salt is tungstate and molybdate; the concentration of the sum of the tungstate radical and the molybdate radical ions in the mixed solution is 1-10 mmol/L;
(2) Placing the mixed salt/KCl intermediate product obtained in the step (1) into ammonia gas flow, and heating to 500-800 DEG C o C, reacting for 1-10 h, and then cooling to room temperature in an ammonia atmosphere to obtain a reaction product; washing the reaction product with deionized water and ethanol, and washing the reaction product at 40-90 DEG C o And C, drying to obtain WN/MoN nano-sheets, namely the tungsten nitride/molybdenum nitride composite material with the layered staggered structure.
3. The method for preparing a layered interlaced structure tungsten nitride/molybdenum nitride composite material according to claim 2, wherein the tungsten is selected from the group consisting ofThe acid salt is ammonium tungstate (NH) 4 ) 6 W 7 O 24 · 6H 2 O, sodium tungstate Na 2 WO 4 ·2H 2 O, ammonium paratungstate (NH) 4 ) 10 W 12 O 41 ·5H 2 O；
The molybdate is ammonium paramolybdate (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O, ammonium molybdate (NH) 4 ) 2 MoO 4 Sodium molybdate Na 2 MoO 4 ·2H 2 O。
4. The method for producing a layered interleaved tungsten nitride/molybdenum nitride composite material according to claim 2 wherein in step (2), the heating rate is 1 to 20 o C/min。
5. Use of a layered interleaved structured tungsten nitride/molybdenum nitride composite material according to claim 1 as supercapacitor electrode material.
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