CN113206244A - Preparation method of vanadium nitride @ nitrogen-doped carbon as electrode material of lithium/zinc ion battery - Google Patents
Preparation method of vanadium nitride @ nitrogen-doped carbon as electrode material of lithium/zinc ion battery Download PDFInfo
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- CN113206244A CN113206244A CN202110449842.5A CN202110449842A CN113206244A CN 113206244 A CN113206244 A CN 113206244A CN 202110449842 A CN202110449842 A CN 202110449842A CN 113206244 A CN113206244 A CN 113206244A
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- ion battery
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The invention particularly relates to a preparation method of vanadium nitride @ nitrogen doped carbon serving as an electrode material of a lithium/zinc ion battery, and belongs to the field of electrochemistry and new energy materials. According to the method, urea or melamine, ammonium metavanadate and glucose are mixed by a solid-phase mixing method by adopting an in-situ preparation method to obtain a reactant raw material, the reactant raw material is transferred into a porcelain boat and subjected to high-temperature calcination in a tubular furnace under a protective atmosphere, and black powder obtained after cooling is the vanadium nitride @ nitrogen doped carbon composite material. The shape of the vanadium nitride nano particle is a rose-shaped lamellar layer, the average particle size of the vanadium nitride nano particle is 2-7nm, and the particles are uniformly distributed on the nitrogen-doped carbon carrier. The nitrogen-doped carbon support acts as a stabilizer and provides a synergistic effect for the vanadium nitride nanoparticles. The composite material has wide application prospect in the field of energy storage materials. The lithium/zinc ion battery electrode material shows higher specific capacity and better cycling stability.
Description
Technical Field
The invention discloses a vanadium nitride @ nitrogen-doped carbon composite material and a preparation method thereof, and belongs to the field of electrochemistry and new energy materials.
Background
In the face of increasing demand for electronic devices, Lithium Ion Batteries (LIBs) have been widely studied in recent decades due to high energy density and long cycle life, and have been used in many electronic devices. The LIBs anode materials currently most widely used are carbon materials with good cycling performance but due to their small theoretical capacity (372 mAh g)-1) And the volume specific capacity is low, so that the carbon cathode material is difficult to meet the requirements of various electronic products and electric automobiles on high capacity of batteries. In recent years, some non-carbon-based materials have become one of the hot spots of current LIBs anode material research due to their high specific capacity, lower lithium intercalation potential and excellent safety performance. Among the novel non-carbon based negative electrode materials studied in many years, Transition Metal Nitrides (TMNs) have gradually become hot materials studied and concerned by scientists due to their low and flat charge-discharge potential platforms, highly reversible reaction characteristics, large capacity and the like. The material is expected to replace graphite and becomes a next-generation novel high-performance LIBs cathode material.
Among all metal nitrides, VN is the most promising candidate, high conductivity (1.6 x 10)6 Ω-1 m -1) Large theoretical specific capacity (LIBs 1238 mAh g-1). Unfortunately, like most negative electrode materials, they vary greatly in volume, Li+Slow diffusion kinetics, large polarization, low utilization rate of electrochemical active particles and rapid capacity decay. To overcome these problems, size reduction of VN anode material to nano-scale size is one of the most effective methods, which not only can buffer volume change, but also promotes Li more easily due to shorter diffusion length caused by size effect+The transfer of (2). However, nanoscale electrode materials expose more active material to the electrolyte surface, forming a thicker Solid Electrolyte Interphase (SEI) layer, consuming Li+Ions and electrolytes. Therefore, in order to solve these problems, stable SEI formation on the electrode is facilitated by introducing VN nanoscale materials into the conductive carbon matrix. In addition, active nanomaterialsThe strong coupling with the conductive carbon matrix can effectively buffer the volume change, so that the structure is complete, and the electrochemical performance is improved. On the other hand, impurity atoms such as nitrogen, phosphorus, sulfur, boron and the like are doped into the carbon material, so that the energy band structure of the material can be changed, the diffusion rate of lithium ions is reduced, the structural defect of the material is caused, and the lithium storage performance of the carbon material is improved. Nitrogen-doped carbon materials have been extensively studied and significantly improve the specific capacity and cycling stability of the materials.
Rechargeable aqueous zinc ion batteries are one of the most promising multivalent ion batteries, and are particularly attractive for large-scale energy storage due to their high safety, environmental friendliness, abundant resources, and high theoretical energy density. In general, a zinc ion battery is composed of a crystalline positive electrode, a zinc metal negative electrode, and a zinc salt water-based electrolyte. Zinc ions are usually excluded from the well-known monovalent ions (Li) due to the strong charge repulsion and the inherently slow kinetics of multivalent ions+Or Na+) Of the electrode material (c). Therefore, the search for suitable cathode materials is crucial to the development of rechargeable zinc ion batteries. Vanadium suboxides or nitrides (e.g. VN)xOy，V2O3VN), although they do not function directly as cathode materials due to unsuitable crystal structures, they are readily electrochemically oxidized to higher valence states with a reasonably significant shift in the physico-chemistry, giving them excellent potential to carry out the conversion process.
In conclusion, by combining the characteristics of the vanadium nitride nanoparticles and the advantages of the nitrogen-doped carbon material, the vanadium nitride @ nitrogen-doped carbon composite material can significantly improve the specific capacity and the cycling stability of the electrode material as the electrode material of the lithium/zinc ion battery.
Disclosure of Invention
The invention aims to provide a preparation method of a vanadium nitride @ nitrogen doped carbon composite material of an electrode material of a lithium/zinc ion battery. The method comprises the steps of mixing urea or melamine, ammonium metavanadate and glucose according to a certain mass ratio by a solid-phase mixing method to obtain a reactant raw material, transferring the reactant raw material into a porcelain boat, carrying out high-temperature calcination in a tubular furnace under a protective atmosphere, and cooling to obtain black powder, namely the vanadium nitride @ nitrogen doped carbon composite material.
The purpose of the invention is realized as follows: a vanadium nitride @ nitrogen doped carbon composite material and a preparation method thereof are disclosed, wherein the preparation method comprises the following process steps:
(1) the solid phase mixing method is any one of grinding in a mortar, planetary ball milling or high-energy ball milling.
(2) Urea or melamine, ammonium metavanadate and glucose were mixed in a 20: 1-2: 0-4, mixing by a solid phase mixing method to obtain reactant raw materials;
(3) the reactant raw materials are placed in a tubular furnace to be calcined for two sections under the protective atmosphere, specifically, the calcination is carried out for 3-4h at the temperature of 500-550 ℃, and then the temperature is raised to 650-950 ℃ to be calcined for 2-4 h.
(4) The protective atmosphere is any one of argon, nitrogen or vacuum.
The reagents described in the present invention are all analytical grade.
The preparation method of the vanadium nitride @ nitrogen-doped carbon composite material provided by the invention has the following beneficial effects:
(1) the one-pot synthesis of the material can be achieved by simply heating a mixture of glucose as a carbon source, urea or melamine as a nitrogen source, and ammonium metavanadate as a vanadium source. The widely used synthesis method for synthesizing vanadium nitride has multi-step reaction, low efficiency and high energy input, especially using dangerous NH3The disadvantage of (2). The method has the advantages of simple process, easy operation, low cost, short time consumption, sustainability and expandability, and creates more opportunities for large-scale production.
(2) The carbon substrate in the electrode material prepared by the method is uniformly doped with nitrogen elements, so that the conductivity of the carbon material can be effectively improved, and the specific capacity and the cycling stability of the composite material are further improved.
(3) The prepared vanadium nitride nano particles are uniformly distributed on the nitrogen-doped carbon substrate, and the agglomeration phenomenon of the vanadium nitride is favorably relieved. The reduction of agglomeration also allows the incorporation of vanadium nitride nanoparticles with Li on nitrogen-doped carbon+Or Zn2+Table of contactThe rate is increased and Li is also shortened+Or Zn2+The transmission distance of the material is long, so that the material shows high and stable cycle performance and rate performance.
Drawings
Figure 1 is an X-ray diffraction (XRD) pattern of the vanadium nitride @ nitrogen doped carbon composite prepared in example 1 of the present invention.
Fig. 2 is a Transmission Electron Microscope (TEM) of the vanadium nitride @ nitrogen doped carbon composite material prepared in example 1 of the present invention.
Fig. 3 is a High Resolution Transmission Electron Microscope (HRTEM) of the vanadium nitride @ nitrogen doped carbon composite material prepared in example 1 of the present invention.
Fig. 4 is a first three-turn charge-discharge curve of the vanadium nitride @ nitrogen-doped carbon composite material prepared in example 1 of the present invention as a negative electrode material of a lithium ion battery.
FIG. 5 shows that the vanadium nitride @ nitrogen-doped carbon composite material prepared in example 1 of the present invention is used as 0.1A g of the negative electrode material of a lithium ion battery-1Cycling stability performance at current density.
FIG. 6 shows that the vanadium nitride @ nitrogen-doped carbon composite material prepared in example 1 of the present invention is 1A g as a negative electrode material of a lithium ion battery-1Long cycle stability at current density.
Fig. 7 shows the rate capability of the vanadium nitride @ nitrogen-doped carbon composite material prepared in example 1 of the present invention as a negative electrode material of a lithium ion battery.
Fig. 8 is an initial charge-discharge voltage curve (including an activation process and the first four cycles) of the vanadium nitride @ nitrogen doped carbon composite material prepared in example 5 of the present invention as a positive electrode material of a zinc ion battery.
Fig. 9 is a first four-turn charge-discharge curve of the vanadium nitride @ nitrogen-doped carbon composite material prepared in example 5 of the present invention as a positive electrode material of a zinc ion battery.
FIG. 10 shows 2A g indicating that the vanadium nitride @ nitrogen doped carbon composite material prepared in example 5 of the present invention is used as the positive electrode material of a zinc ion battery-1Cycling stability performance at current density.
Detailed Description
The present invention is further illustrated by the following specific examples.
Example 1 vanadium nitride @ nitrogen-doped carbon composite material as lithium ion battery negative electrode material I
In a typical procedure, urea (4 g), ammonium metavanadate (0.4 g) and glucose (0.4 g) were mixed together by grinding in a mortar to form a homogeneous mixture. The mixture was then placed in a porcelain boat with a lid and kept at 3 ℃ for min under a stream of nitrogen (400 sccm)-1Is heated to 550 ℃. After 4 hours of holding, at 3 ℃ min-1The temperature was raised to 750 ℃ and maintained at this temperature for 2 hours. Subsequently, the furnace was slowly cooled to room temperature and VN/NC nanocomposites were obtained without further work-up. The mixture was calcined under nitrogen atmosphere using a two-stage heating method throughout the experiment. In the first stage, during pyrolysis, urea releases ammonia, nitrogen and other cyanides, and gradually from NH, due to the various oxidation states of vanadium (II-V)4VO3Transition to VN. At the same time, the thermal decomposition of urea at 550 ℃ produces a laminar graphitic carbonitride (g-C)3N4) G to C3N4Incorporating glucose-derived carbon and vanadium nitride into their interlayer spacing. Thus, g-C of the layer3N4The aggregation of VN nanoparticles is limited. In the second stage, g-C is mixed3N4Used as template and completely decomposed at 750 ℃. At the same time, since the atomic size difference between N and C is small, it will be derived from g-C3N4The nitrogen of (a) is introduced into the carbon skeleton. Finally, VNC nanocomposites can be obtained without any post-treatment. FIG. 1 is an XRD pattern of the prepared vanadium nitride @ nitrogen doped carbon composite material, and it can be seen that there are strong diffraction peaks at 2 theta values of 37.6 deg., 43.7 deg., 63.6 deg., 76.3 deg., indicating that cubic VN (JCPDS, No, 73-0528) has been prepared. It is located at about 26.2 ° and corresponds to the graphite (002) plane. It can be seen that the electrode material prepared contains carbon and vanadium nitride. Fig. 2 is a Transmission Electron Microscope (TEM) image of the prepared vanadium nitride @ nitrogen-doped carbon composite material, and it can be seen that the morphology of the material synthesized by us is a rose-like lamellar structure. Vanadium nitride @ nitrogen doped carbon nano-scale prepared in figure 3High resolution microscopy images (HRTEM) of the composite material show that nanoparticles with a particle size of 2-7nm are uniformly dispersed on the N-doped carbon matrix. From the upper left inset of fig. 3, a diffraction ring is visible in the selected area electron diffraction pattern, indicating that the material on the surface is crystalline. The lower right inset of fig. 3 can see the lattice fringes of the nanoparticles with a distance of 0.238nm, which is equal to the (111) plane of VN. Successful preparation of VN/NC materials can thus be further demonstrated. Mixing the synthesized VN/NC material, namely the active substance, a conductive agent, acetylene black and a bonding agent (PVDF) according to the mass ratio of 8: 1: 1, and coating the mixture on a copper foil (current collector) as a negative electrode material of a lithium ion battery. The electrode is used as a working electrode, a lithium sheet is used as a counter electrode, and the electrolyte is a universal lithium ion battery electrolyte 1M LiPF6EC =1: 1, a 2025 coin cell was prepared. At 0.1A g-1The first 3 times of charge-discharge curve of the electrode is shown in FIG. 4, and it can be seen that the first discharge capacity of the material is 1160 mAh g-1The first reversible charge capacity is 775 mAh g-1The second reversible capacity is 780 mAh g-1. FIG. 5 shows the electrode at 0.1A g-1The current density of the electrode was determined, and it can be seen that the reversible capacity of the electrode was still as high as 750 mAh g after 100 cycles-1Therefore, the material shows good cycle stability. This may be attributed to the synergistic effect exhibited by nitrogen-doped carbon and the incorporated VN nanocrystals, which can improve electron transport and suppress cubic expansion, increasing their reversible capacity. FIG. 6 shows the electrode at 1A g-1Long cycle stability at current density, it can be seen that the electrode still exhibits high capacity retention after 800 cycles. FIG. 7 is a graph of rate capability of electrode materials with current densities from 0.1A g-1Gradually increase to 2A g-1Then gradually decreases to 0.1A g-1. It can be seen that the capacity of the material gradually decreases as the current density increases, but when the current density is again at 0.1A g-1In the process, the capacity of the material returns to the initial specific capacity, which shows that the electrode material has excellent rate performance. These results confirm the nitridation prepared by this methodThe vanadium @ nitrogen doped carbon composite material as a lithium ion battery cathode material shows higher reversible capacity and excellent cycling stability.
Example 2 vanadium nitride @ nitrogen-doped carbon composite material as lithium ion battery negative electrode material II
In a typical procedure, urea (4 g), NH was ground in a mortar for 30 min4VO3(0.2 g) and glucose (0.4 g) were mixed together to form a homogeneous mixture. The mixture was then placed in a porcelain boat with a lid and heated at 3 ℃ for min under argon flow (400 sccm)-1Is heated to 550 ℃. After 4 hours, the temperature is kept at 3 ℃ for min-1The temperature was raised to 850 ℃ and maintained at this temperature for 2 hours. Subsequently, the furnace was slowly cooled to room temperature and VN/NC nanocomposites were obtained without further work-up. The electrode material was tested under the conditions described in example 1, using 0.1A g as a negative electrode material for lithium ion batteries-1Charging and discharging at current density, and first reversible capacity of 650 mAh g-1And the reversible capacity after 100 cycles is 630 mAh g-1。
Example 3 vanadium nitride @ nitrogen-doped carbon composite material as lithium ion battery negative electrode material III
In a typical procedure, urea (4 g), NH, was milled by high energy ball milling for 30 min4VO3(0.4 g) and glucose (0.4 g) were mixed together to form a homogeneous mixture. The mixture was then placed in a porcelain boat with a lid and heated at 3 ℃ for min under argon flow (400 sccm)-1Is heated to 550 ℃. After 4 hours, the temperature is kept at 3 ℃ for min-1The temperature was raised to 850 ℃ and maintained at this temperature for 2 hours. Subsequently, the furnace was slowly cooled to room temperature and VN/NC nanocomposites were obtained without further work-up. The electrode material was tested under the conditions described in example 1, using 0.1A g as a negative electrode material for lithium ion batteries-1Charging and discharging at current density, and first reversible capacity of 760 mAh g-1And the reversible capacity after 100 cycles is 720 mAh g-1。
Example 4 vanadium nitride @ nitrogen-doped carbon composite material as lithium ion battery negative electrode material IV
In a typical procedure, urea (4 g), NH was ball milled by a planetary ball mill for 30 min4VO3(0.4 g) and glucose (0.8 g) were mixed together to form a homogeneous mixture. The mixture was then placed in a porcelain boat with a lid and heated at 3 ℃ for min under argon flow (400 sccm)-1Is heated to 550 ℃. After 4 hours, the temperature is kept at 3 ℃ for min-1The temperature was raised to 650 ℃ and maintained at this temperature for 4 hours. Subsequently, the furnace was slowly cooled to room temperature and VN/NC nanocomposites were obtained without further work-up. The electrode material was tested under the conditions described in example 1, using 0.1A g as a negative electrode material for lithium ion batteries-1Charging and discharging at current density, and first reversible capacity of 650 mAh g-1And the reversible capacity after 100 cycles is 600 mAh g-1。
Example 5 vanadium nitride @ nitrogen-doped carbon composite as negative electrode material V of lithium ion battery
In a typical procedure, melamine (4 g), NH was ground in a mortar for 30 min4VO3(0.4 g) and glucose (0.8 g) were mixed together to form a homogeneous mixture. The mixture was then placed in a porcelain boat with a lid and heated at 3 ℃ for min under argon flow (400 sccm)-1Is heated to 550 ℃. After 4 hours, the temperature is kept at 3 ℃ for min-1The temperature was raised to 650 ℃ and maintained at this temperature for 4 hours. Subsequently, the furnace was slowly cooled to room temperature and VN/NC nanocomposites were obtained without further work-up. The electrode material was tested under the conditions described in example 1, using 0.1A g as a negative electrode material for lithium ion batteries-1Charging and discharging at current density, the first reversible capacity is 630 mAh g-1And the reversible capacity after 100 cycles is 570 mAh g-1。
Example 6 vanadium nitride @ nitrogen-doped carbon composite as positive electrode material VI of zinc ion battery
In a typical procedure, melamine (4 g) and NH were ground in a mortar for 30 min4VO3(0.4 g) were mixed together to form a homogeneous massAnd (3) mixing. The mixture was then placed in a porcelain boat with a lid and heated at 3 ℃ for min under argon flow (400 sccm)-1Is heated to 550 ℃. After 4 hours of holding, at 3 ℃ min-1The temperature was raised to 800 ℃ and maintained at this temperature for 2 hours. Subsequently, the furnace was slowly cooled to room temperature and VN/NC composites were obtained without further post-treatment. Mixing the synthesized VN/NC material, namely the active substance, the conductive agent acetylene black and the adhesive PVDF according to the mass ratio of 7: 2: 1, and coating the mixture on a titanium foil (current collector) as a positive electrode material of a zinc ion battery. Using the electrode as a working electrode and a zinc sheet as a counter electrode, 3M Zn (CF)3SO3)2Assembling 2025 type button cell in air with water system solution as electrolyte and mass load of 0.8-1.2 mg cm-2. As shown in FIG. 8, the cell passed at 50 mA g before cycling test-1And a voltage range of 0.2-1.8V by continuous galvanostatic charging. During this activation, VN/NC material was applied at ≈ 1.7v for Zn2+the/Zn site provides a very long plateau, which disappears during subsequent charging (fig. 8). Starting from the first charge, there are two plateaus at ≈ 0.65 and ≈ 1.0 v. This indicates that for new materials with high zinc storage capacity there must be a conversion reaction at initial charge. Notably, the charge branches tend to be stable from cycle 4, indicating a gradual decrease in coulombic efficiency to 100%, which may be attributed to non-aggressive activation prior to cycling. As a result, at 50 mA g-1Can realize 400 mAh g under the current density-1The discharge specific capacity is higher than that of the zinc ion battery reported under most of the current. As shown in FIG. 9, the current density was 1000 mA g-1The cell can then provide 290 mAh g after 180 cycles-1High capacity and corresponding capacity retention of 85.2%. The coulombic efficiency remained at 100% throughout, except for the first few cycles, indicating the exceptional reversibility of the cell after the activation process. These results prove that the vanadium nitride @ nitrogen-doped carbon composite material prepared by the method as the positive electrode material of the zinc ion battery shows higher reversible capacity and better cycle stability。
Example 7 vanadium nitride @ nitrogen-doped carbon composite as positive electrode material VII of Zinc ion Battery
In a typical procedure, melamine (4 g), NH was ground in a mortar for 30 min4VO3(0.4 g) and glucose (0.4 g) were mixed together to form a homogeneous mixture. The mixture was then placed in a porcelain boat with a lid and heated at 3 ℃ for min under argon flow (400 sccm)-1Is heated to 550 ℃. After 4 hours, the temperature is kept at 3 ℃ for min-1The temperature was raised to 750 ℃ and maintained at this temperature for 3 hours. Subsequently, the furnace was slowly cooled to room temperature and VN/NC nanocomposites were obtained without further work-up. The electrode material was tested as described in example 6, using 1000 mA g of positive electrode material for zinc ion battery-1Charging and discharging at current density, and reversible capacity of 250 mAh g after 180 cycles-1。
Claims (5)
1. A preparation method of vanadium nitride @ nitrogen doped carbon as an electrode material of a lithium/zinc ion battery is characterized by comprising the following steps of: mixing urea or melamine, ammonium metavanadate and glucose according to a certain mass ratio by a solid-phase mixing method to obtain reactant raw materials, transferring the reactant raw materials into a porcelain boat, carrying out high-temperature calcination in a tubular furnace under a protective atmosphere, and cooling to obtain black powder, namely the vanadium nitride @ nitrogen doped carbon composite material.
2. The method for preparing the vanadium nitride @ nitrogen doped carbon as the electrode material of the lithium/zinc ion battery as defined in claim 1, wherein: the solid phase mixing method is any one of grinding in a mortar, planetary ball milling or high-energy ball milling.
3. The method for preparing the vanadium nitride @ nitrogen doped carbon as the electrode material of the lithium/zinc ion battery as defined in claim 1, wherein: urea or melamine, ammonium metavanadate and glucose were mixed according to a 20: 1-2: 0-4 by mass ratio.
4. The method for preparing the vanadium nitride @ nitrogen doped carbon as the electrode material of the lithium/zinc ion battery as defined in claim 1, wherein: the protective atmosphere is any one of argon, nitrogen or vacuum.
5. The method for preparing the vanadium nitride @ nitrogen doped carbon as the electrode material of the lithium/zinc ion battery as defined in claim 1, wherein: the high-temperature calcination condition is to carry out two-stage calcination, specifically to calcine for 3-4h at the temperature of 500-550 ℃, and then heat up to the temperature of 650-950 ℃ to calcine for 2-4 h.
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