CN112820885A - Preparation method of nitrogen-doped carbon-coated titanium nitride nanoparticle composite material - Google Patents
Preparation method of nitrogen-doped carbon-coated titanium nitride nanoparticle composite material Download PDFInfo
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- 239000002105 nanoparticle Substances 0.000 title claims abstract description 39
- 239000002131 composite material Substances 0.000 title claims abstract description 38
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 title claims abstract description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims abstract description 23
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 239000011259 mixed solution Substances 0.000 claims abstract description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims abstract description 6
- 239000012153 distilled water Substances 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000004321 preservation Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 29
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 19
- 239000004408 titanium dioxide Substances 0.000 abstract description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 8
- 238000001354 calcination Methods 0.000 abstract description 6
- 239000002245 particle Substances 0.000 abstract description 5
- -1 transition metal nitride Chemical class 0.000 abstract description 5
- 229910052723 transition metal Inorganic materials 0.000 abstract description 4
- 239000010406 cathode material Substances 0.000 abstract description 2
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- 230000008569 process Effects 0.000 description 7
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- 238000001514 detection method Methods 0.000 description 5
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- 238000012360 testing method Methods 0.000 description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
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- 150000003609 titanium compounds Chemical class 0.000 description 3
- 238000004627 transmission electron microscopy Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000008859 change Effects 0.000 description 2
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- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
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- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
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- 229910052708 sodium Inorganic materials 0.000 description 1
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- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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Abstract
The invention relates to the technical field of zinc-air battery cathode materials, and particularly discloses a preparation method of a nitrogen-doped carbon-coated titanium nitride nanoparticle composite material, which comprises the following steps: uniformly stirring P123 and isopropyl titanate, dropwise adding an ethanol solution containing hydrochloric acid, uniformly stirring, adding distilled water to obtain a mixed solution, and carrying out heating reaction in an oil bath kettle to obtain a mixed solution; adding dicyandiamide into the mixed solution, heating and stirring until the mixture is evaporated to dryness to obtain a precursor material; and heating the precursor material to not lower than 750 ℃ under the protection of nitrogen, and carrying out heat preservation to obtain the nitrogen-doped carbon-coated titanium nitride nanoparticle composite material. The preparation method solves the problems that the prior mainstream transition metal nitride preparation process has large titanium dioxide particle size, is easy to agglomerate, and adopts ammonia gas for calcination to seriously pollute the environment.
Description
Technical Field
The invention relates to the technical field of zinc-air battery cathode materials, in particular to a preparation method of a nitrogen-doped carbon-coated titanium nitride nanoparticle composite material.
Background
The increasing energy crisis and environmental pollution problems are the focus of attention in today's society. As a result, clean and sustainable green energy sources are being developed to replace the ever-decreasing fossil fuels and the demand for sustainable energy conversion and storage devices is increasing. Among energy devices, metal air batteries are considered to be very competitive energy devices due to their advantages of little environmental pollution, high conversion rate, high energy density, and the like. The metal-air battery uses air (oxygen) as a cathode active material and metal as an anode active material, and the metal comprises active metal such as lithium, sodium, potassium, iron, magnesium, zinc, aluminum and the like. The zinc metal has the advantages of environmental friendliness, low cost, abundant resources, easiness in recovery and the like, and has a very wide commercialization prospect. The theoretical energy density is 1312Wh kg-1Approximately 2-5 times or even higher than current lithium ion technology. In addition, after a period of development, the application of the zinc-air battery to a new energy automobile becomes possible. Therefore, the zinc-air battery gradually attracts the attention of the researchers.
The air electrode (cathode) is an important component of the zinc-air battery and is generally composed of three parts, namely a conductive current collector, a waterproof breathable layer and a catalytic layer. And the catalyst layer is the core part of the air electrode, and the performance of the catalyst directly influences the performance of the zinc-air battery. The Oxygen Reduction Reaction (ORR) is an important issue for zinc-air batteries, and its kinetics slowly hinder the energy utilization and large-scale application of zinc-air batteries. To increase the ORR reaction rate, highly active catalysts were developed. Currently, noble platinum catalysts are considered to be effective catalysts for ORR, but their high cost and poor stability have prevented their commercial application. Therefore, it is a research focus to search and develop a catalyst with low cost, high activity and high stability to improve the performance of the zinc-air battery. The main disadvantages of the existing catalysts are as follows: the first is the development of low platinum catalysts; the second is the development of non-noble metal or metal-free catalysts. The second approach is a more efficient solution in the long term.
Transition metal nitride is a non-noble metal catalyst currently under study, and the preparation methods of the main methods are mainly two: the first method comprises the following steps: firstly, preparing a carbon-coated titanium dioxide nanoparticle composite material by a one-pot method, and then calcining at the temperature of more than 800 ℃ in an ammonia atmosphere to prepare a nitrogen-doped carbon-coated titanium nitride nanoparticle composite material; the disadvantages of this method are: the titanium dioxide has larger grain diameter and is easy to agglomerate; the titanium nitride is prepared by calcining ammonia gas, so that the cost is high, the requirement on equipment is high, and the environment is polluted.
And the second method comprises the following steps: firstly, preparing uniform titanium dioxide nano particles by a hydrolysis method, then coating a layer of carbon material on the outer surface of the titanium dioxide nano particles, and calcining the obtained precursor at the temperature of more than 800 ℃ in an ammonia atmosphere to prepare the nitrogen-doped carbon-coated titanium nitride nano particle composite material. The disadvantages of this method are: the preparation process is complicated, and most importantly, the titanium nitride is prepared by calcining with ammonia gas, so that the cost is high, the requirement on equipment is high, and the environment is polluted.
Therefore, in view of the problems of the above mainstream processes, there is an urgent need to develop a simple, efficient, environmentally friendly and low-cost method for preparing a transition metal nitride catalyst.
Disclosure of Invention
The invention provides a preparation method of a nitrogen-doped carbon-coated titanium nitride nanoparticle composite material, which aims to solve the problems that titanium dioxide is large in particle size and easy to agglomerate and the environment is seriously polluted by ammonia gas calcination in the existing mainstream transition metal nitride preparation process.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a preparation method of a nitrogen-doped carbon-coated titanium nitride nanoparticle composite material comprises the following steps:
step 1: uniformly stirring P123 and isopropyl titanate, dropwise adding the mixture into an ethanol solution containing hydrochloric acid, uniformly stirring the mixture, adding distilled water to obtain a mixed solution, and carrying out heating reaction in an oil bath kettle to obtain a mixed solution;
step 2: adding dicyandiamide into the mixed solution obtained in the step 1, heating and stirring until the mixture is evaporated to dryness to obtain a precursor material;
and step 3: and (3) heating the precursor material obtained in the step (2) to not less than 750 ℃ under the protection of nitrogen, and preserving heat to obtain the nitrogen-doped carbon-coated titanium nitride nanoparticle composite material.
The technical principle and the effect of the technical scheme are as follows:
1. in the scheme, the triblock copolymer P123 is used as a structure directing agent, titanium dioxide nanoparticles can be coated in the process of forming colloid, so that the titanium dioxide nanoparticles do not have chance to agglomerate, in addition, because dicyandiamide contains a large amount of N elements and carbon-nitrogen triple bonds (has certain reducibility), but when the temperature is higher than 80 ℃, dicyandiamide is decomposed, and in the scheme, a large amount of functional groups contained in P123 can react with dicyandiamide to inhibit the decomposition of dicyandiamide, so that at the high temperature of step 3, a part of dicyandiamide reacts with the titanium dioxide nanoparticles to generate titanium nitride nanoparticles, and the other part of dicyandiamide and P123 are pyrolyzed at the high temperature to generate the nitrogen-doped carbon material.
2. In the scheme, dicyandiamide with reducibility is used as a nitrogen source to prepare titanium nitride nanoparticles, and the triblock copolymer P123 is used as a carbon source and nitrogen source fixing agent, so that the titanium nitride nanoparticles have the advantages that: (1) the titanium nitride nanoparticles are prepared by using dicyandiamide as a nitrogen source, so that the method is environment-friendly and economic (the method is characterized in that the position harmful to the environment is not released or volatilized in the preparation process), and the requirement on equipment is low (the method is characterized in that only the precursor material is heated to the temperature of evaporation to dryness in the preparation process); (2) in the obtained composite material, the nano-scale titanium nitride nano-particles can be uniformly dispersed on the nitrogen-doped carbon material, namely, the titanium nitride nano-particles are not agglomerated together in a large amount; (3) the triblock copolymer P123 not only acts as a carbon source but also suppresses decomposition of dicyandiamide.
Further, the molar ratio of P123 to isopropyl titanate in the step 1 is 1: 0.0121.
has the advantages that: if too much raw material P123 is added, the material contains more oxygen atoms, the content of the oxygen atoms in the nitrogen-doped carbon-coated titanium nitride nanoparticle composite material is increased, the material is impure, and the synthesis and the appearance of the material are adversely affected by adding too little P123.
Further, the heating temperature of the oil bath kettle in the step 1 is 40-50 ℃.
Has the advantages that: if the heating temperature is too high, TiO2The nano particles are easy to agglomerate, the particle size is large, the hydrolysis of isopropyl titanate is incomplete when the temperature is too low, and the self-assembly process of the triblock copolymer P123 can be completely carried out in the temperature range.
Further, the molar ratio of dicyandiamide to isopropyl titanate in the step 2 is 1.76-26.41: 1.
has the advantages that: beyond this range of molar ratio in the present scheme, although the nitrogen-doped carbon-coated titanium nitride nanoparticle composite material can still be prepared, the nitrogen-doped carbon layer becomes thicker and thicker as the amount of dicyandiamide increases, which adversely affects the catalytic activity of the composite material.
Further, the heating temperature in the step 2 is 40-45 ℃.
Has the advantages that: at the temperature, the mixed solution is subjected to rapid reaction to obtain a precursor material, and when the temperature is too high, DCDA (dicyandiamide) is decomposed, and TiO is caused2The particles grow and eventually TiN particles grow.
Further, the temperature of the temperature rise in the step 3 is 800-1000 ℃, and the heat preservation time is 1-1.5 h.
Has the advantages that: the temperature is verified by experiments, and TiO is2Can fully react with surrounding nitrogen atoms to generate TiN, and if the temperature is higher than 1000 ℃, the TiN @ NC composite material can also be preparedHowever, since the requirement for equipment is high, it is preferable that the temperature is raised to 800 ℃ to 1000 ℃ in connection with actual production.
Drawings
FIG. 1 is a SEM test result chart of TiN @ NC-1 composite material obtained in example 1 of the invention;
FIG. 2 is a TEM inspection result of TiN @ NC-1 composite material obtained in example 1 of the present invention;
FIG. 3 is a diagram showing XRD detection results of TiN @ NC composite materials obtained in examples 1 to 12 of the present invention;
FIG. 4 is a polarization curve diagram of TiN @ NC composite materials obtained in embodiments 4-7 of the invention;
FIG. 5 is a graph of a half-slope potential of TiN @ NC composite material obtained in examples 4 to 7 of the present invention;
FIG. 6 is a graph of the limiting diffusion current density of TiN @ NC composite materials obtained in examples 4 to 7 of the present invention;
FIG. 7 is a graph showing the change in current density after 1000 cycles in example 5 of the present invention.
FIG. 8 is a discharge polarization curve and corresponding power density curve for a zinc-air cell in accordance with example 5 of the present invention;
fig. 9 is a graph of cycle testing in a zinc-air cell according to example 5 of the present invention.
Detailed Description
The following is further detailed by way of specific embodiments:
example 1:
a preparation method of a nitrogen-doped carbon-coated titanium nitride nanoparticle composite material comprises the following steps:
step 1: mixing a mixture of 1: 0.0128 of polyethylene oxide-polypropylene oxide-polyethylene oxide (P123) and isopropyl titanate (TTIP) are placed in a 10mL glass bottle, uniformly stirred, and then gradually dripped into an ethanol solution containing hydrochloric acid (HCl) after stirring for 10min, wherein the concentration of the hydrochloric acid is 36%, distilled water is added after stirring for 10min, the volume ratio of the distilled water to the TTIP is 1:1, stirring is carried out at room temperature for 30min to obtain a mixed solution, the mixed solution is placed in an oil bath pot for heating reaction to obtain a mixed solution, and the heating temperature is 40 ℃.
Step 2: adding dicyandiamide (DCDA) into the mixed solution reacted in the step 1, heating to 40 ℃, stirring until the mixed solution is evaporated to dryness, and obtaining a precursor material, wherein the molar ratio of the added DCDA to the TTIP is 1.76: 1.
and step 3: and (3) placing the precursor material obtained in the step (2) into a corundum crucible, then placing the corundum crucible into a tube furnace, heating to 800 ℃ under the protection of nitrogen, preserving the heat for 1.5 hours, and then cooling to room temperature to obtain the nitrogen-doped carbon-coated titanium nitride nanoparticle composite material, namely the TiN @ NC composite material, wherein the number of the TiN @ NC composite material obtained in the embodiment 1 is TiN @ NC-1 for the convenience of comparison.
Example 2 to example 12:
the difference from example 1 is that the raw material ratios or the process parameters prepared in examples 2 to 12 are different, specifically as shown in tables 1 and 2 below, and P123: TTIP and DCDA: TTIP are molar ratios in tables 1 and 2.
Table 1 is a table of raw material ratios and process parameters in examples 2 to 8
Table 2 shows the raw material ratios and process parameters in examples 9 to 12
Comparative example 1:
the difference from example 1 is that: in the step 1, a dropwise adding mode is not adopted, and the P123 and the TTIP are directly added into the ethanol solution containing the hydrochloric acid after being stirred.
Comparative example 2:
the difference from example 1 is that: in step 1, P123 and TTIP are stirred and then added dropwise into hydrochloric acid aqueous solution.
The experimental tests of examples 1 to 12 and comparative examples 1 to 2 were carried out:
1. scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM) and X-ray diffraction (XRD) are adopted for detection, taking example 1 as an example, wherein the detection result of SEM is shown in figure 1, the detection result of TEM is shown in figure 2, and the XRD detection results of examples 1-12 are shown in figure 3.
As can be seen from the FIG. 1, the N-doped carbon-coated titanium nitride nanoparticle composite material prepared by the preparation method of example 1 is shown to be agglomerated by a large amount of carbon material in bulk, since titanium is a compound of Titanium (TiO) throughout the entire process of preparing TiN @ NC composite material in the present application2Or TiN), so that even if a large amount of carbon atoms exists around the titanium compound, the titanium compound hardly induces the carbon atoms to form a structure of carbon nanotubes or nanowires, thereby causing the carbon material around the titanium compound to exist in a bulk form.
As shown in fig. 2, the results show that the nanoparticles of titanium nitride in the composite material of nitrogen-doped carbon-coated titanium nitride nanoparticles prepared by the preparation method of example 1 are uniformly distributed on the nitrogen-doped carbon material, and the size of the nanoparticles is not more than 20 nm.
In combination with the graph shown in fig. 3, the peak near 25.9 ° in the graph corresponds to a typical graphitized carbon peak, and the three diffraction peaks at 36.7 °, 42.6 °, 74.1 ° and 77.9 ° respectively correspond to the (200), (222), (311) and (222) crystal planes of the face-centered cubic structure TiN, which proves the main components of the nitrogen-doped carbon-coated titanium nitride nanoparticle composite material prepared by the present application.
2. Electrochemical testing
FIG. 4 is a polarization graph of TiN @ NC-4, TiN @ NC-5, TiN @ NC-6, and TiN @ NC-7; FIG. 5 is a graph of the half-slope potentials of TiN @ NC-4, TiN @ NC-5, TiN @ NC-6, and TiN @ NC-7; FIG. 6 is a diagram of the limiting diffusion current density of TiN @ NC-4, TiN @ NC-5, TiN @ NC-6, and TiN @ NC-7; as can be observed from FIGS. 4 to 6, the catalytic activity sequence of the prepared TiN @ NC composite material is as follows: TiN @ NC-5, NC-4, TiN @ NC-6, TiN @ NC-7 show the optimal catalytic activity of TiN @ NC-5.
FIG. 7 shows the current density after 1000 cycles of TiN @ NC-5A change curve of the degree; it can be shown from the figure that the limit current density of TiN @ NC-5 is attenuated by 0.22mA cm after 1000 cycles-2The attenuation is low.
FIG. 8 is a discharge polarization curve of TiN @ NC-5 in a zinc-air cell and its corresponding power density curve; as can be seen from FIG. 8, the open circuit voltage was 1.45V, and the current density and the power density reached maximum values at 0.51V, which were 154.38mW · cm, respectively-278.27mW cm-2。
FIG. 9 is a graph showing the cycle test of TiN @ NC-5 in a zinc-air battery (cycle period: 10 min); from the graph, it can be observed that the current density is 10mA cm-2When the cycle period is 10min, 782 cycles can be performed (130 h).
The foregoing is merely an example of the present invention and common general knowledge of the known specific materials and characteristics thereof has not been described herein in any greater extent. It should be noted that, for those skilled in the art, without departing from the scope of the invention, several variations and modifications can be made, which should also be regarded as the protection scope of the invention, and these will not affect the effect of the implementation of the invention and the practicability of the patent. The scope of the claims of the present application shall be determined by the contents of the claims, and the description of the embodiments and the like in the specification shall be used to explain the contents of the claims.
Claims (6)
1. A preparation method of a nitrogen-doped carbon-coated titanium nitride nanoparticle composite material is characterized by comprising the following steps of: the method comprises the following steps:
step 1: uniformly stirring P123 and isopropyl titanate, dropwise adding the mixture into an ethanol solution containing hydrochloric acid, uniformly stirring the mixture, adding distilled water to obtain a mixed solution, and carrying out heating reaction in an oil bath kettle to obtain a mixed solution;
step 2: adding dicyandiamide into the mixed solution obtained in the step 1, heating and stirring until the mixture is evaporated to dryness to obtain a precursor material;
and step 3: and (3) heating the precursor material obtained in the step (2) to not less than 750 ℃ under the protection of nitrogen, and preserving heat to obtain the nitrogen-doped carbon-coated titanium nitride nanoparticle composite material.
2. The method for preparing the nitrogen-doped carbon-coated titanium nitride nanoparticle composite material according to claim 1, wherein the method comprises the following steps: the molar ratio of isopropyl titanate to P123 in the step 1 is 1: 0.0064-0.0128.
3. The method for preparing the nitrogen-doped carbon-coated titanium nitride nanoparticle composite material according to claim 1, wherein the method comprises the following steps: the heating temperature of the oil bath kettle in the step 1 is 40-50 ℃.
4. The method for preparing the nitrogen-doped carbon-coated titanium nitride nanoparticle composite material according to claim 1, wherein the method comprises the following steps: in the step 2, the molar ratio of dicyandiamide to isopropyl titanate is 1.68-25.14: 1.
5. the method for preparing the nitrogen-doped carbon-coated titanium nitride nanoparticle composite material according to claim 1, wherein the method comprises the following steps: the heating temperature in the step 2 is 40-45 ℃.
6. The method for preparing the nitrogen-doped carbon-coated titanium nitride nanoparticle composite material according to claim 1, wherein the method comprises the following steps: the temperature of the temperature rise in the step 3 is 800-1000 ℃, and the heat preservation time is 1-1.5 h.
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