CN114937561A - 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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention relates to a tungsten nitride/molybdenum nitride composite material with a layered staggered structure, a preparation method and application thereof. The material is a compound of WN and MoN, has a three-dimensional staggered layered composite structure, and is formed by mutually interpenetrating ultrathin WN nanosheets and MoN nanosheets to form a three-dimensional structure; in the preparation method, a salt template synthesis method is adopted, and WN/MoN composite material with a layered staggered structure is prepared by controlling the mass ratio of template salt to tungsten/molybdate in reactants, the using amount of molybdate in the reactants, the calcination temperature, the calcination time and other conditions. When the WN/MoN composite material synthesized by the invention is used as an electrode material of a super capacitor, the WN/MoN 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 super capacitor 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, the SC has 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)366), so that the SC is widely applied to the fields of electric automobiles, distributed communication equipment, clean energy storage, high-cold communication, industrial control and the like, and forms a market (APL Mater.7(2019)100901) exceeding billions of dollars. However, the energy density of SC is about one order of magnitude lower compared to secondary batteries, where a key factor affecting the performance of SC is the electrode material.
Transition 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 ideal electrode materials of super capacitors (nat. Rev. Mater.2(2017) 16098; Ceram. int.45(2019) 21062-. Currently, the methods for preparing TMNs mainly include precursor ammoniation, chemical vapor deposition, solvothermal method, solid-state displacement method, molecular precursor cracking method, and salt template method (Frontiers in Chemistry,9 (2021)) 638216. Among them, the precursor ammonification method usually uses a corresponding transition metal oxide or carbide as a raw material in ammonia (NH) 3 ) TMNs were prepared by an ammoniation reaction under an atmosphere. The method generally needs higher synthesis temperature, and the product appearance is not controllable. The chemical vapor deposition method uses halide of transition metal as raw material in N 2 Or NH 3 And depositing and growing the TMNs on the substrate under the atmosphere. This method requires precise control of the synthesis process, and the reaction raw materials are expensive and toxic. The solvent thermal method uses azide as a reaction raw material to carry out high-pressure reaction to prepare TMNs, and the method has harsh preparation conditions and dangerous reaction process. The salt template method utilizes the lattice matching between the surface of the salt template and a target crystal to prepare the TMNs, and is a high-efficiency and extensible method for preparing transition metal nitrides. Xu et al prepared ultra-thin MoN nano-particles with excellent electrochemical properties by using salt template methodPlate (ACS Nano,11(2017) 2180-2186). The salt template method has the advantages of large yield, controllable product structure, recyclable template salt and the like.
The binary phase diagrams of Mo-N and W-N are both relatively complex and contain multiple phases of different stoichiometry. Therefore, the preparation conditions, such as reaction temperature, precursor composition, ammonia gas flow size and the like, have significant influence on the phase composition, the micro-morphology and the electrochemical energy storage performance of the final product. Lv et al prepared N-doped carbon cloth-loaded MoN electrode by simple nitridation process, and prepared flexible helical-structure supercapacitor with ultra-long cycle life and 467.6mF/cm 2 High area specific capacitance (ACS Applied Materials)&Interfaces,13(2021) 29780-29787). The MoN nano-particles with high ion affinity and thermodynamic stability are grown on the phosphorus-doped carbon cloth by Dubal et al, the nano composite material improves the surface redox kinetics, and the pseudocapacitance reaches 400mF/cm at the rapid charge-discharge rate 2 (2 times higher than MoN-based electrodes) (Isscience, 16(2019) 50-62). Salman et al prepared a reduced graphene oxide fiber (rGOF) composite electrode coated with WN at 0.05A/cm -3 Under the current density of (2), 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 (Nanoscale 12(2020) 20239-20249). In general, although several MoN and WN-based composite electrodes are reported in the current research, high-performance WN/MoN composite electrodes with controllable microstructure are not reported yet.
Disclosure of Invention
The invention aims to provide a tungsten nitride/molybdenum nitride composite material with a layered staggered structure and a preparation method and application thereof, aiming at the defects of the current electrode material of a super capacitor. 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 WN/MoN composite material with a layered staggered structure is prepared by controlling the mass ratio of template salt to tungsten/molybdate in reactants, the using amount of molybdate in the reactants, the calcination temperature, the calcination time and other conditions. The WN/MoN composite material synthesized by the invention has excellent electrochemical energy storage property, and 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.
The technical scheme adopted by the invention for solving the technical problem is as follows:
the tungsten nitride/molybdenum nitride composite material with a layered staggered structure is a composite of WN and MoN, wherein the molar ratio of WN to MoN is 90 percent to 10 to 96 percent to 4 percent;
the material is of a three-dimensional staggered layered composite structure, an ultrathin WN nanosheet and a MoN nanosheet are mutually interpenetrated to form a three-dimensional structure, the thickness of the two nanosheets is 2-10 nm, and the width of the two nanosheets is 200-600 nm.
The preparation method of the WN/MoN nano composite material 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 of addition is 5-15 min, continuing stirring at 40-90 ℃ for 2-6 hours after the KCl powder is added, and drying after stirring to obtain a mixed salt/KCl intermediate product;
wherein the molar ratio of W/Mo in tungstate and molybdate is 90 percent to 10 percent to 80 percent to 20 percent; the mixed solution comprises 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 tungstate ions and molybdate 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) in ammonia gas flow, heating to 500-800 ℃, reacting for 1-10 h, and then cooling to room temperature in an 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 nanosheets, namely the tungsten nitride/molybdenum nitride composite material with the layered staggered structure;
in the step (2), the heating rate is 1-20 ℃/min.
The tungsten nitride/molybdenum nitride composite material with the layered staggered structure is applied to serve as an electrode material of a super capacitor.
The invention has the following beneficial effects:
1. the WN/MoN composite electrode with the three-dimensional layered staggered structure is prepared, 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 by using a mixed salt of ammonium tungstate and ammonium molybdate in a molar ratio of 85% and 15% as a reactant. 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 material is referred to herein as WM-85. By inductively coupled plasma mass spectrometry (ICP-MS) quantitative analysis, the molar ratio of WN/MoN in the WM-85 composite product can be determined to be 93.5% to 6.5%. Excess Mo source and related products are washed away during the manufacturing process. FIG. 2 is a Scanning Electron Microscope (SEM) picture of the microstructure of the WM-85 composite. FIG. 3 is a Transmission Electron Microscope (TEM) picture of the microstructure of the above composite material and a lattice fringe phase. The WM-85 composite material has a three-dimensional layered staggered structure, namely formed by staggered stacking of WN and MoN sheets with the thickness of 2-10 nm, and the structure enables the composite material to expose more surface active sites and is beneficial to diffusion and migration of ions in an electrolyte solution. FIG. 4 shows the results at 0.5M H for a three-electrode test system 2 SO 4 In the electrolyte solution, the obtained WM-85 composite electrode has Cyclic Voltammetry (CV) curve, constant current charge and discharge (GCD) curve, and specific mass capacity under different current densitiesAnd Electrochemical Impedance Spectroscopy (EIS). Under the test current density of 0.5A/g, the discharge time of the WM-85 composite electrode is as high as 5000s, and the calculated 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 specific capacity of the composite electrode can still reach 2300F/g. As shown in FIG. 4(d), the internal resistance of the WM-85 composite electrode was lower than that of the WN electrode and the MoN electrode. FIG. 5 shows a three-electrode test system with 0.5M K 2 SO 4 The solution is an electrolyte, and a CV curve and a GCD curve of the WM-85 composite electrode are measured. Under the current density of 0.5A/g, the discharge time of the WM-85 composite electrode is 1370s, and the calculated specific mass capacity is 1625F/g. Therefore, the WN/MoN electrode shows excellent electrochemical energy storage performance in both acidic and neutral electrolytes. As shown in fig. 6, the specific capacity retention of the electrode is still as high as 90.3% after 3000 cycles under the test current density of 20A/g. The above results indicate that the WN/MoN nanocomposite having a three-dimensional layered staggered structure is an electrode material for a supercapacitor, which has excellent properties.
2. The salt template method used by the invention is a simple, high-efficiency and low-cost WN/MoN composite material preparation method. The method utilizes the lattice mismatching characteristic among MoN with a cubic structure, WN with a hexagonal structure and KCl molten salt with a cubic structure to realize different oriented growth of the MoN nanosheets and the WN nanosheets and form a three-dimensional structure formed by staggered ultrathin MoN nanosheets and WN nanosheets. This structure not only effectively prevents stacking of the nanoplates and exposes more active sites, but also provides more ion transport channels. The preparation method has the advantages of simple required equipment, controllable product structure and capability of recycling KCl template salt, so that the method is an efficient WN/MoN composite material preparation method.
Drawings
The invention is further described with reference to the following figures and detailed description.
FIG. 1 is an X-ray diffraction pattern of the WM-85 composite prepared by the salt template method of example 1. In the preparation process of the composite material, the molar ratio of ammonium tungstate to ammonium molybdate in reactants is 85% to 15%.
FIG. 2 SEM picture of the microstructure of the WM-85 composite synthesized in example 1; wherein FIG. 2(a) is an SEM picture at a magnification of 10000 times, FIG. 2(b) is an SEM picture at a magnification of 30000 times,
FIG. 3 TEM picture of the microstructure and lattice fringe phase of the WM-85 composite synthesized in example 1; wherein, fig. 3(a) is a lattice fringe phase of WN nanosheets, fig. 3(b) is a lattice fringe phase of MoN nanosheets, fig. 3(c) is a low resolution TEM picture of WN/MoN composite, and fig. 3(d) is a high resolution TEM picture of WN/MoN composite.
FIG. 4 at 0.5M H 2 SO 4 The aqueous solution is an electrolyte, and the characterization of the electrochemical energy storage performance of the WM-85 composite material obtained in example 1 is measured in a three-electrode system. Wherein, fig. 4(a) is a cyclic voltammetry curve, fig. 4(b) is a constant current charging and discharging curve, fig. 4(c) is a variation curve of the mass specific capacity along with the measured current density, and fig. 4(d) is an alternating current impedance curve.
The working electrode is prepared by uniformly dripping the prepared composite material on a glassy carbon electrode, a graphite rod electrode is used as a counter electrode, and an Ag/AgCl electrode is used as a reference electrode.
FIG. 5 at K of 0.5M 2 SO 4 The water solution is electrolyte, and the WM-85 composite electrode obtained by measurement in a three-electrode system has cyclic voltammetry curve (a) and constant current charging and discharging curve (b).
Figure 6 WN/MoN composite electrodes prepared in example 1 were tested for specific capacity stability over 3000 cycles at a current density of 20A/g.
FIG. 7 SEM pictures of the microstructure of WN/MoN composites of different compositions; wherein, 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 as a reaction raw material in a molar ratio of 95% to 5%, 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 as a reaction raw material in a molar ratio of 75% to 25%.
FIG. 8 is a graph showing the electrochemical energy storage behavior of WN/MoN composite materials with different chemical compositions; in FIG. 8(a), CV curves of different electrodes are shown, and FIG. 8(b)) GCD curves for different electrodes. The electrolyte used for the test was 0.5M H 2 SO 4 An aqueous solution.
Detailed Description
Example 1
(1) 0.170mmol (0.321g) (NH) was taken 4 ) 6 W 7 O 24 ·6H 2 O and 0.030mmol (0.037g) (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O is dispersed in a mixed solution consisting of 20mL of deionized water and 10mL of ethanol, heated to 60 ℃ and stirred for 2h until the solution is transparent. Adding 107.4g of KCl powder into the transparent colorless precursor solution for 6 times, wherein the interval between the two times of adding KCl is 10min, continuing stirring at 60 ℃ for 4h after the KCl powder is added, and drying.
(2) Placing the dried mixed powder in the step (1) in a horizontal tube furnace, introducing ammonia gas flow, raising the temperature to 700 ℃ at the speed of 1 ℃/min, reacting for 5h, and then cooling to room temperature in the atmosphere of ammonia gas to obtain a reaction product; and (3) sequentially cleaning the reaction product by using deionized water and ethanol, and drying at 60 ℃ to obtain the WM-85 composite electrode material.
FIG. 1 is an X-ray diffraction pattern of the WM-85 composite. From the figure, X-ray diffraction peaks ascribed to WN and MoN were observed, and XRD peaks ascribed to the remaining impurities were not observed, indicating that a WN/MoN composite material was obtained. Through the quantitative analysis of inductively coupled plasma mass spectrometry (ICP-MS), the molar ratio of WN/MoN in the WM-85 composite material is 93.5% to 6.5%. This indicates that not all of the ammonium molybdate in the reaction feed produced MoN nanoplatelets. FIG. 2 is a scanning electron micrograph of the microstructure of the WM-85 composite. The MoN nanosheets and the WN nanosheets are subjected to oriented growth in different directions, a three-dimensional structure formed by staggered ultrathin nanosheets is formed, and the nanosheets 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 fig. 4 and 5. The electrochemical energy storage performance of the WM-85 electrode is tested by adopting a three-electrode system so as toThe graphite rod electrode is a counter electrode, the Ag/AgCl electrode is a reference electrode, and 0.5M H 2 SO 4 The aqueous solution is an electrolyte. Dispersing 5mg WM-85 composite material in a mixed solution of ethanol (950 mu L) and naphthol (50 mu L), performing ultrasonic dispersion, then taking 2 mu L of suspension liquid drop to coat the surface of a clean glassy carbon electrode, and drying to obtain the working electrode. Under the test current density of 0.5A/g, the mass specific capacity of the WM-85 composite electrode reaches 3125F/g. As shown in FIG. 4(c), the specific capacity of the composite electrode is still as high as 2300F/g as the test current density is increased from 0.5A/g to 5A/g. In fig. 6, the specific capacity retention of the electrode is 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 temperature in step (2) was 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 example 1 except that the calcination time in step (2) was changed to 1 hour and 10 hours, to obtain the product same as example 1.
Examples 7, 8 and 9
The other steps are the same as example 1 except that the temperature rise rate in step (2) is changed to 5 ℃/min, 10 ℃/min and 20 ℃/min to obtain the product similar to example 1.
Examples 10 and 11
The other steps were the same as example 1 except that the KCl usage in step (1) was changed to 35.8 and 358g, to obtain the same product as in example 1.
Example 12
The other steps were the same as in example 1 except that the amounts of deionized water and ethanol used in step (1) were changed to 20mL and 5mL, to obtain the same product as in example 1.
Example 13
The other steps are the same as example 1, except that the amounts of deionized water and ethanol used in step (1) were changed to 10mL and 20mL, to obtain the same product as in example 1.
Example 14
The 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
The 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 and 19
The other steps are the same as example 1 except that the drying temperature in step (1) is changed to 40, 50, 70 and 90 ℃ to obtain the product the same as example 1.
Example 20
The other steps are the same as example 1 except that ammonium tungstate in step (1) is changed to sodium tungstate (Na) 2 WO 4 ·2H 2 O), ammonium molybdate is changed to sodium molybdate (Na) 2 MoO 4 ·2H 2 O), and weighing 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 obtain the same products as in example 1.
Example 21
The other steps are the same as example 1 except that ammonium tungstate ((NH) in step (1) is used 4 ) 6 W 7 O 24 ·6H 2 O) and ammonium molybdate ((NH) 4 ) 6 Mo 7 O 24 ·4H 2 O) is adjusted to 0.180 and 0.020mmol respectively, namely the mass is 0.340 and 0.025g respectively; the amount of KCl salt was adjusted to 109.4g to obtain the same product as in example 1. Other synthesis processes are the same as those in the example 1, the molar ratio of WN/MoN in the product is 96% to 4% through ICP-MS measurement, and the electrochemical energy storage performance of the composite electrode is obtained through testing, so that the product is the same as that in the example 1.
Example 22
The other steps are the same as example 1 except that ammonium tungstate ((NH) in step (1) is used 4 ) 6 W 7 O 24 ·6H 2 O) and ammonium molybdate ((NH) 4 ) 6 Mo 7 O 24 ·4H 2 O) is adjusted to 0.160 and 0.040mmol respectively, i.e. the mass is 0.302 and 0.049g respectively; the amount of KCl salt was adjusted to 105.4 g. The other synthesis processes are the same as those in example 1, the molar ratio of WN/MoN in the composite material prepared by ICP-MS measurement is 90% to 10%, and the electrochemical energy storage performance of the composite electrode is obtained by testing, so that the product is the same as that in example 1.
Comparative example 1
The other steps are the same as example 1 except that ammonium tungstate ((NH) in the mixed dispersion liquid in the step (1) is added 4 ) 6 W 7 O 24 ·6H 2 O) and ammonium molybdate ((NH) 4 ) 6 Mo 7 O 24 ·4H 2 O) was adjusted to 0.190 and 0.010mmol, respectively, i.e., the mass was 0.359 and 0.012g, respectively, and the KCl amount was changed to 111.4 g. As shown in fig. 7(a), the prepared WM-95 composite material has a sheet-like agglomerated structure. As shown in FIG. 8, the electrochemical energy storage performance of the electrode is reduced sharply, and the specific mass capacity is 769F/g.
Comparative example 2
The other steps were the same as in example 1 except that ammonium tungstate ((NH) was added to the dispersion mixture in step (1) 4 ) 6 W 7 O 24 ·6H 2 O) and ammonium molybdate ((NH) 4 ) 6 Mo 7 O 24 ·4H 2 O) was adjusted to 0.150 and 0.050mmol, i.e. 0.283 and 0.062g mass, respectively, and KCl was changed to 103.5 g. As shown in FIG. 7(b), the WM-75 composite was prepared to have a laminate-like microstructure. The specific mass 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 example 1 except that the calcination temperature in step (2) is adjusted to 450 ℃, the interface bonding of the obtained composite product is not tight, the specific mass capacity is 500F/g, and is only slightly higher than WN (158F/g).
Comparative example 4
The other steps are the same as example 1, except that the calcination temperature in step (5) is respectively adjusted to 850 ℃, WN and MoN react, and a WN/MoN composite material cannot be obtained.
As can be seen from the above examples and comparative examples, the inventors of the present invention have conducted extensive studies to find that the molar ratio of tungstate to molybdate in the raw materials and the calcination temperature must be strictly controlled during the preparation, otherwise the final product will not have a three-dimensional structure formed by interleaving ultrathin nanosheets and excellent energy storage performance due to the structure. Therefore, the proper process is the key for preparing WN/MoN composite materials with ultrathin nanosheet structures.
The invention is not the best known technology.
Claims (5)
1. The 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 is 90 percent to 10-96 percent to 4 percent;
the material is of a three-dimensional staggered layered composite structure, an ultrathin WN nanosheet and a MoN nanosheet are staggered with each other to form a three-dimensional structure, the thickness of the two nanosheets is 2-10 nm, and the width of the two nanosheets is 200-600 nm.
2. The method for preparing WN/MoN nanocomposite with a layered staggered structure according to claim 1, wherein the method 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 of addition is 5-15 min, continuing stirring at 40-90 ℃ for 2-6 hours after the KCl powder is added, and drying after stirring to obtain a mixed salt/KCl intermediate product;
wherein the molar ratio of W/Mo in tungstate and molybdate is 90 percent to 10 percent to 80 percent to 20 percent; the mixed solution comprises 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 tungstate ions and molybdate ions in the mixed solution is 1-10 mmol/L;
(2) placing the mixed salt/KCl intermediate product obtained in the step (1) in ammonia gas flow, heating to 500-800 ℃, reacting for 1-10 h, and then cooling to room temperature in an ammonia gas atmosphere to obtain a reaction product; and washing the reaction product by using deionized water and ethanol, and drying at 40-90 ℃ to obtain WN/MoN nanosheets, namely the tungsten nitride/molybdenum nitride composite material with the layered staggered structure.
3. The method according to claim 2, wherein 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), ammonium molybdate ((NH) 4 ) 2 MoO 4 ) Sodium molybdate (Na) 2 MoO 4 ·2H 2 O)。
4. The method for preparing WN/MoN nanocomposite with a layered staggered structure as claimed in claim 2, wherein in the step (2), the temperature rise rate is 1-20 ℃/min.
5. Use of the tungsten nitride/molybdenum nitride composite material with a layered staggered structure according to claim 1 as an electrode material for a supercapacitor.
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