CN106684383B - Mesoporous molybdenum nitride nanowire and preparation method and application thereof - Google Patents

Mesoporous molybdenum nitride nanowire and preparation method and application thereof Download PDF

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CN106684383B
CN106684383B CN201710055127.7A CN201710055127A CN106684383B CN 106684383 B CN106684383 B CN 106684383B CN 201710055127 A CN201710055127 A CN 201710055127A CN 106684383 B CN106684383 B CN 106684383B
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麦立强
姜亚龙
董君
魏湫龙
安琴友
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Wuhan University of Technology WUT
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Abstract

The invention belongs to the technical field of nano materials and electrochemistry, and particularly relates to a preparation method of an ordered mesoporous molybdenum nitride nanowire, which can be used as a high-power long-life sodium ion battery cathode active material, the length of the material is 4-6 microns, the diameter of the material is 100 plus one 150 nanometers, the nanowire contains rich mesoporous structures and is in a slit shape, and the specific surface area of the nanowire can reach 55m2Per g, pore volume up to 0.087cm3(ii) in terms of/g. The invention has the beneficial effects that: based on a nanostructure optimization mechanism, the ordered mesoporous molybdenum nitride nanowire is synthesized by a simple and ingenious water bath-calcination method. When the ordered mesoporous molybdenum nitride nanowire prepared by the method is used as a negative electrode material of a sodium ion battery, the ordered mesoporous molybdenum nitride nanowire has excellent rate performance and cycling stability, and is a potential negative electrode material of a high-performance sodium ion battery.

Description

Mesoporous molybdenum nitride nanowire and preparation method and application thereof
Technical Field
The invention belongs to the technical field of nano materials and electrochemistry, and particularly relates to a preparation method of an ordered mesoporous molybdenum nitride nanowire, which can be used as a high-power long-life sodium ion battery cathode active material.
Background
As a green energy storage device, a lithium ion battery has been widely used in daily life of people, such as portable electronic devices and electric vehicles. It is worth noting that lithium is limited in its content on earth, and the price of lithium is on the rise due to large-scale demand. Compared with lithium, sodium is more widely and abundantly available and has lower cost. Meanwhile, since sodium has physical and chemical properties similar to those of lithium, a sodium ion battery can operate as a lithium ion battery and is stable and safe. Therefore, the development of a sodium ion battery energy storage system based on high capacity, high power and low cost is the direction with great application prospect in the current low-carbon economic era.
It is well known that the electrochemical performance of a battery depends mainly on the properties of the electrode material. The vanadium sodium phosphate which is widely researched at present has excellent electrochemical performance and can be used as the anode material of a sodium-ion battery. However, the commercial graphite which is more mature in application at present is difficult to be used as the negative electrode material of the sodium-ion battery. Therefore, the development of a negative electrode material for a sodium ion battery with high capacity, high power and long cycle life is a key problem to be solved urgently at present. Compared with a lithium ion battery, a sodium ion battery has the advantages of low price and wide source, but the ionic radius of sodium ions is 1.43 times that of lithium ions, so that the sodium ions have a slower ion diffusion rate, and therefore, the cathode material of a general sodium ion battery has a lower ion and electron diffusion rate, so that the rate characteristic is poor, the power density is low, and further development of the sodium ion battery in portable equipment and application of the sodium ion battery in a hybrid electric vehicle are limited.
In recent years, nano materials have attracted more and more attention in the fields of electrochemistry and energy because of a series of excellent characteristics such as high specific surface area, better reactivity and the like. When the battery electrode material is subjected to nanocrystallization, the contact area of the material and an electrolyte is increased, the ion deintercalation distance is shortened, and the realization of high-rate charge and discharge performance is facilitated. Meanwhile, the nano structure is beneficial to stress release in the circulation process, the structure is stabilized, and longer circulation life is obtained.
Transition metal nitrides are considered potential battery negative electrode materials due to their high electronic conductivity, high theoretical specific capacity, and pseudocapacitance characteristics. However, the general transition metal nitride undergoes a large volume expansion during charge and discharge, and finally causes structural destruction, resulting in poor cycle stability. Meanwhile, the stable nitride structure enables the activity of the nitride to be not very high in the electrochemical reaction process, so that the capacity of the nitride is not high and is far lower than the theoretical specific capacity of the nitride. In recent years, the electrochemical properties of molybdenum nitride have been studied gradually, but it has never been reported as a negative electrode material for sodium ion batteries. Therefore, designing and synthesizing appropriate nano-structures and improving the electrochemical activity of molybdenum nitride are the key points for obtaining high-performance sodium-ion battery cathode materials.
Disclosure of Invention
The invention aims to solve the technical problem of providing a mesoporous molybdenum nitride nanowire and a preparation method thereof aiming at the prior art, the process is simple, and the obtained ordered mesoporous molybdenum nitride nanowire has excellent electrochemical performance as a cathode material of a sodium ion battery.
The technical scheme adopted by the invention for solving the technical problems is as follows: the mesoporous molybdenum nitride nanowire has the length of 4-6 microns and the diameter of 100-150 nanometers, the nanowire contains rich mesoporous structures and is in a slit shape, and the specific surface area of the nanowire can reach 55m2Per g, pore volume up to 0.087cm3/g。
The preparation method of the mesoporous molybdenum nitride nanowire is characterized by comprising the following steps:
1) weighing ammonium heptamolybdate, dissolving the ammonium heptamolybdate in deionized water, and fully stirring to obtain a clear solution;
2) adding the aniline solution into the clear solution obtained in the step 1), and fully reacting for 10-20 minutes;
3) adjusting the pH value of the solution obtained in the step 2) by the prepared hydrochloric acid solution;
4) reacting the mixture obtained in the step 3) under the condition of water bath to obtain white precipitate;
5) washing the white precipitate obtained in the step 4), and drying in an oven to obtain a white nanowire precursor;
6) heating the white nanowire precursor obtained in the step 5) in an ammonia atmosphere, carrying out heat preservation sintering, naturally cooling to room temperature, and taking out to obtain the ordered mesoporous molybdenum nitride nanowire.
According to the scheme, the dosage of the ammonium heptamolybdate in the step 1) is 1-2g, the dosage of the deionized water is 15-20ml, and the dosage of the aniline solution is 1-2 g.
According to the scheme, the concentration of the hydrochloric acid solution in the step 3) is 1-1.5mol/L, and the pH value of the solution is adjusted to be 4-5.
According to the scheme, the water bath condition in the step 4) is 50-60 ℃ and the time is 6-8 hours.
According to the scheme, the white precipitate obtained in the step 4) is washed for 5-7 times by alcohol in the step 5), and then dried in an oven at the temperature of 60-80 ℃.
According to the scheme, the sintering temperature in the step 6) is 500-900 ℃, and the sintering time is 2-6 hours.
The mesoporous molybdenum nitride nanowire is applied as a cathode active material of a mixed sodium-ion capacitor.
The invention effectively increases the contact area of the electrolyte and the electrode material by utilizing the large specific surface area of the mesoporous nano-wire, and simultaneously ensures good electron transport by the one-dimensional nano-wire structure; the micro nanowire structure greatly shortens the diffusion distance of sodium ions and realizes good rate performance; the ordered mesopores uniformly distributed on the nanowires can effectively release internal stress caused by expansion and contraction of the material in the charge-discharge process, effectively prevent the structural collapse of the electrode material in the circulation process, and improve the circulation stability of the material. Experiments prove that the ordered mesoporous molybdenum nitride nanowire has high specific capacity, good rate performance and long cycle life, and is a sodium ion battery cathode material with high practical application value.
The invention has the beneficial effects that: based on a nanostructure optimization mechanism, the ordered mesoporous molybdenum nitride nanowire is synthesized by a simple and ingenious water bath-calcination method. When the ordered mesoporous molybdenum nitride nanowire prepared by the method is used as a negative electrode material of a sodium ion battery, the ordered mesoporous molybdenum nitride nanowire has excellent rate performance and cycling stability, and is a potential negative electrode material of a high-performance sodium ion battery.
Drawings
FIG. 1 is an XRD pattern of ordered mesoporous molybdenum nitride nanowires of example 1 of the present invention;
FIG. 2 is a transmission electron micrograph and an elemental distribution of the ordered mesoporous molybdenum nitride nanowires of example 1 of the present invention;
FIG. 3 is a nitrogen adsorption isotherm and a pore size distribution diagram of the ordered mesoporous molybdenum nitride nanowires of example 1 of the present invention;
FIG. 4 is an XPS plot of ordered mesoporous molybdenum nitride nanowires of example 1 of the present invention;
FIG. 5 is a graph of battery cycle performance at current densities of 0.1A/g and 1.0A/g when the ordered mesoporous molybdenum nitride nanowire of example 1 of the present invention is used as a cathode of a sodium ion battery;
FIG. 6 is a graph of rate capability of the ordered mesoporous molybdenum nitride nanowires of example 1 of the present invention as a negative electrode of a sodium ion battery;
fig. 7 is an ac impedance spectrum of the ordered mesoporous molybdenum nitride nanowire of example 1 of the present invention as a negative electrode of a sodium ion battery.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
Example 1:
the preparation method of the mesoporous molybdenum nitride nanowire comprises the following steps:
1) weighing 1.24g of ammonium heptamolybdate, dissolving the ammonium heptamolybdate in 20ml of deionized water, and fully stirring until the ammonium heptamolybdate is completely dissolved;
2) weighing 1.67g of aniline solution, dropwise adding the aniline solution into the clear solution obtained in the step 1), and fully reacting for 10 minutes;
3) 1mol L of the prepared-1Adjusting the pH value of the solution obtained in the step 2) to 4-5 by using a hydrochloric acid solution;
4) the mixture obtained in the step 3) is reacted for 8 hours in a water bath at the temperature of 50 ℃ to obtain white precipitate.
5) Cleaning the white precipitate obtained in the step 4) for 5 times by using alcohol, and then drying the white nanowire precursor in an oven at the temperature of 60 ℃ all night.
6) Heating the white precursor nanowire obtained in the step 5) at 500 ℃ in an ammonia atmosphere, preserving the heat for 6 hours, naturally cooling to room temperature, and taking out to obtain the molybdenum nitride nanowire with the ordered mesopores.
Taking the mesoporous molybdenum nitride nanowire product of the present embodiment as an example, the structure of the mesoporous molybdenum nitride nanowire is determined by an X-ray diffraction (XRD) spectrum. As shown in the XRD spectrum of figure 1, the mesoporous molybdenum nitride nanowire is a pure phase molybdenum nitride phase (JCPDS card number 01-089-5025). As shown in the transmission electron microscope picture of FIG. 2, the mesoporous nanowires have a size of 4-6 μm in length and a diameter of 100-150 nm, and the mesopores are in the shape of a special slit and are distributed on the nanowires in order. As shown in FIG. 3, it can be seen from the nitrogen desorption isotherm diagram that the specific surface area thereof can reach 55m2Per g, wherein the pore volume can reach 0.087cm3The pore size distribution indicates that the main pore size is around 5nm and the average pore size is 7.94 nm.
As shown in FIG. 4, XPS analysis shows that the ordered mesoporous molybdenum nitride nanowire has a large amount of oxygen doping, wherein the content of hexavalent molybdenum reaches 27.4%. By scanning the element distribution under TEM, as shown in fig. 2, it can be obtained that Mo, N, O, and C elements are uniformly distributed. The ordered mesoporous molybdenum nitride nanowire is proved to be oxygen-rich doped, and higher element valence provides higher reaction activity and capacity for the reaction process.
The ordered mesoporous molybdenum nitride nanowire prepared in the embodiment is used as a negative electrode active material of a sodium ion battery, and other steps of the preparation method of the electrode plate are the same as those of a common preparation method. The preparation method of the cathode plate comprises the following steps of adopting the ordered mesoporous molybdenum nitride nanowires as an active material, acetylene black as a conductive agent and CMC as a binder, wherein the mass ratio of the active material to the acetylene black to the CMC is 80:15: 5; after fully mixing the raw materials in proportion, uniformly coating the mixture on a copper foil; and (3) drying the coated negative plate in a vacuum oven at 120 ℃ for 10 hours for later use. 1mol/L NaClO4Dissolving in EC and DMC (EC to DMC volume ratio of 1:1)5% of FEC additive is added as electrolyte, sodium sheet is counter electrode, glass fiber is diaphragm, CR2016 type stainless steel is battery case to assemble button sodium ion battery.
When the ordered mesoporous molybdenum nitride nanowire prepared in the embodiment is used as a negative electrode material of a sodium ion battery, as shown in fig. 5, excellent cycling stability is demonstrated. When the current density is 0.1A/g, the reversible capacity is 300 mAh/g; under the current density of 1A/g, the reversible capacity is still 273.2mAh/g, and the reversible capacity has excellent cycle stability, for example, the capacity can reach 207.6mAh/g after the current density is 1A/g and the cycle is carried out for 1000 times. As shown in FIG. 6, the excellent rate capability is demonstrated, and the reversible capacity still has 42.5mAh/g capacity at a current density of 30A/g. Meanwhile, through an alternating current impedance spectrum test, as shown in fig. 7, the charge transfer resistance of the capacitor is only 206 Ω. The measured result shows that the ordered mesoporous molybdenum nitride nanowire has excellent high rate performance and long cycle life, and is a potential high-performance sodium ion battery cathode material.
Example 2:
the preparation method of the ordered mesoporous molybdenum nitride nanowire comprises the following steps:
1) weighing 1.24g of ammonium heptamolybdate, dissolving the ammonium heptamolybdate in 20ml of deionized water, and fully stirring until the ammonium heptamolybdate is completely dissolved;
2) weighing 1.67g of aniline solution, dropwise adding the aniline solution into the clear solution obtained in the step 1), and fully reacting for 10 minutes;
3) 1mol L of the prepared-1Adjusting the pH value of the solution obtained in the step 2) to 4-5 by using a hydrochloric acid solution;
4) the mixture obtained in the step 3) is reacted for 6 hours in a water bath at the temperature of 50 ℃ to obtain a white precipitate.
5) Cleaning the white precipitate obtained in the step 4) for 5 times by using alcohol, and then drying the white nanowire precursor in an oven at the temperature of 60 ℃ all night.
6) Heating the white precursor nanowire obtained in the step 5) at 600 ℃ in an ammonia atmosphere, preserving the heat for 6 hours, naturally cooling to room temperature, and taking out to obtain the molybdenum nitride nanowire with the ordered mesopores.
When the ordered mesoporous molybdenum nitride nanowire prepared by the embodiment is used as a negative electrode material of a sodium ion battery, the reversible capacity is 150mAh/g when the current density is 0.1A/g, the capacity is still 54.4mAh/g under the current density of 8A/g, the cycling stability is excellent, and the capacity can reach 78.2mAh/g after the current density is 1A/g is cycled for 1000 times. The charge transfer resistance of the material is 467 omega through an alternating current impedance spectrum test.
Example 3:
the preparation method of the ordered mesoporous molybdenum nitride nanowire comprises the following steps:
1) weighing 1.24g of ammonium heptamolybdate, dissolving the ammonium heptamolybdate in 20ml of deionized water, and fully stirring until the ammonium heptamolybdate is completely dissolved;
2) weighing 1.67g of aniline solution, dropwise adding the aniline solution into the clear solution obtained in the step 1), and fully reacting for 10 minutes;
3) 1mol L of the prepared-1Adjusting the pH value of the solution obtained in the step 2) to 4-5 by using a hydrochloric acid solution;
4) the mixture obtained in the step 3) is reacted for 8 hours in a water bath at the temperature of 50 ℃ to obtain white precipitate.
5) Cleaning the white precipitate obtained in the step 4) for 5 times by using alcohol, and then drying the white nanowire precursor in an oven at the temperature of 60 ℃ all night.
6) Heating the white precursor nanowire obtained in the step 5) at 700 ℃ in an ammonia atmosphere, preserving the heat for 6 hours, naturally cooling to room temperature, and taking out to obtain the ordered mesoporous molybdenum nitride nanowire.
When the ordered mesoporous molybdenum nitride nanowire prepared in the embodiment is used as a negative electrode material of a sodium ion battery, the reversible capacity is 105mAh/g when the current density is 0.1A/g, the capacity is still 26.8mAh/g under the current density of 8A/g, the cycling stability is excellent, and the capacity is still 40.9mAh/g after the current density is 1A/g and the cycling is 1000. The charge transfer resistance of the material is 956 omega by an alternating current impedance spectroscopy test.
Example 4:
the preparation method of the ordered mesoporous molybdenum nitride nanowire comprises the following steps:
1) weighing 1.24g of ammonium heptamolybdate, dissolving the ammonium heptamolybdate in 20ml of deionized water, and fully stirring until the ammonium heptamolybdate is completely dissolved;
2) weighing 1.67g of aniline solution, dropwise adding the aniline solution into the clear solution obtained in the step 1), and fully reacting for 10 minutes;
3) 1mol L of the prepared-1Adjusting the pH value of the solution obtained in the step 2) to 4-5 by using a hydrochloric acid solution;
4) the mixture obtained in the step 3) is reacted for 6 hours in a water bath at the temperature of 50 ℃ to obtain a white precipitate.
5) Cleaning the white precipitate obtained in the step 4) for 5 times by using alcohol, and then drying the white nanowire precursor in an oven at the temperature of 60 ℃ all night.
6) Heating the white precursor nanowire obtained in the step 5) at 800 ℃ in an ammonia atmosphere, preserving the heat for 6 hours, naturally cooling to room temperature, and taking out to obtain the ordered mesoporous molybdenum nitride nanowire
When the ordered mesoporous molybdenum nitride nanowire prepared in the embodiment is used as a cathode material of a sodium-ion battery, the reversible capacity is 76mAh/g when the current density is 0.1A/g, the capacity is still 19.5mAh/g under the current density of 8A/g, the cycling stability is excellent, and the capacity is still 32.3mAh/g after the current density is 1A/g and the cycling is 1000. The charge transfer resistance of the material is 1210 omega by an alternating current impedance spectrum test.
Example 5:
the preparation method of the ordered mesoporous molybdenum nitride nanowire comprises the following steps:
1) weighing 1.24g of ammonium heptamolybdate, dissolving the ammonium heptamolybdate in 20ml of deionized water, and fully stirring until the ammonium heptamolybdate is completely dissolved;
2) weighing 1.67g of aniline solution, dropwise adding the aniline solution into the clear solution obtained in the step 1), and fully reacting for 10 minutes;
3) 1mol L of the prepared-1Adjusting the pH value of the solution obtained in the step 2) to 4-5 by using a hydrochloric acid solution;
4) the mixture obtained in the step 3) is reacted for 8 hours in a water bath at the temperature of 50 ℃ to obtain white precipitate.
5) Cleaning the white precipitate obtained in the step 4) for 5 times by using alcohol, and then drying the white nanowire precursor in an oven at the temperature of 60 ℃ all night.
6) Heating the white precursor nanowire obtained in the step 5) at 500 ℃ in an ammonia atmosphere, preserving the heat for 2 hours, naturally cooling to room temperature, and taking out to obtain the ordered mesoporous molybdenum nitride nanowire.
When the ordered mesoporous molybdenum nitride nanowire prepared in the embodiment is used as a negative electrode material of a sodium ion battery, the reversible capacity is 253mAh/g when the current density is 0.1A/g, the capacity is still 94mAh/g under the current density of 8A/g, the cycling stability is excellent, and the capacity is still 162.3mAh/g after the current density is 1A/g and the cycling is 1000. The charge transfer resistance of the material was 393 Ω by ac impedance spectroscopy.
Example 6:
the preparation method of the ordered mesoporous molybdenum nitride nanowire comprises the following steps:
1) weighing 1.24g of ammonium heptamolybdate, dissolving the ammonium heptamolybdate in 20ml of deionized water, and fully stirring until the ammonium heptamolybdate is completely dissolved;
2) weighing 1.67g of aniline solution, dropwise adding the aniline solution into the clear solution obtained in the step 1), and fully reacting for 10 min;
3) 1mol L of the prepared-1Adjusting the pH value of the solution obtained in the step 2) to 4-5 by using a hydrochloric acid solution;
4) the mixture obtained in the step 3) is reacted for 6 hours in a water bath at the temperature of 50 ℃ to obtain a white precipitate.
5) Cleaning the white precipitate obtained in the step 4) for 5 times by using alcohol, and then drying the white precursor nanowire in an oven at the temperature of 60 ℃ all night.
6) Heating the white precursor nanowire obtained in the step 5) at 500 ℃ in an ammonia atmosphere, preserving the heat for 4 hours, naturally cooling to room temperature, and taking out to obtain the ordered mesoporous molybdenum nitride nanowire.
When the ordered mesoporous molybdenum nitride nanowire prepared in the embodiment is used as a negative electrode material of a sodium ion battery, the reversible capacity is 286mAh/g when the current density is 0.1A/g, the capacity is still 105mAh/g under the current density of 8A/g, the cycling stability is excellent, and the capacity is still 185.2mAh/g after the current density is 1A/g and the cycling is 1000. The charge transfer resistance of the material is 354 omega by an alternating current impedance spectrum test.

Claims (4)

1. The preparation method of the ordered mesoporous molybdenum nitride nanowire comprises the steps of preparing the ordered mesoporous molybdenum nitride nanowire with the length of 4-6 microns and the diameter of 100-150 nanometers, wherein the nanowire contains rich mesoporous structures and is in a slit shape, and the specific surface area of the nanowire reaches 55m2Per g, pore volume up to 0.087cm3(g) containing the higher valent element molybdenum Mo6+Element, characterized in that it comprises the following steps:
1) weighing ammonium heptamolybdate, dissolving the ammonium heptamolybdate in deionized water, and fully stirring to obtain a clear solution;
2) adding the aniline solution into the clear solution obtained in the step 1), and fully reacting for 10-20 minutes;
3) adjusting the pH value of the solution obtained in the step 2) by using a prepared hydrochloric acid solution;
4) reacting the mixture obtained in the step 3) under the condition of water bath to obtain white precipitate; the water bath condition is 50-60 ℃ and the time is 6-8 hours;
5) washing the white precipitate obtained in the step 4), and drying in an oven to obtain a white nanowire precursor;
6) heating the white nanowire precursor obtained in the step 5) in an ammonia atmosphere, and carrying out heat preservation sintering at the sintering temperature of 500-900 ℃ for 2-6 hours; and naturally cooling to room temperature, and taking out to obtain the ordered mesoporous molybdenum nitride nanowire.
2. The method for preparing ordered mesoporous molybdenum nitride nanowires of claim 1, wherein the amount of ammonium heptamolybdate in step 1) is 1-2g, the amount of deionized water is 15-20ml, and the amount of aniline solution in step 2) is 1-2 g.
3. The method for preparing the ordered mesoporous molybdenum nitride nanowires of claim 1, wherein the concentration of the hydrochloric acid solution in the step 3) is 1-1.5mol/L, and the pH value of the solution is adjusted to 4-5.
4. The method for preparing the ordered mesoporous molybdenum nitride nanowires of claim 1, wherein the white precipitates obtained in the step 4) are washed with alcohol for 5-7 times in the step 5), and then dried in an oven at 60-80 ℃.
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