CN112225251A - Shell layer limited niobium pentoxide nanocrystalline hollow carbon sphere, preparation method and application - Google Patents
Shell layer limited niobium pentoxide nanocrystalline hollow carbon sphere, preparation method and application Download PDFInfo
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Abstract
The invention discloses a shell-confined niobium pentoxide nanocrystalline hollow carbon sphere, a preparation method and application thereof, belonging to the technical field of nano materials and comprising the following steps: s1, mixing ammonium niobate oxalate, aniline, pyrrole and a surfactant in water to prepare a uniform dispersion liquid; adding an initiator into the uniform dispersion liquid at 0 ℃ to initiate a series reaction to prepare an intermediate product; s2, under the atmosphere of protective gas, carbonizing the intermediate product prepared in the step S1 at 700-900 ℃ to prepare a shell layer limited niobium pentoxide nanocrystalline hollow carbon sphere; the in-situ micelle interfacial polymerization strategy provided by the invention can construct a hollow structure without any template, avoids the complicated preparation process of the traditional template method, and realizes the uniform loading of the niobium pentoxide nanocrystal in the hollow carbon sphere shell layer.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a shell layer confinement niobium pentoxide hollow carbon sphere, a preparation method and application thereof.
Background
As an important porous carbon material, the hollow carbon sphere has a unique nano cavity and a carbon shell structure with rich pores, and has a potential application prospect in the fields of energy storage, biomedicine, adsorption, separation, catalysis, nano reactors and the like. However, the lack of functionalized sites limits further exertion of the electrochemical energy storage properties of the hollow carbon spheres. The hollow carbon sphere functionally modified by the nano-crystal can combine the advantages of the nano-crystal and the hollow sphere, and the electrochemical energy storage performance of the material is improved through the structure synergistic effect. For example, as a sulfur carrier for the positive electrode of a lithium sulfur battery, the nanopores in the shell layer of the hollow carbon sphere can inhibit the dissolution of polysulfide through the physical adsorption effect, and the internal cavity provides a nano space required by high sulfur loading; the loaded superfine oxide nanocrystal, such as niobium pentoxide nanocrystal, can improve the problem of low utilization rate of the sulfur of the positive active material in the lithium-sulfur battery through the cooperation of chemical anchoring and catalytic action, and realize the construction of an electrochemical energy storage system with long cycle life, high energy density and excellent rate performance.
However, most of the existing preparation methods of the metal oxide nanoparticle-loaded hollow carbon spheres need to use a template, and the process is complicated. Meanwhile, the crystal phase forming temperature of the niobium pentoxide is generally higher, the grain size of the niobium pentoxide is often larger under higher heat treatment conditions, and the niobium pentoxide nanocrystal cannot be uniformly loaded in the shell layer of the hollow carbon sphere, so that the shape of the hollow carbon sphere is not favorably maintained. Therefore, how to construct the hollow carbon sphere of shell-layer confined niobium pentoxide nanocrystal through a simple and efficient preparation strategy is a problem to be solved urgently in the field.
Disclosure of Invention
In order to solve the problems, the invention discloses a shell layer limited niobium pentoxide nanocrystalline hollow carbon sphere, a preparation method and application thereof.
The invention aims to provide a preparation method of a shell layer limited niobium pentoxide nanocrystalline hollow carbon sphere, which comprises the following steps:
s1, mixing ammonium niobate oxalate, aniline, pyrrole and a surfactant in water to prepare a uniform dispersion liquid; adding an initiator into the uniform dispersion liquid at 0 ℃ to initiate reaction to prepare an intermediate product;
and S2, under the atmosphere of protective gas, carbonizing the intermediate product prepared in the S1 at 700-900 ℃ to prepare the shell layer limited niobium pentoxide nanocrystalline hollow carbon sphere.
Preferably, the hollow carbon sphere of shell-layer confined niobium pentoxide nanocrystal prepared by S2 can be subjected to oxidation treatment at 300-400 ℃.
Preferably, in the oxidation treatment process, the heating rate is 2 ℃/min, and after keeping the temperature for 3 hours, the mixture is naturally cooled to the room temperature.
Preferably, in S1, the initiator is ammonium persulfate, and the ratio of aniline: pyrrole: ammonium niobate oxalate: the dosage ratio of ammonium persulfate is 2.72 mL: 2.11 mL: 1-2 g: 13.72 g.
Preferably, in S1, the surfactant is Triton X-100, the ratio of aniline: triton X-100: the dosage ratio of water is 8.17 mL: 1 g: 900 mL.
Preferably, in S1, after the initiator is added, the mixture is left to stand at 0 ℃ for reaction for 12 hours, and after the reaction is finished, the product is washed to be neutral and then dried.
Preferably, in S2, the temperature rising rate is 5 ℃/min, the temperature is kept for 3h, and then the product is naturally cooled to the room temperature.
The second purpose of the invention is to provide the hollow carbon ball with the shell layer limited niobium pentoxide nanocrystal prepared by the preparation method, wherein the surface of the hollow carbon ball is a porous shell layer, and the niobium pentoxide nanocrystal is uniformly loaded in the shell layer of the hollow carbon ball.
The third purpose of the invention is to provide the application of the hollow carbon sphere of the shell-layer-confinement niobium pentoxide nanocrystal in the sulfur-carrying material of the positive electrode of the lithium-sulfur battery.
Compared with the prior art, the invention has the following beneficial effects:
(1) the in-situ micelle interface polymerization strategy provided by the invention can construct a hollow structure without any template, thereby avoiding the complicated preparation process of the traditional template method;
(2) the niobium pentoxide crystal phase is usually formed at a higher temperature, while the niobium pentoxide crystal grain formed at the higher temperature is usually larger in size, the niobium pentoxide precursor is anchored under the action of secondary valence bonds (hydrogen bonds, chelation and electrostatic force) between the niobium pentoxide precursor and aniline, and the niobium pentoxide crystal grains are prevented from being agglomerated in the carbonization process to form niobium pentoxide nanocrystals, so that the niobium pentoxide nanocrystals are uniformly loaded in the hollow carbon sphere shell;
(3) according to the method, the content of niobium pentoxide, the thickness of the shell layer and the specific surface area in the hollow carbon ball of the shell layer limited niobium pentoxide nanocrystal are successfully and finely regulated by utilizing a strategy of reoxidizing the carbonized product and through ablation decomposition of the carbon shell layer skeleton in the air atmosphere; the content of niobium pentoxide in the composite material is 13-86 wt%, and the specific surface area is 138-2The shell layer with smaller thickness is beneficial to the infiltration of electrolyte so as to improve the utilization rate of active substance sulfur of the positive electrode of the lithium-sulfur battery, and the niobium pentoxide nanocrystal can effectively catalyze the conversion of polysulfide to a discharge product in the discharge process of the lithium-sulfur battery and inhibit the shuttle effect of the polysulfide, thereby showing better electrochemical performance.
Drawings
FIG. 1 is a scanning electron microscope image of a hollow carbon sphere of shell-confined niobium pentoxide nanocrystal prepared in example 1 of the present invention;
FIG. 2 is a TEM image of the hollow carbon sphere of shell-confined niobium pentoxide nanocrystal prepared in example 1 of the present invention;
FIG. 3 is a thermal weight loss curve diagram of a hollow carbon sphere of shell-confined niobium pentoxide nanocrystal prepared in example 1 of the present invention;
fig. 4 is a performance diagram of specific cyclic capacity and coulombic efficiency of the shell-confined niobium pentoxide nanocrystalline hollow carbon sphere as the sulfur-loaded material of the lithium-sulfur battery positive electrode, prepared in example 5 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention. Unless otherwise specifically stated, the various starting materials, reagents, instruments and equipment used in the following examples of the present invention are either commercially available or prepared by conventional methods. Test methods in which specific conditions are not specified in the following examples are generally carried out under conventional conditions or under conditions recommended by the respective manufacturers.
Example 1
The preparation method of the shell layer limited niobium pentoxide nanocrystalline hollow carbon sphere provided by the embodiment 1 of the invention comprises the following steps:
s1, dissolving 2.5g of Triton X-100 in 250mL of ultrapure water at room temperature to prepare 0.01g/mL of Triton X-100 aqueous solution, adding 54mL of ultrapure water and 0.36g of ammonium niobate oxalate into a 100mL container, stirring for 5min to dissolve, then adding 6mL of Triton X-100 aqueous solution (0.01g/mL), then sequentially adding 0.49mL of aniline and 0.38mL of pyrrole, magnetically stirring for 30min, and ultrasonically dispersing for 30 min; then placing the mixture in a low-temperature constant-temperature reaction bath at the temperature of 0 ℃ and stirring for 30 min; then adding ammonium persulfate aqueous solution which is pre-cooled to 0 ℃ (wherein the ammonium persulfate aqueous solution is obtained by dissolving 2.47g of ammonium persulfate in 5mL of ultrapure water), and rapidly stirring for 30s by magnetic force for mixing; then placing the mixture into a low-temperature constant-temperature reaction bath at 0 ℃ for standing reaction for 12h, washing the product with ultrapure water in the process of reduced pressure filtration until the filtrate is nearly neutral, and placing the washed product into a 60 ℃ forced air drying oven for drying for 12h to obtain an aniline-pyrrole copolymer hollow sphere loaded by a niobium pentoxide precursor;
and S2, placing the solid product obtained in the step S1 in a nitrogen atmosphere of 100mL/min, heating to 900 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 3 hours, and naturally cooling to room temperature to obtain the shell layer confinement niobium pentoxide nanocrystal hollow carbon sphere.
We performed performance tests on the hollow carbon sphere of shell-confined niobium pentoxide nanocrystal prepared in example 1, and fixed the prepared hollow carbon sphere of shell-confined niobium pentoxide nanocrystal on a sample stage with a conductive adhesive, and observed the structural morphology of the sample with a Nova field emission scanning electron microscope produced by FEI of america, to obtain a scanning electron microscope image of the hollow carbon sphere of shell-confined niobium pentoxide nanocrystal as shown in fig. 1. As can be seen from figure 1, the prepared hollow carbon sphere of shell-confined niobium pentoxide nanocrystal consists of monodisperse nanospheres with the outer diameter of 125nm, and the morphology and the size of the sphere are uniform.
Fully grinding the prepared hollow carbon sphere of the shell-layer-limited niobium pentoxide nanocrystal, placing a small amount of sample powder in absolute ethyl alcohol for ultrasonic dispersion, fishing out a part of the sample by using a copper mesh, observing the structure of the sample by using a transmission electron microscope after the absolute ethyl alcohol is volatilized, and obtaining a transmission electron microscope image of the hollow carbon sphere of the shell-layer-limited niobium pentoxide nanocrystal, wherein the transmission electron microscope image is shown in fig. 2. The hollow nanostructure can be clearly seen from fig. 2(a), and fig. 2(b) shows that the thickness of the shell layer is about 43nm and the niobium pentoxide nanocrystals are uniformly distributed in the shell layer.
The thermogravimetric curves of the samples were analyzed with a mertler-toledo TGA/DSC simultaneous thermogram analyzer, switzerland. Taking about 3-5 mg of prepared shell layer limited niobium pentoxide nanocrystal blankPlacing the sample into a 60 ℃ blast oven for about 3-5 h before testing, drying the moisture in the sample, then heating to 800 ℃ in air atmosphere at a heating rate of 10 ℃/min, wherein the gas flow is about 100mL/min, and then naturally cooling to room temperature. The test results are shown in FIG. 3, and the content of niobium pentoxide in the hollow carbon sphere sample of shell confinement niobium pentoxide nanocrystal is about 26 wt%. The specific surface area is about 138m by calculation through nitrogen adsorption and desorption test2/g。
Example 2
The preparation method of the shell layer limited niobium pentoxide nanocrystalline hollow carbon sphere provided by the embodiment 2 of the invention comprises the following steps:
s1, preparing niobium pentoxide precursor-loaded aniline-pyrrole copolymer hollow spheres according to the step of S1 in the embodiment 1;
and S2, placing the solid product obtained in the step S1 in a nitrogen atmosphere of 100mL/min, heating to 800 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 3 hours, and naturally cooling to room temperature to obtain the shell layer confinement niobium pentoxide nanocrystal hollow carbon sphere.
The content of niobium pentoxide in the prepared hollow carbon ball sample of shell-confined niobium pentoxide nanocrystal is about 19 wt%, and the specific surface area of the hollow carbon ball sample is about 611m2Per g, the test procedure is as in example 1.
Example 3
The preparation method of the shell layer limited niobium pentoxide nanocrystal hollow carbon sphere provided by the embodiment 3 of the invention comprises the following steps:
s1, preparing niobium pentoxide precursor-loaded aniline-pyrrole copolymer hollow spheres according to the step of S1 in the embodiment 1;
and S2, placing the solid product obtained in the step S1 in a nitrogen atmosphere of 100mL/min, heating to 700 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 3 hours, and naturally cooling to room temperature to obtain the shell layer confinement niobium pentoxide nanocrystal hollow carbon sphere.
The content of niobium pentoxide in the prepared hollow carbon ball sample of shell-confined niobium pentoxide nanocrystal is about 13 wt%, and the specific surface area of the hollow carbon ball sample is about 368m2/g，The test method was the same as in example 1.
The method can be obtained from the embodiments 1 to 3, the in-situ micelle interface polymerization strategy provided by the invention can construct a hollow structure without any template, and the complicated and complicated preparation process of the traditional template method is avoided; the niobium pentoxide crystal phase is usually formed at a higher temperature, while the niobium pentoxide crystal grain size formed at the higher temperature is usually larger, the niobium pentoxide precursor is anchored under the action of secondary valence bonds (hydrogen bonds, chelation and electrostatic force) between the niobium pentoxide precursor and aniline, and the niobium pentoxide crystal grains are prevented from being agglomerated in the carbonization process to form the niobium pentoxide nanocrystal, so that the niobium pentoxide nanocrystal is uniformly loaded in the hollow carbon sphere shell.
Example 4
The preparation method of the shell layer limited niobium pentoxide nanocrystal hollow carbon sphere provided by the embodiment 4 of the invention comprises the following steps:
s1, preparing niobium pentoxide precursor-loaded aniline-pyrrole copolymer hollow spheres according to the step of S1 in the embodiment 1;
s2, preparing a hollow carbon sphere of shell layer confined niobium pentoxide nanocrystal according to the step S2 in the embodiment 1;
and S3, carrying out oxidation treatment on the hollow carbon ball of the shell-layer confined niobium pentoxide nanocrystal obtained in the step S2 in an air atmosphere, raising the temperature to 350 ℃ at a heating rate of 2 ℃/min, preserving the temperature for 3h, and naturally cooling to room temperature to obtain the oxidized hollow carbon ball of the shell-layer confined niobium pentoxide nanocrystal.
The content of niobium pentoxide in the prepared hollow carbon ball sample of the shell-layer confined niobium pentoxide nanocrystal after oxidation treatment is about 28 wt%, and the specific surface area is about 798m2Per g, shell thickness of about 41nm, as measured in example 1.
Example 5
The preparation method of the shell layer limited niobium pentoxide nanocrystal hollow carbon sphere provided by the embodiment 5 of the invention comprises the following steps:
s1, preparing niobium pentoxide precursor-loaded aniline-pyrrole copolymer hollow spheres according to the step of S1 in the embodiment 1;
s2, preparing a hollow carbon sphere of shell layer confined niobium pentoxide nanocrystal according to the step S2 in the embodiment 1;
and S3, carrying out oxidation treatment on the hollow carbon ball of the shell-layer confined niobium pentoxide nanocrystal obtained in the step S2 in an air atmosphere, raising the temperature to 380 ℃ at a heating rate of 2 ℃/min, preserving the temperature for 3h, and naturally cooling to room temperature to obtain the oxidized hollow carbon ball of the shell-layer confined niobium pentoxide nanocrystal.
The content of niobium pentoxide in the prepared hollow carbon sphere sample of the shell-layer confined niobium pentoxide nanocrystal after oxidation treatment is about 32 wt%, and the specific surface area of the hollow carbon sphere sample is about 494m2Per g, shell thickness of about 40nm, as measured in example 1.
Fig. 4 shows the specific capacity performance of the hollow carbon sphere of shell-confined niobium pentoxide nanocrystal prepared in example 5 as the sulfur-carrying material of the positive electrode of the lithium-sulfur battery under the current density of 0.2C (the current density of the first two circles is 0.1C, and 1C is 1675mAh/g), the specific capacity of the battery in the first constant current charging and discharging test is 1200mAh/g, the first coulombic efficiency is 97%, and the battery shows better electrochemical performance.
Example 6
The preparation method of the shell layer limited niobium pentoxide nanocrystal hollow carbon sphere provided by the embodiment 6 of the invention comprises the following steps:
s1, preparing niobium pentoxide precursor-loaded aniline-pyrrole copolymer hollow spheres according to the step of S1 in the embodiment 1;
s2, preparing a hollow carbon sphere of shell layer confined niobium pentoxide nanocrystal according to the step S2 in the embodiment 1;
and S3, carrying out oxidation treatment on the hollow carbon ball of the shell-layer confined niobium pentoxide nanocrystal obtained in the step S2 in an air atmosphere, raising the temperature to 390 ℃ at a heating rate of 2 ℃/min, preserving the temperature for 3h, and naturally cooling to room temperature to obtain the oxidized hollow carbon ball of the shell-layer confined niobium pentoxide nanocrystal.
The content of niobium pentoxide in the prepared hollow carbon ball sample of the shell-layer confined niobium pentoxide nanocrystal after oxidation treatment is about78 wt% and a specific surface area of about 375m2Per g, a shell thickness of about 17nm, as measured in example 1.
From the above examples 4-6, the method successfully realizes the fine regulation and control of the content of niobium pentoxide, the thickness of the shell layer and the specific surface area in the hollow carbon sphere of the shell layer confined niobium pentoxide nanocrystal by utilizing the strategy of reoxidation of the carbonized product and the ablation and decomposition of the carbon shell layer skeleton in the air atmosphere; and the shell layer with smaller thickness is beneficial to the infiltration of electrolyte, so as to improve the utilization rate of active substance sulfur of the anode of the lithium-sulfur battery, and the niobium pentoxide nanocrystal can effectively catalyze the conversion of polysulfide to a discharge product in the discharge process of the lithium-sulfur battery, inhibit the shuttle effect of the polysulfide, and show better electrochemical performance.
It should be noted that when the following claims refer to numerical ranges, it should be understood that both ends of each numerical range and any value between the two ends can be selected, and since the steps and methods used are the same as those of the embodiments, the preferred embodiments and effects thereof are described in the present invention for the sake of avoiding redundancy, but once the basic inventive concept is known, those skilled in the art may make other changes and modifications to the embodiments. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, it is intended that such changes and modifications be included within the scope of the appended claims and their equivalents.
Claims (9)
1. A preparation method of a shell layer confinement niobium pentoxide nanocrystalline hollow carbon sphere is characterized by comprising the following steps:
s1, mixing ammonium niobate oxalate, aniline, pyrrole and a surfactant in water to prepare a uniform dispersion liquid; adding an initiator into the uniform dispersion liquid at 0 ℃ to initiate reaction to prepare an intermediate product;
and S2, under the atmosphere of protective gas, carbonizing the intermediate product prepared in the S1 at 700-900 ℃ to prepare the shell layer limited niobium pentoxide nanocrystalline hollow carbon sphere.
2. The preparation method of the hollow carbon sphere of the shell-layer-confined niobium pentoxide nanocrystal, according to claim 1, is characterized in that the hollow carbon sphere of the shell-layer-confined niobium pentoxide nanocrystal prepared in S2 can be subjected to oxidation treatment at 300-400 ℃.
3. The preparation method of the hollow carbon sphere of the shell-confined niobium pentoxide nanocrystal as claimed in claim 2, wherein in the oxidation treatment process, the temperature rise rate is 2 ℃/min, the temperature is kept for 3 hours at a constant temperature, and then the hollow carbon sphere is naturally cooled to room temperature.
4. The method for preparing the hollow carbon sphere of the shell-confined niobium pentoxide nanocrystal according to claim 1, wherein in S1, the initiator is ammonium persulfate, and the aniline: pyrrole: ammonium niobate oxalate: the dosage ratio of ammonium persulfate is 2.72 mL: 2.11 mL: 1-2 g: 13.72 g.
5. The method for preparing the hollow carbon sphere of the shell-confined niobium pentoxide nanocrystal as claimed in claim 1, wherein in S1, the surfactant is Triton X-100, and the ratio of aniline: triton X-100: the dosage ratio of water is 8.17 mL: 1 g: 900 mL.
6. The preparation method of the hollow carbon sphere of the shell-confined niobium pentoxide nanocrystal as claimed in claim 1, wherein the initiator is added to S1, and then the mixture is allowed to stand at 0 ℃ for 12 hours, and after the reaction is finished, the product is washed to be neutral, and then dried.
7. The preparation method of the hollow carbon sphere of the shell-confined niobium pentoxide nanocrystal as claimed in claim 1, wherein in S2, the temperature rise rate is 5 ℃/min, the temperature is kept at a constant temperature for 3 hours, and then the hollow carbon sphere is naturally cooled to room temperature.
8. The hollow carbon sphere with the shell layer limited niobium pentoxide nanocrystal prepared by the preparation method of any one of claims 1 to 7, wherein the surface of the hollow carbon sphere is a porous shell layer, and the niobium pentoxide nanocrystal is uniformly loaded in the shell layer of the hollow carbon sphere.
9. The use of the hollow carbon sphere of shell-confined niobium pentoxide nanocrystal according to claim 8 in a sulfur-loaded material for a lithium-sulfur battery positive electrode.
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| CN104591127A (en) * | 2015-01-09 | 2015-05-06 | 中山大学 | Ultrahigh-specific-area hollow carbon nano-spheres as well as preparation method and application thereof |
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| CN111410177A (en) * | 2020-04-23 | 2020-07-14 | 西北工业大学 | Hollow carbon sphere packaged superfine inorganic particle composite material and preparation method and application thereof |
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| CN104591127A (en) * | 2015-01-09 | 2015-05-06 | 中山大学 | Ultrahigh-specific-area hollow carbon nano-spheres as well as preparation method and application thereof |
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| CN108899507A (en) * | 2018-07-03 | 2018-11-27 | 长沙理工大学 | A kind of preparation method of the double-deck carbon coating metal sulfide combination electrode material with core-shell structure |
| CN108751165A (en) * | 2018-07-17 | 2018-11-06 | 西北工业大学 | A kind of hollow carbon nanospheres and the preparation method and application thereof based on ammonia auxiliary carbonization |
| CN109216691A (en) * | 2018-11-06 | 2019-01-15 | 桑德集团有限公司 | A kind of positive electrode active materials and preparation method thereof and lithium battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114300665A (en) * | 2021-12-30 | 2022-04-08 | 华南师范大学 | Niobium-based metal oxide mesoporous carbon sphere composite material and sodium ion battery anode material containing same |
| CN114300665B (en) * | 2021-12-30 | 2024-04-09 | 华南师范大学 | Niobium-based metal oxide mesoporous carbon sphere composite material and sodium ion battery anode material containing same |
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| CN112225251B (en) | 2023-03-24 |
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