CN113571674A - Preparation method and application of in-situ carbon-coated binary transition metal oxide heterojunction bowl-shaped nano composite material - Google Patents
Preparation method and application of in-situ carbon-coated binary transition metal oxide heterojunction bowl-shaped nano composite material Download PDFInfo
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Abstract
The invention discloses a preparation method and application of an in-situ carbon-coated binary transition metal oxide heterojunction bowl-shaped nano composite materialPrecursor powder of carbon-coated binary transition metal oxide heterojunction bowl-shaped nano composite material is calcined in argon atmosphere to obtain a bowl-shaped in-situ carbon-coated binary transition metal oxide heterojunction nano composite material, and the nano composite material shows excellent potassium storage performance when used as a potassium electric cathode3O4The @ C-N bowl-shaped nano composite material has uniform appearance, rapid preparation and uniform grain size distribution.
Description
Technical Field
The invention belongs to the technical field of potassium ion battery cathode materials, and particularly relates to a preparation method of an in-situ carbon-coated binary transition metal oxide heterojunction bowl-shaped nano composite material and application of the composite material in a potassium ion battery.
Background
Energy is an important pillar of our lives. Lithium ion batteries, one of the representatives of higher performance energy storage devices, have improved our lives to a great extent. With the rapid popularization and application of small electronic devices such as smart phones, ipads and large energy storage devices such as household electric cars and electric automobiles, the content distribution of lithium in the earth crust is only 0.0065%, and the lithium resource distribution is not uniform, so that the development of the lithium ion battery in the large-scale energy storage field is limited to a great extent. In order to overcome the serious obstacle, a novel replaceable energy storage battery is urgently needed to be developed, and a potassium ion battery enters the visual field of people due to the advantages of low cost, similar physical properties to lithium and wide resource distribution, so that the development of researches on the potassium ion battery and electrode materials is of great significance.
The potassium ion battery has unique advantages as a novel energy storage battery. However, in order to fully understand and utilize the advantages and disadvantages (the ionic radius is large, the volume expansion of the material is obvious when the material is embedded, the battery cycle life is short, and the rate capability is poor) of the transition metal oxide, deep research is needed, so that the development of an electrode material with large capacity and good rate and cycle performance has great significance for the research and further development of the potassium ion battery, and in view of the above, many methods have been developed to solve the problem of the transition metal oxide as the negative electrode material. An effective method is that the composite material forms a heterojunction due to electron affinity energy and band gap width difference, and the Fermi level effect formed by a heterojunction interface is utilized to improve the interface carrier migration rate; on the other hand, the morphological structure of the metal oxide is changed to increase the specific surface area of the metal oxide, so that the ion transmission is accelerated, and the comprehensive performance of the potassium ion battery is finally improved.
Disclosure of Invention
The technical problem to be solved by the invention is to provide the preparation method of the in-situ carbon-coated binary transition metal oxide heterojunction bowl-shaped nano composite material which has the advantages of good safety, high stability, low cost, mild reaction condition and good rate capability and cycle performance.
The invention adopts the following technical scheme for solving the technical problems, and the preparation method of the in-situ carbon-coated binary transition metal oxide heterojunction bowl-shaped nano composite material is characterized by comprising the following specific steps of:
step S1: uniformly mixing absolute ethyl alcohol and primary deionized water according to the volume ratio of 2:1 to obtain a solvent A, dissolving polyvinylpyrrolidone in the solvent A to form a colorless solution, continuously stirring, and adding manganese acetate tetrahydrate into the stirring colorless solution to obtain a clear and transparent solution X;
step S2: preparing solvent A 'with the same proportion and volume as solvent A in step S1, adding trimesic acid into solvent A' and stirring uniformly to obtain solution Y, and stirring while using a peristaltic pump to make solution Y into 1.0-2.5mL S-1Adding the solution to the clear transparent solution X obtained in the step S1, controlling the speed of nucleation, the size of nucleation, the appearance of bowl shape, the size of bowl shape and the uniformity of bowl shape diameter by controlling the flow rate of the solution Y, standing, performing suction filtration to obtain a reaction product, washing the obtained reaction product with absolute ethyl alcohol for more than three times to remove residual surfactant polyvinylpyrrolidone and acetate ions, and reactingDrying the product in a vacuum drying oven to rapidly dry the nucleation product to obtain primary particles of the carbon-coated binary transition metal oxide heterojunction nano composite material, and simultaneously obtaining bowl-shaped precursor powder assembled by the primary particles;
step S3: the precursor powder obtained in the step S2 is put in an argon atmosphere at the temperature of 1-25 ℃ for min-1The temperature is raised to 350-880 ℃ at the temperature raising rate for heat treatment for 0.3-16h, and then the temperature is raised for 1-15 min-1The temperature reduction rate is reduced to room temperature at a constant speed, and finally the target product in-situ carbon-coated binary transition metal oxide heterojunction bowl-shaped nano composite material is obtained, wherein the in-situ carbon-coated binary transition metal oxide heterojunction bowl-shaped nano composite material is specifically MnO-Mn3O4@ C-N composite, MnO and Mn3O4Are all crystal materials.
Further defined, the MnO-Mn3O4In the @ C-N nano composite material, MnO accounts for MnO-Mn3O4The mass percent of the @ C-N nano composite material is 25-92 percent, and Mn3O4In MnO-Mn3O4The mass percent of the @ C-N nano composite material is 5-70%, and the balance is N and amorphous C.
Further limiting, the feeding mass ratio of the polyvinylpyrrolidone, the manganese acetate tetrahydrate and the trimesic acid is 5-7:1-2.5: 2-3.5.
The in-situ carbon-coated binary transition metal oxide heterojunction bowl-shaped nano composite material is applied as a high-performance potassium ion battery cathode material.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the BT100-2J peristaltic pump is used as a key for forming a binary transition metal oxide heterojunction bowl-shaped nano composite material, and the microstructure and special morphology of the composite material are formed by the following mechanisms: (1) solution Y was pumped at a flow rate (1.0-2.5 mL s) using a BT100-2J peristaltic pump-1) Injected into the solution X, is beneficial to the uniform nucleation and growth of primary particles of the binary transition metal oxide heterojunction, and does not grow when the formation of the primary particles reaches the maximum value, so as to obtain the primary particles with uniform particle size(ii) a (2) After the primary particles are formed, in the processes of continuous stirring and aging, in order to reduce the surface energy of the primary particles, the primary particles gradually form a bowl-shaped appearance, the injection flow rate of the solution Y plays a critical role in the nucleation and growth of the primary particles in the forming process, and plays a decisive role in the construction of a special structure of the composite material and the improvement of the potassium storage performance; (3) the homogeneous nucleation is beneficial to forming a binary transition metal oxide heterojunction in situ, and the heterojunction can effectively reduce the band gap of the metal composite material and further improve the potassium storage performance of the heterojunction; (4) the liquid phase reaction is simple to operate and high in repeatability due to the fact that an accurate BT100-2J peristaltic pump is used for controlling, and the binary transition metal oxide heterojunction bowl-shaped nano composite material with a novel structure and a novel appearance can be efficiently prepared.
2. The invention combines the advantages of a liquid phase reaction method, and has the advantages of high safety and stability, low cost, mild reaction conditions, and good rate capability and cycle performance.
3. The target product in-situ carbon-coated binary transition metal oxide heterojunction bowl-shaped nano composite material prepared by the method has the structural advantages that: compared with a solid sphere and the like prepared without using a BT100-2J peristaltic pump, the hollow bowl-shaped nano structure prepared by the invention is a solid sphere and the like, wherein the bowl-shaped nano structure is prepared from primary particles MnO-Mn3O4The secondary particle composed of @ C-N, while the solid sphere in the comparative example has smooth surface, therefore, the bowl-shaped nano structure has larger specific surface area, which is beneficial to increasing the reactive active sites of the nano composite material and increasing K+Diffusion channel and effective shortening of K+The diffusion path further effectively improves the comprehensive performance of the potassium ion battery.
4. The target product in-situ carbon-coated binary transition metal oxide heterojunction bowl-shaped nanocomposite prepared by the invention has the advantages that the conductivity of the nanocomposite is effectively improved, the Fermi level effect formed on a heterojunction interface can improve the interface carrier migration rate, the electron mobility is enhanced, and the Fermi level effect simultaneously promote ion transmission, so that the nanocomposite has relatively high specific capacity, good rate capability and stable cycle performance when being used as a negative electrode material of a potassium ion battery.
5. The target product prepared by the invention is MnO-Mn3O4@ C-N, the target product being formed during the calcination of manganese trimesate at an optimum temperature, MnO and Mn3O4The two semiconductors with different crystal forms form a heterojunction in situ at an optimized temperature, and a heterojunction transition metal oxide is formed by close contact and a common heterointerface between the two semiconductors. Theoretically, the heterojunction material has a narrower band gap than a single corresponding semiconductor, so that the interface migration kinetic property of potassium ions can be effectively improved, and the energy storage property is improved.
6. MnO and Mn in the target product in-situ carbon-coated binary transition metal oxide heterojunction bowl-shaped nano composite material prepared by the invention3O4Simultaneously participate in electrochemical reaction, promote reaction kinetics to go on fast, thereby the promotion of promotion material capacity is promoted in the increase of charge transfer quantity, and this reversible reaction is: MnO +2K++2e-⇋Mn+K2O 、Mn3O4 +8K++8e-⇋3Mn+4K2O。
7. The bowl-shaped precursor powder of the carbon-coated binary transition metal oxide heterojunction nano composite material is obtained by a hydrolysis method, and then the bowl-shaped in-situ carbon-coated binary transition metal oxide heterojunction nano composite material is obtained by calcining in an argon atmosphere3O4@ C-N-1 composite material and solid spherical MnO/Mn prepared by setting different flow rates by using peristaltic pump3O4@ C-N-2 composite and solid spherical MnO/Mn3O4@ C-N-3 composite, commercial MnO and commercial Mn3O4The excellent potassium storage performance, namely rate capability (shown in figure 8) and cycle performance (shown in figure 9), can be used as a negative electrode material of a high-performance potassium ion battery.
Drawings
FIG. 1 shows MnO-Mn obtained in example 13O4X-ray diffraction pattern of @ C-N nanocomposite;
FIGS. 2 and 3 show MnO-Mn obtained in example 13O4Scanning electron microscopy of the @ C-N nanocomposite, wherein FIG. 3 is an enlarged view of a portion of FIG. 2;
FIG. 4 shows MnO-Mn obtained in example 13O4A high resolution transmission electron micrograph of @ C-N nanocomposite;
FIG. 5 shows MnO/Mn obtained in comparative example 13O4Scanning electron microscopy of @ C-N-1 nanocomposites;
FIG. 6 shows MnO/Mn obtained in comparative example 23O4Scanning electron microscopy of @ C-N-2 nanocomposites;
FIG. 7 shows MnO/Mn obtained in comparative example 33O4Scanning electron microscopy of @ C-N-3 nanocomposites;
FIG. 8 shows MnO-Mn obtained in example 13O4@ C-N nanocomposite, solid spherical product MnO/Mn prepared without using BT100-2J peristaltic pump3O4@ C-N-1 nanocomposite, commercial MnO and commercial Mn3O4MnO/Mn prepared in comparative example 23O4@ C-N-2 nanocomposite, MnO/Mn prepared in comparative example 33O4A corresponding rate performance graph when the @ C-N-3 nano composite material is used as a negative electrode material of the potassium ion battery;
FIG. 9 shows MnO-Mn obtained in example 13O4@ C-N nanocomposites and commercial Mn3O4Solid spherical product MnO/Mn prepared without using BT100-2J peristaltic pump3O4@ C-N-1 nanocomposite, commercial MnO, MnO prepared in comparative example 23O4@ C-N-2 nanocomposite, MnO/Mn prepared in comparative example 33O4And the corresponding cycle performance diagram when the @ C-N-3 nano composite material is used as a negative electrode material of the potassium ion battery.
Detailed Description
The present invention is described in further detail below with reference to examples, but it should not be construed that the scope of the above subject matter of the present invention is limited to the following examples, and that all the technologies realized based on the above subject matter of the present invention belong to the scope of the present invention.
Example 1
Preparation of MnO-Mn3O4@ C-N nanocomposite
Dispersing 5.6g of polyvinylpyrrolidone into a mixed solution of 100mL of absolute ethyl alcohol and primary deionized water (volume ratio is 2: 1), stirring and mixing uniformly at 300rpm, adding 1.1g of manganese acetate tetrahydrate at the same rotating speed, stirring and mixing uniformly to obtain a clear and transparent solution X; dissolving 2.0g of trimesic acid in 100mL of a mixed solution of absolute ethyl alcohol and primary deionized water (volume ratio of 2: 1) and uniformly mixing with stirring to obtain a solution Y, and then using a BT100-2J peristaltic pump to pump the solution Y at 300rpm for 1.30mL s-1Adding the mixture into the clear transparent solution X obtained in the step S1 at a flow rate, standing for several hours, then centrifugally collecting the obtained precipitate, washing the obtained precipitate for multiple times by using absolute ethyl alcohol to remove a surfactant and residual ions, then drying the obtained product in a vacuum drying oven at 75 ℃ for 10 hours to obtain primary particles of the carbon-coated binary transition metal oxide heterojunction nano composite material, and simultaneously obtaining bowl-shaped precursor powder assembled by the primary particles; in a tube furnace at 1 deg.C for min under argon atmosphere-1Heating to 480 deg.C at a heating rate, calcining the precursor powder for 2h, and then heating at 1 deg.C for min-1The temperature is reduced to room temperature at a constant speed to obtain a target product MnO-Mn3O4@ C-N nanocomposites.
Example 2
Preparation of MnO-Mn3O4@ C-N nanocomposite
Dispersing 6.1g of polyvinylpyrrolidone into a mixed solution of 120mL of anhydrous ethanol and primary deionized water (volume ratio is 2: 1), stirring and mixing uniformly at 350rpm, adding 1.6g of manganese acetate tetrahydrate at the same rotating speed, stirring and mixing uniformly to obtain a clear and transparent solution X; 2.8g of trimesic acid was dissolved in a mixture of 100mL of absolute ethanol and once deionized water (volume ratio: 2: 1)Mixing the solution, stirring and mixing uniformly to obtain solution Y, and then using a BT100-2J peristaltic pump to pump the solution Y at the speed of 350rpm for 1.0mL s-1Adding the mixture into the clear transparent solution X obtained in the step S1 at a flow rate, standing for several hours, then centrifugally collecting the obtained precipitate, washing the obtained precipitate for multiple times by using absolute ethyl alcohol to remove a surfactant and residual ions, then drying the obtained product in a vacuum drying oven at 70 ℃ for 10 hours to obtain primary particles of the carbon-coated binary transition metal oxide heterojunction nano composite material, and simultaneously obtaining bowl-shaped precursor powder assembled by the primary particles; in a tube furnace at 1 deg.C for min under argon atmosphere-1The temperature is raised to 600 ℃ at the temperature raising rate to calcine the precursor powder for 1.8h, and then the precursor powder is calcined at the temperature of 2 ℃ for min-1The temperature is reduced to room temperature at a constant speed to obtain a target product MnO-Mn3O4@ C-N nanocomposites.
Example 3
Preparation of MnO-Mn3O4@ C-N nanocomposite
Dispersing 6.8g of polyvinylpyrrolidone in 180mL of a mixed solution of absolute ethyl alcohol and primary deionized water (volume ratio is 2: 1), stirring and mixing uniformly at 410rpm, adding 2.3g of manganese acetate tetrahydrate at the same rotating speed, stirring and mixing uniformly to obtain a clear and transparent solution X; dissolving 3.2g of trimesic acid in 180mL of a mixed solution of absolute ethyl alcohol and primary deionized water (volume ratio of 2: 1) and uniformly mixing with stirring to obtain a solution Y, and then using a BT100-2J peristaltic pump to pump the solution Y at 410rpm for 2.50mL of s-1Adding the mixture into the clear transparent solution X obtained in the step S1 at a flow rate, standing for several hours, then centrifugally collecting the obtained precipitate, washing the obtained precipitate for multiple times by using absolute ethyl alcohol to remove a surfactant and residual ions, then drying the obtained product in a vacuum drying oven at 80 ℃ for 10 hours to obtain primary particles of the carbon-coated binary transition metal oxide heterojunction nano composite material, and simultaneously obtaining bowl-shaped precursor powder assembled by the primary particles; in a tube furnace at 2 deg.C for min under argon atmosphere-1Heating to 700 deg.C at a heating rate, calcining the precursor powder for 2h, and then heating at 10 deg.C for min-1The temperature is reduced to room temperature at a constant speed to obtain a target product MnO-Mn3O4@ C-N nanocomposites.
Comparative example 1
Preparation of MnO/Mn3O4@ C-N-1 nanocomposite
Dispersing 5.6g of polyvinylpyrrolidone into a mixed solution of 100mL of absolute ethyl alcohol and primary deionized water (volume ratio is 2: 1), stirring and mixing uniformly at 300rpm, adding 1.1g of manganese acetate tetrahydrate at the same rotating speed, stirring and mixing uniformly to obtain a clear and transparent solution X; dissolving 2.0g of trimesic acid in 100mL of a mixed solution of absolute ethyl alcohol and primary deionized water (volume ratio is 2: 1), uniformly stirring and mixing to obtain a solution Y, then adding the solution Y into the clear transparent solution X obtained in the step S1 under the condition of 300rpm, standing and storing for several hours, then centrifugally collecting the obtained precipitate, washing the obtained precipitate for multiple times by using absolute ethyl alcohol to remove a surfactant and residual ions, then drying the obtained product in a vacuum drying oven at 75 ℃ for 10 hours to obtain primary particles of the carbon-coated binary transition metal oxide heterojunction nano composite material, and simultaneously obtaining bowl-shaped precursor powder assembled by the primary particles; in a tube furnace at 1 deg.C for min under argon atmosphere-1Heating to 480 deg.C at a heating rate, calcining the precursor powder for 2h, and then heating at 1 deg.C for min-1The temperature is reduced to room temperature at a constant speed to obtain a target product MnO/Mn3O4@ C-N-1 composite material.
Comparative example 2
Preparation of MnO/Mn3O4@ C-N-2 nanocomposite
Dispersing 5.6g of polyvinylpyrrolidone into a mixed solution of 100mL of absolute ethyl alcohol and primary deionized water (volume ratio is 2: 1), stirring and mixing uniformly at 300rpm, adding 1.1g of manganese acetate tetrahydrate at the same rotating speed, stirring and mixing uniformly to obtain a clear and transparent solution X; dissolving 2.0g of trimesic acid in 100mL of a mixed solution of absolute ethyl alcohol and primary deionized water (volume ratio of 2: 1) and uniformly mixing with stirring to obtain a solution Y, and then using a BT100-2J peristaltic pump to pump the solution Y at 300rpm for 0.8mL of s-1Adding the solution Y into the clear and transparent solution X obtained in the step S1 at a flow rate, standing for several hours,then centrifugally collecting the obtained precipitate, washing the obtained precipitate for multiple times by using absolute ethyl alcohol to remove a surfactant and residual ions, and then drying the obtained product in a vacuum drying oven at 75 ℃ for 10 hours to obtain carbon-coated binary transition metal oxide solid spherical composite material precursor powder; in a tube furnace at 1 deg.C for min under argon atmosphere-1Heating to 480 deg.C at a heating rate, calcining the precursor powder for 2h, and then heating at 1 deg.C for min-1The temperature is reduced to room temperature at a constant speed to obtain a solid spherical target product MnO/Mn3O4@ C-N-2 composite material.
Comparative example 3
Preparation of MnO/Mn3O4@ C-N-3 nanocomposite
Dispersing 5.6g of polyvinylpyrrolidone into a mixed solution of 100mL of absolute ethyl alcohol and primary deionized water (volume ratio is 2: 1), stirring and mixing uniformly at 300rpm, adding 1.1g of manganese acetate tetrahydrate at the same rotating speed, stirring and mixing uniformly to obtain a clear and transparent solution X; dissolving 2.0g of trimesic acid in 100mL of a mixed solution of absolute ethyl alcohol and primary deionized water (volume ratio of 2: 1) and uniformly mixing with stirring to obtain a solution Y, and then using a BT100-2J peristaltic pump to pump the solution Y at 300rpm for 3.0mL s-1Adding the solution Y into the clear transparent solution X obtained in the step S1 at a flow rate, standing for several hours, centrifuging to collect the obtained precipitate, washing the obtained precipitate with absolute ethyl alcohol for multiple times to remove a surfactant and residual ions, and drying the obtained product in a vacuum drying oven at 75 ℃ for 10 hours to obtain carbon-coated binary transition metal oxide solid spherical composite material precursor powder; in a tube furnace at 1 deg.C for min under argon atmosphere-1Heating to 480 deg.C at a heating rate, calcining the precursor powder for 2h, and then heating at 1 deg.C for min-1The temperature is reduced to room temperature at a constant speed to obtain a solid spherical target product MnO/Mn3O4@ C-N-3 composite material.
MnO-Mn prepared in example 13O4Mixing the @ C-N nano composite material, super P and binder in a mass ratio of 60:30:10 to prepare slurry, uniformly coating the slurry on a working electrode obtained on a steel mesh current collector, and adding potassiumMetal as counter electrode, glass fiber microporous filter membrane as diaphragm, 1mol L-1 KPF6(the solvent is a mixed solution of ethylene carbonate and dimethyl carbonate with the volume ratio of 1: 1) as an electrolyte, and the battery is assembled in a vacuum glove box.
And (3) carrying out charge and discharge tests on the assembled battery on a charge and discharge tester, wherein the tested charge and discharge interval is 0.005-3V. At 20mA g-1、30mA g-1、50mA g-1、80mA g-1、120mA g-1，150mA g-1And 20mA g-1The rate performance of the assembled battery was tested at charge and discharge rates of (a). Then at 50mA g-1The cycle performance of the assembled battery was tested under the rate conditions of (1).
As shown in FIG. 8, MnO-Mn obtained in example 13O4Rate performance graph of @ C-N nanocomposite as negative electrode material of potassium ion battery, from which the MnO-Mn3O4@ C-N nanocomposites at 20mA g-1Under the current density, the charging specific capacity of the first loop can reach 325mA h g-1When different flow rates were set using the BT100-2J peristaltic pump, the product was MnO/Mn obtained in comparative example 23O4@ C-N-2 nanocomposite and MnO/Mn obtained in comparative example 33O4The charging specific capacity of the @ C-N-3 nano composite material is 30-60mA h g lower than that of the target product prepared in the embodiment 1-1About MnO/Mn obtained without using BT100-2J peristaltic pump3O4The highest specific charge capacity of the @ C-N-1 composite material (prepared by the comparative example 1) can only reach 231mA h g-1The specific capacity of commercial MnO can be maintained only at 70mA hr g-1Commercial Mn3O4The specific capacity of the catalyst can be only kept at 50mA h g-1FIG. 9 shows MnO-Mn obtained in example 13O4The circulation performance graph of the @ C-N nano composite material as the negative electrode material of the potassium ion battery can be seen, and MnO-Mn can be seen from the graph3O4@ C-N nanocomposite at 50mA g-1Under the current density, the first reversible specific capacity reaches 217mA h g-1After 300 cycles, the current can still be kept at 206mA h g-1The specific capacity retention rate reaches 94 percent. The products obtained in comparative examples 2 and 3 begin to rapidly decay in capacity when the circulation time is less than 100 circles, and can only be maintained at 100mA h g after 300 circles of circulation-1Both the capacity and the cycling stability are poorer than those of the product obtained in example one, viewed as a whole. Solid spherical MnO/Mn3O4The specific capacity of the @ C-N-1 composite material is attenuated to 110mA h g through three hundred circles of circulation specific capacity under the same current density-1The specific capacity retention rate is only 60 percent, and the commercial MnO can be stabilized at 22mA h g-1Commercial Mn3O4The capacity can only be kept at 10mA h g after walking for 100 circles-1Thus, solid spherical MnO/Mn3O4@ C-N-1 composite, commercial MnO and commercial Mn3O4Compared with the above-mentioned Mn ratio, it was revealed that the MnO-Mn ratio was very different3O4The @ C-N nano composite material shows better rate performance and cycle performance when used as a potassium ion battery cathode material, and similarly, when the BT100-2J peristaltic pump is set at different flow rates, the capacity and the stability of the obtained products are different.
Characterization of MnO-Mn prepared in examples by XRD and SEM3O4@ C-N nanocomposite, FIG. 1 MnO-Mn prepared in example 13O4The XRD pattern of the @ C-N nano composite material shows that the MnO-Mn synthesized by the pattern3O4The @ C-N nano composite material contains crystal forms MnO and Mn3O4. FIG. 2 shows MnO-Mn obtained in example 13O4SEM image of @ C-N nano composite material, MnO-Mn can be seen from the image3O4The @ C-N nano composite material is in a hollow bowl-shaped nano structure; FIG. 3 is an enlarged view of a portion of FIG. 2, showing the bowl-like structure surface comprised of primary particles; FIG. 4 shows MnO-Mn obtained in example 13O4High resolution transmission electron microscopy of @ C-N nanocomposite material indicates that the heterojunction has a particle size of 5nm, and is coated with a 3nm carbon coating layer, likewise MnO and Mn3O4The lattice fringe information of (a) again confirms that both are crystal structures in fig. 1; FIG. 5 shows MnO/Mn of a comparative sample3O4Of @ C-N-1 composite materialsScanning electron microscopy images from which the conclusion can be drawn: under the condition of not using a BT100-2J peristaltic pump, the prepared product is a smooth solid spherical nano structure; FIG. 6 shows MnO/Mn obtained in comparative example 23O4Scanning electron microscopy of @ C-N-2 nanocomposites, which are solid spheres of non-uniform size; FIG. 7 shows MnO/Mn obtained in comparative example 33O4Scanning electron microscope images of the @ C-N-3 nanocomposite material, which is irregularly-shaped cluster particles, comparison of the images in FIG. 6 and FIG. 7 shows that the morphology of the product is different when the BT100-2J peristaltic pump is used at different flow rates.
The foregoing embodiments illustrate the principles, principal features and advantages of the invention, and it will be understood by those skilled in the art that the invention is not limited to the foregoing embodiments, which are merely illustrative of the principles of the invention, and that various changes and modifications may be made therein without departing from the scope of the principles of the invention.
Claims (4)
1. A preparation method of an in-situ carbon-coated binary transition metal oxide heterojunction bowl-shaped nano composite material is characterized by comprising the following specific steps:
step S1: uniformly mixing absolute ethyl alcohol and primary deionized water according to the volume ratio of 2:1 to obtain a solvent A, dissolving polyvinylpyrrolidone in the solvent A to form a colorless solution, continuously stirring, and adding manganese acetate tetrahydrate into the stirring colorless solution to obtain a clear and transparent solution X;
step S2: preparing solvent A 'with the same proportion and volume as solvent A in step S1, adding trimesic acid into solvent A' and stirring uniformly to obtain solution Y, and stirring while using a peristaltic pump to make solution Y into 1.0-2.5mL S-1Adding the solution to the clear transparent solution X obtained in the step S1, controlling the speed of nucleation, the size of nucleation, the appearance of bowl shape, the size of bowl shape and the uniformity of bowl shape diameter by controlling the flow rate of the solution Y, standing, performing suction filtration to obtain a reaction product, and washing the reaction product with absolute ethyl alcohol for more than three times to remove the residual surfactant polyethyleneThe preparation method comprises the following steps of (1) putting an obtained reaction product into a vacuum drying oven to be dried so as to quickly dry a nucleation product, so as to obtain primary particles of the carbon-coated binary transition metal oxide heterojunction nano composite material, and simultaneously obtain bowl-shaped precursor powder assembled by the primary particles;
step S3: the precursor powder obtained in the step S2 is put in an argon atmosphere at the temperature of 1-25 ℃ for min-1The temperature is raised to 350-880 ℃ at the temperature raising rate for heat treatment for 0.3-16h, and then the temperature is raised for 1-15 min-1The temperature reduction rate is reduced to room temperature at a constant speed, and finally the target product in-situ carbon-coated binary transition metal oxide heterojunction bowl-shaped nano composite material is obtained, wherein the in-situ carbon-coated binary transition metal oxide heterojunction bowl-shaped nano composite material is specifically MnO-Mn3O4@ C-N composite, MnO and Mn3O4Are all crystal materials.
2. The method for preparing the bowl-shaped in-situ carbon-coated binary transition metal oxide heterojunction nanocomposite material according to claim 1, wherein the method comprises the following steps: the MnO-Mn3O4In the @ C-N nano composite material, MnO accounts for MnO-Mn3O4The mass percent of the @ C-N nano composite material is 25-92 percent, and Mn3O4In MnO-Mn3O4The mass percent of the @ C-N nano composite material is 5-70%, and the balance is N-doped amorphous C.
3. The method for preparing the bowl-shaped in-situ carbon-coated binary transition metal oxide heterojunction nanocomposite material according to claim 1, wherein the method comprises the following steps: the feeding mass ratio of the polyvinylpyrrolidone, the tetrahydrate manganese acetate and the trimesic acid is 5-7:1-2.5: 2-3.5.
4. The application of the in-situ carbon-coated binary transition metal oxide heterojunction bowl-shaped nano composite material prepared by the method according to any one of claims 1 to 3 as a high-performance potassium ion battery negative electrode material.
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