CN114293321A - Low-cost room-temperature rapid batch preparation method and equipment for special-shaped vanadium oxide nanofibers and aggregates thereof - Google Patents
Low-cost room-temperature rapid batch preparation method and equipment for special-shaped vanadium oxide nanofibers and aggregates thereof Download PDFInfo
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- CN114293321A CN114293321A CN202111661141.4A CN202111661141A CN114293321A CN 114293321 A CN114293321 A CN 114293321A CN 202111661141 A CN202111661141 A CN 202111661141A CN 114293321 A CN114293321 A CN 114293321A
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Abstract
The invention discloses a low-cost room-temperature rapid batch preparation method of special-shaped vanadium oxide nano fibers and aggregates thereof, which comprises the following steps: mixing and stirring ammonium polyvanadate and an acid solution to obtain a vanadium intermediate nanofiber dispersion liquid; separating the vanadium intermediate nanofiber dispersion liquid to obtain vanadium intermediate nanofibers and aggregates thereof; and washing, drying and calcining the vanadium intermediate nanofiber and the vanadium intermediate nanofiber aggregate to obtain the vanadium oxide nanofiber with the special-shaped structure and the vanadium oxide nanofiber aggregate. The invention also discloses a preparation device of the vanadium oxide nanofiber with the special-shaped structure and the aggregate thereof. The method adopts the vanadium source ammonium polyvanadate with low cost to disperse in the acid water solution, fully stirs and mixes the solution to ensure that the vanadium source ammonium polyvanadate and the acid water solution quickly exchange ions and grow in a recrystallization orientation mode, has short reaction time period, quick reaction process, strong temperature adaptability and strong container expansibility, and is suitable for large-scale, low-cost and quick production of the vanadium oxide nano-fiber with the special-shaped structure and the aggregate thereof in a factory.
Description
Technical Field
The invention relates to the field of preparation of nano materials, in particular to a low-cost room-temperature rapid batch preparation method and equipment for special-shaped vanadium oxide nano fibers and aggregates thereof.
Background
The vanadium resources in China, particularly the Panxi area, are extremely rich and are the vast countries of the vanadium resource reserves and the vanadium products. Vanadium is an industrially important additive, and is called industrial monosodium glutamate. The development of high added value vanadium products is not only beneficial to the adjustment and upgrade of industrial structure, but also beneficial to the development of economy and the enhancement of national strength. Vanadium oxide is the most important vanadium functional material and intermediate, and has important application value in the fields of special steel, industrial colorants, catalysts and electrochemical energy storage materials. The one-dimensional vanadium oxide nanowire has a unique effect on the preparation of flexible electronic devices, catalysis and material performance optimization due to the large specific surface area, multiple active points and good mechanical flexibility. At present, hydrothermal methods (201910038538.4, 201210352298.3), template methods (201310276103.6), sol-gel methods (201410396489.9), precipitation methods (201410485637.4) and other physical and chemical methods are mainly used for synthesizing the one-dimensional vanadium oxide nano material.
The vanadium oxide special-shaped structure nanowire woven non-woven fabric has wider and special application such as catalysis, energy storage and multi-stage structure materials due to the special macro morphology and microstructure of the vanadium oxide special-shaped structure nanowire woven non-woven fabric. At present, the traditional vanadium pentoxide (V) can be obtained by suction filtration2O5) And (3) carrying out nano wire (201410436433.1, 202110736817.5) or electrostatic spinning on the vanadium intermediate compound, and calcining to obtain the large-area vanadium pentoxide fiber non-woven fabric. However, these methods are expensive, long in preparation period, or complicated in process. For example, most current methods use Ammonium Metavanadate (AMV) or V2O5Vanadium oxide nanofibers are prepared from raw materials, but the cost of the raw materials is high; most of the prior processes have the problems of harsh reaction conditions, long preparation period and the like. For example, hydrothermal method has high temperature and high pressure (generally over 180 ℃), long reaction time (generally over ten hours), and is difficult to produce on a large scale.The sol-gel method generally needs cation exchange resin, and has high cost, complex process or long preparation period (generally more than several days). The precipitation method needs additional mineralizer and has long reaction period (generally several days). The template method and the electrostatic spinning method have complex process and high cost, and the addition of the auxiliary agent causes low fiber strength and the like. At present, the method for preparing the special-shaped nanofiber non-woven fabric and the special-shaped nanofiber aggregate by adopting a more primary vanadium intermediate Ammonium Polyvanadate (APV), simple processes (acid solution dispersion, stirring and filtering), an ultra-short period (a few minutes) and room temperature and normal pressure (lowest energy consumption) has important technical value and market prospect, and the technology and the process are not reported yet.
Disclosure of Invention
In view of this, an object of the embodiments of the present invention is to provide a low-cost room-temperature rapid batch preparation method and apparatus for a special-shaped vanadium oxide nanofiber and an aggregate thereof, so as to solve the technical problems of high cost, long preparation period, complex process, unsuitability for mass production in factories, and the like of the preparation method in the prior art. The method adopts the vanadium source ammonium polyvanadate with low cost to disperse in the acid water solution, fully stirs and mixes the solution to ensure that the vanadium source ammonium polyvanadate and the acid water solution quickly exchange ions and grow in a recrystallization orientation mode, has short reaction time period, quick reaction process, strong temperature adaptability and strong container expansibility, and is suitable for large-scale, low-cost and quick production of the vanadium oxide nano-fiber with the special-shaped structure and the aggregate thereof in a factory.
In view of the above objects, an aspect of the embodiments of the present invention provides a low-cost room-temperature rapid batch preparation method of profiled vanadium oxide nanofibers and their aggregates, comprising the following steps: mixing and stirring ammonium polyvanadate and an acid solution to obtain a vanadium intermediate nanofiber dispersion liquid; separating the vanadium intermediate nanofiber dispersion liquid to obtain vanadium intermediate nanofibers and aggregates thereof; and washing, drying and calcining the vanadium intermediate nanofiber and the vanadium intermediate nanofiber aggregate to obtain the vanadium oxide nanofiber with the special-shaped structure and the vanadium oxide nanofiber aggregate. The diameter of the vanadium oxide nanofiber with the special-shaped structure obtained by the method is 20-1000nm, the purity of the vanadium oxide nanofiber aggregate with the special-shaped structure is more than or equal to 95%, the thickness or the particle size of the vanadium oxide nanofiber aggregate with the special-shaped structure is 0.01-100mm, and the diameter obtained by changing the ratio of ammonium polyvanadate to acid is adjustable. Meanwhile, the method adopts the ammonium polyvanadate and the acid solution to mix and stir, the reaction process is simple, the cost of the required vanadium source ammonium polyvanadate is low, and the method is favorable for large-scale application in factories; and the ammonium polyvanadate and the acid solution have short chemical reaction time period and strong temperature adaptability in the reaction process, can react at normal temperature and at higher or lower temperature, and are favorable for realizing large-scale, low-cost and rapid preparation of the specially-shaped vanadium oxide nanofibers and the aggregates thereof in factories.
In some embodiments, the ammonium polyvanadate is mixed with the acid solution in a mass ratio of (0.2-20) to 100, and the concentration of the acid solution is 2-200 g/L. According to the mass ratio and the concentration, the reaction time period of the ammonium polyvanadate and the acid solution is short, and the large-scale, low-cost and rapid preparation of the vanadium oxide nano-fiber with the special-shaped structure and the aggregate thereof in a factory is facilitated.
In some embodiments, the ammonium polyvanadate and the acid solution are preferably mixed in a mass ratio of (1-10) to 100, and the concentration of the acid solution is 10-100 g/L. According to the mass ratio and the concentration, the reaction is favorably carried out and the chemical reaction limit is improved, so that the large-scale, low-cost and quick preparation of the specially-shaped vanadium oxide nanofiber aggregate in a factory is favorably realized.
In some embodiments, mixing and stirring the ammonium polyvanadate with the acid solution comprises: and mixing, shearing and stirring the ammonium polyvanadate and the acid solution at normal temperature and normal pressure.
In some embodiments, the ammonium polyvanadate comprises technical grade ammonium polyvanadate, and the acid solution comprises any one of the group consisting of nitric acid, hydrochloric acid, sulfuric acid, oxalic acid, phosphoric acid, and acetic acid. The method preferably adopts industrial ammonium polyvanadate and acid solution, the required cost is further reduced, and the acid solution can be recycled, thereby being beneficial to large-scale production of factories, energy conservation and environmental protection.
In some embodiments, separating the vanadium intermediate nanofiber dispersion comprises: and carrying out suction filtration on the vanadium intermediate nanofiber dispersion liquid to obtain a vanadium intermediate nanofiber membrane, washing, drying and calcining the vanadium intermediate nanofiber membrane to obtain a specially-shaped structure vanadium oxide nanofiber membrane, and crushing the specially-shaped structure vanadium oxide nanofiber membrane to obtain nanofiber particles or powder. The method can obtain the vanadium intermediate nanofiber membrane by performing suction filtration and separation, and further obtains the vanadium oxide nanofiber membrane with the special-shaped structure by washing, drying and calcining.
In some embodiments, the method further comprises the steps of: and adjusting the calcining temperature to change the crystal form and the color of the specially-shaped structure vanadium oxide nanofiber membrane.
In some embodiments, separating the vanadium intermediate nanofiber dispersion comprises: and carrying out filter pressing on the vanadium intermediate nanofiber dispersion liquid to obtain a vanadium intermediate nanofiber block, washing, drying and calcining the vanadium intermediate nanofiber block to obtain a specially-shaped vanadium oxide nanofiber block, and crushing the specially-shaped vanadium oxide nanofiber block to obtain specially-shaped vanadium oxide nanofiber particles or powder.
In some embodiments, separating the vanadium intermediate nanofiber dispersion comprises: and freeze-drying the vanadium intermediate nanofiber dispersion liquid to obtain vanadium intermediate nanofiber aerogel, and calcining the vanadium intermediate nanofiber aerogel to obtain the vanadium oxide nanofiber aerogel with the special-shaped structure.
Another aspect of the embodiments of the present invention provides a device for preparing vanadium oxide nanofibers with a special-shaped structure and aggregates thereof, which is used for implementing the method of the present invention.
By adopting the technical method, the invention at least has the following beneficial effects:
the invention provides a low-cost room-temperature rapid batch preparation method of special-shaped vanadium oxide nanofibers and aggregates thereof. The method has the advantages that the cost of vanadium source ammonium polyvanadate is low, the process flow of mixing and stirring ammonium polyvanadate and an acid solution is simple, the time period required by the reaction process of the ammonium polyvanadate and the acid solution is short, the temperature adaptability is strong, the ammonium polyvanadate and the acid solution can react at room temperature or even at lower temperature or higher temperature, the expansibility of a container for reacting the ammonium polyvanadate and the acid solution is strong, the acid solution is recycled, the energy conservation and environmental protection of industrial large-scale production can be realized, and based on the method, the preparation method of the special-shaped structure vanadium oxide nanofiber aggregate is favorable for realizing large-scale, low-cost, rapid, energy conservation and environmental protection preparation of the special-shaped structure vanadium oxide nanofiber and the special-shaped structure vanadium oxide nanofiber aggregate in a factory.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other embodiments can be obtained by using the drawings without creative efforts.
FIG. 1 is a schematic diagram of an embodiment of a low-cost room temperature rapid batch preparation method of profiled vanadium oxide nanofibers and their aggregates according to the present invention;
FIG. 2 is a schematic diagram of an embodiment of a low-cost room temperature rapid batch preparation method of the profiled vanadium oxide nanofibers and their aggregates according to the present invention;
figure 3 shows an XRD pattern of a commercial grade vanadium derived polyvanadate Amine (APV) powder;
figure 4 shows an XRD pattern of the intermediate vanadium intermediate nanofiber membrane;
fig. 5(a) shows an SEM image of the intermediate vanadium intermediate nanofiber membrane at magnification of 300 ×;
fig. 5(b) shows an SEM image of the intermediate vanadium intermediate nanofiber membrane at magnification of 3000 ×;
fig. 5(c) shows an SEM image of the intermediate vanadium intermediate nanofiber membrane at magnification of 30000 ×;
fig. 5(d) shows an SEM image of the intermediate vanadium intermediate nanofibrous membrane at magnification 100000 ×;
fig. 6(a) shows SEM images of the reaction product irregularly structured vanadium oxide nanofiber membranes at magnifications of 300 × respectively;
fig. 6(b) shows SEM images of the reaction product irregularly structured vanadium oxide nanofiber membranes at magnifications of 1000 × respectively;
fig. 6(c) shows SEM images of the reaction product irregularly structured vanadium oxide nanofiber membranes at magnifications of 3000 × respectively;
fig. 6(d) shows SEM images of the reaction product heterostructured vanadium oxide nanofiber membrane at magnifications of 10000 × respectively;
fig. 6(e) shows SEM images of the reaction product irregularly structured vanadium oxide nanofiber membranes at magnifications of 30000 × respectively;
FIG. 7 shows XRD patterns of the specially-shaped structure vanadium oxide nanofiber membranes obtained at the calcining temperatures of 350 ℃, 450 ℃ and 600 ℃ respectively;
FIG. 8 is a schematic diagram of a preferred embodiment of the low-cost room temperature rapid batch preparation method of the profiled vanadium oxide nanofibers and their aggregates provided by the present invention.
Detailed Description
Embodiments of the present invention are described below. However, it is to be understood that the disclosed embodiments are merely examples and that other embodiments may take various and alternative forms.
In addition, it should be noted that all expressions using "first" and "second" in the embodiments of the present invention are used for distinguishing two entities with the same name but different names or different parameters, and it should be noted that "first" and "second" are only used for convenience of expression and should not be construed as a limitation to the embodiments of the present invention, and the descriptions thereof in the following embodiments are omitted. The terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
One or more embodiments of the present application will be described below with reference to the accompanying drawings.
Based on the above purposes, the embodiment of the invention provides a low-cost room-temperature rapid batch preparation method of special-shaped vanadium oxide nanofibers and aggregates thereof. FIG. 1 is a schematic diagram of an embodiment of a low-cost room temperature rapid batch preparation method of the profiled vanadium oxide nanofibers and the aggregates thereof provided by the invention. As shown in fig. 1, the low-cost room-temperature rapid batch preparation method of the special-shaped vanadium oxide nanofibers and the aggregates thereof according to the embodiment of the present invention includes the following steps:
s1, mixing and stirring ammonium polyvanadate and an acid solution to obtain a vanadium intermediate nanofiber dispersion solution;
s2, separating the vanadium intermediate nanofiber dispersion liquid to obtain vanadium intermediate nanofibers and aggregates thereof; and
and S3, washing, drying and calcining the vanadium intermediate nanofiber and the vanadium intermediate nanofiber aggregate to obtain the vanadium oxide nanofiber with the special-shaped structure and the vanadium oxide nanofiber aggregate.
FIG. 2 is a schematic diagram of an embodiment of a low-cost room temperature rapid batch preparation method of the profiled vanadium oxide nanofibers and the aggregates thereof provided by the invention. As shown in FIG. 2, the steps of the low-cost room temperature rapid batch preparation method of the special-shaped vanadium oxide nano-fiber and the special-shaped vanadium oxide nano-aggregate comprise: weighing a certain amount of ammonium polyvanadate, dispersing in a dilute sulfuric acid solution, and stirring at a high speed at room temperature for no more than 10 minutes to obtain a vanadium intermediate nanofiber dispersion solution; carrying out suction filtration on the obtained dispersion liquid to obtain a vanadium intermediate nanofiber membrane; leaching the obtained vanadium intermediate nanofiber membrane with deionized water, and drying in an oven at 80 ℃; and placing the obtained dried vanadium intermediate nanofiber membrane in a muffle furnace for calcining to obtain the vanadium oxide nanofiber membrane with the special-shaped structure. According to the embodiment of the present invention, the concentration of the dilute sulfuric acid, the stirring time, the obtained intermediate product, and the calcination temperature and the calcination time can be varied to obtain the reaction product as shown in table 1 below.
TABLE 1
Figure 3 shows the XRD pattern of industrial grade vanadium-derived polyoxovanadoamine (APV) for a low cost room temperature rapid batch process of low cost of profiled vanadium oxide nanofibers and their aggregates.
Fig. 4 shows XRD patterns of intermediate products (vanadium-based intermediates), i.e., vanadium intermediate nanofiber films, obtained by an embodiment of a low-cost room-temperature rapid batch preparation method of profiled vanadium oxide nanofibers and aggregates thereof.
Fig. 5(a), (b), (c), (d) show SEM images of the intermediate vanadium intermediate nanofiber membrane obtained in the example of the low-cost room temperature fast batch preparation method of a profiled vanadium oxide nanofiber and its aggregate at magnifications of 300 ×, 3000 ×, 30000 ×, and 100000 ×, respectively.
Fig. 6(a), (b), (c), (d), (e) show SEM images of the reaction product, heterostructured vanadium oxide nanofiber membrane obtained in the example of the low-cost room temperature rapid batch preparation method of a heterostructured vanadium oxide nanofiber and its aggregate, at magnifications of 300 ×, 1000 ×, 3000 ×, 10000 ×, and 30000 ×, respectively.
Fig. 7 shows XRD patterns of the specially-shaped structure vanadium oxide nanofiber films obtained at calcination temperatures of 350 ℃, 450 ℃ and 600 ℃ respectively in an example of a low-cost room-temperature rapid batch preparation method of specially-shaped vanadium oxide nanofibers and their aggregates.
In view of the fact that the growth time, the temperature and the concentration of the mixed solution are properly matched, the reaction of the ammonium polyvanadate and the acid solution is favorably carried out, and the chemical reaction limit is improved, it is preferable that the concentration of the hydrochloric acid solution is 10-100g/L, and the ammonium polyvanadate and the hydrochloric acid solution are mixed according to the mass ratio of (1-10) to 100 for reaction.
FIG. 8 is a schematic diagram of a preferred embodiment of the low-cost room temperature rapid batch preparation method of the profiled vanadium oxide nanofibers and their aggregates provided by the present invention. As shown in fig. 8, the steps of the low-cost room temperature rapid batch preparation method of the profiled vanadium oxide nanofibers and the aggregates thereof include: weighing a certain amount of ammonium polyvanadate, dispersing in a dilute hydrochloric acid solution, and stirring at a high speed at room temperature for no more than 10 minutes to obtain a vanadium intermediate nanofiber dispersion liquid; carrying out filter pressing on the obtained dispersion liquid to obtain a vanadium intermediate nanofiber block; leaching the obtained vanadium intermediate nanofiber block with deionized water, and drying in an oven at 80 ℃; placing the obtained dried vanadium intermediate nanofiber block in a muffle furnace for calcining to obtain a special-shaped vanadium oxide nanofiber block; and crushing the obtained vanadium oxide nanofiber block with the special-shaped structure to obtain vanadium oxide nanofiber particles or powder with the special-shaped structure. According to the embodiment of the present invention, the concentration of the diluted hydrochloric acid, the stirring time, the obtained intermediate product, and the calcination temperature and the calcination time can be varied to obtain the reaction product, for example, as shown in the following table 2.
TABLE 2
The present invention will be further described with reference to specific examples, which should not be construed as limiting the scope of the invention.
Example 1
A method for preparing special-shaped vanadium oxide nano-fibers and aggregates thereof uses ammonium polyvanadate as a main raw material, and prepares the special-shaped vanadium oxide nano-fibers and the aggregates thereof by room-temperature shearing stirring and high-temperature calcination, and comprises the following steps:
(1) a certain amount of ammonium polyvanadate is weighed and dispersed in a dilute sulfuric acid (2g/L) solution, and the mixture is stirred at high speed for 10 minutes at room temperature.
(2) And (3) carrying out suction filtration on the dispersion liquid obtained in the step (1) to obtain the vanadium-based intermediate nanofiber membrane.
(3) And (3) leaching the vanadium-based intermediate nanofiber membrane obtained in the step (2) with deionized water, and drying in an oven at 80 ℃.
(4) And (4) placing the dried vanadium-based intermediate nanofiber membrane obtained in the step (3) in a muffle furnace for heat treatment at 450 ℃ for 2h to obtain the special-shaped vanadium oxide nanofiber membrane.
Example 2
A method for preparing special-shaped vanadium oxide nano-fibers and aggregates thereof uses ammonium polyvanadate as a main raw material, and prepares the special-shaped vanadium oxide nano-fibers and the aggregates thereof by room-temperature shearing stirring and high-temperature calcination, and comprises the following steps:
(1) a certain amount of ammonium polyvanadate is weighed and dispersed in a dilute sulfuric acid (30g/L) solution, and the mixture is stirred at high speed for 3 minutes at room temperature.
(2) And (3) carrying out suction filtration on the dispersion liquid obtained in the step (1) to obtain the vanadium-based intermediate nanofiber membrane.
(3) And (3) leaching the vanadium-based intermediate nanofiber membrane obtained in the step (2) with deionized water, and drying in an oven at 80 ℃.
(4) And (4) placing the dried vanadium-based intermediate nanofiber membrane obtained in the step (3) in a muffle furnace for heat treatment at 350 ℃ for 2h to obtain the special-shaped vanadium oxide nanofiber membrane.
Example 3
A method for preparing special-shaped vanadium oxide nano-fibers and aggregates thereof uses ammonium polyvanadate as a main raw material, and prepares the special-shaped vanadium oxide nano-fibers and the aggregates thereof by room-temperature shearing stirring and high-temperature calcination, and comprises the following steps:
(1) a certain amount of ammonium polyvanadate is weighed and dispersed in a sulfuric acid (200g/L) solution, and the mixture is stirred at high speed for 3 minutes at room temperature.
(2) And (3) carrying out suction filtration on the dispersion liquid obtained in the step (1) to obtain the vanadium-based intermediate nanofiber membrane.
(3) And (3) leaching the vanadium-based intermediate nanofiber membrane obtained in the step (2) with deionized water, and drying in an oven at 80 ℃.
(4) And (4) placing the dried vanadium-based intermediate nanofiber membrane obtained in the step (3) in a muffle furnace for heat treatment at 600 ℃ for 0.1h to obtain the special-shaped vanadium oxide nanofiber membrane.
(5) And (4) crushing the dried vanadium-based intermediate nanofiber membrane obtained in the step (4) to obtain nanofiber particles or powder.
Example 4
A method for preparing special-shaped vanadium oxide nano-fibers and aggregates thereof uses ammonium polyvanadate as a main raw material, and prepares the special-shaped vanadium oxide nano-fibers and the aggregates thereof by room-temperature shearing stirring and high-temperature calcination, and comprises the following steps:
(1) a certain amount of ammonium polyvanadate is weighed and dispersed in a dilute hydrochloric acid (0.2g/L) solution, and the mixture is stirred at high speed for 5 minutes at room temperature.
(2) And (3) carrying out suction filtration on the dispersion liquid obtained in the step (1) to obtain the vanadium-based intermediate nanofiber membrane.
(3) And (3) leaching the vanadium-based intermediate nanofiber membrane obtained in the step (2) with deionized water, and drying in an oven at 80 ℃.
(4) And (4) placing the dried vanadium-based intermediate nanofiber membrane obtained in the step (3) in a muffle furnace for heat treatment at 600 ℃ for 0.5h to obtain the special-shaped vanadium oxide nanofiber membrane.
(5) And (4) crushing the dried vanadium-based intermediate nanofiber membrane obtained in the step (4) to obtain nanofiber particles or powder.
Example 5
A method for preparing special-shaped vanadium oxide nano-fibers and aggregates thereof uses ammonium polyvanadate as a main raw material, and prepares the special-shaped vanadium oxide nano-fibers and the aggregates thereof by room-temperature shearing stirring and high-temperature calcination, and comprises the following steps:
(1) a certain amount of ammonium polyvanadate is weighed and dispersed in a hydrochloric acid (200g/L) solution, and the mixture is stirred at high speed for 5 minutes at room temperature.
(2) And (3) carrying out filter pressing on the dispersion liquid obtained in the step (1) to obtain a vanadium-based intermediate nanofiber block.
(3) And (3) leaching the vanadium-based intermediate nanofiber block obtained in the step (2) with deionized water, and drying in an oven at 60 ℃.
(4) And (4) placing the dried vanadium-based intermediate nanofiber block obtained in the step (3) in a muffle furnace for heat treatment at 350 ℃ for 1h to obtain the special-shaped vanadium oxide nanofiber block.
(5) And (4) crushing the dried vanadium-based intermediate nanofiber block obtained in the step (4) to obtain nanofiber particles or powder.
Example 6
A method for preparing special-shaped vanadium oxide nano-fibers and aggregates thereof uses ammonium polyvanadate as a main raw material, and prepares the special-shaped vanadium oxide nano-fibers and the aggregates thereof by room-temperature shearing stirring and high-temperature calcination, and comprises the following steps:
(1) a certain amount of ammonium polyvanadate is weighed and dispersed in a hydrochloric acid (10g/L) solution, and the mixture is stirred at high speed for 10 minutes at room temperature.
(2) And (3) freeze-drying the dispersion liquid obtained in the step (1) to obtain the vanadium-based intermediate nanofiber aerogel.
(3) And (3) placing the vanadium-based intermediate nanofiber aerogel obtained in the step (2) in a muffle furnace for heat treatment at 450 ℃ for 0.5h to obtain the special-shaped vanadium oxide nanofiber aerogel.
(4) The vanadium oxide nanofiber aerogel obtained in the step (3) can be further crushed to obtain nanofiber particles or powder; pressing can result in a relatively denser vanadium oxide nanofiber membrane.
Another aspect of the present invention provides a device for preparing specially-shaped structure vanadium oxide nanofibers and their aggregates, which is configured to implement the above method for preparing specially-shaped structure vanadium oxide nanofibers and their aggregates.
The foregoing is an exemplary embodiment of the present disclosure, but it should be noted that various changes and modifications could be made herein without departing from the scope of the present disclosure as defined by the appended claims. The functions, steps and/or actions of the method claims in accordance with the disclosed embodiments described herein need not be performed in any particular order. Furthermore, although elements of the disclosed embodiments of the invention may be described or claimed in the singular, the plural is contemplated unless limitation to the singular is explicitly stated.
It should be understood that, as used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, unless the context clearly supports the exception. It should also be understood that "and/or" as used herein is meant to include any and all possible combinations of one or more of the associated listed items.
The numbers of the embodiments disclosed in the embodiments of the present invention are merely for description, and do not represent the merits of the embodiments.
Those of ordinary skill in the art will understand that: the discussion of any embodiment above is meant to be exemplary only, and is not intended to intimate that the scope of the disclosure, including the claims, of embodiments of the invention is limited to these examples; within the idea of an embodiment of the invention, also technical features in the above embodiment or in different embodiments may be combined and there are many other variations of the different aspects of the embodiments of the invention as described above, which are not provided in detail for the sake of brevity. Therefore, any omissions, modifications, substitutions, improvements, and the like that may be made without departing from the spirit and principles of the embodiments of the present invention are intended to be included within the scope of the embodiments of the present invention.
Claims (10)
1. A low-cost room-temperature rapid batch preparation method of special-shaped vanadium oxide nanofibers and aggregates thereof is characterized by comprising the following steps:
mixing and stirring ammonium polyvanadate and an acid solution to obtain a vanadium intermediate nanofiber dispersion liquid;
separating the vanadium intermediate nanofiber dispersion liquid to obtain vanadium intermediate nanofibers and aggregates thereof;
and washing, drying and calcining the vanadium intermediate nanofiber and the vanadium intermediate nanofiber aggregate to obtain the vanadium oxide nanofiber with the special-shaped structure and the vanadium oxide nanofiber aggregate.
2. The method according to claim 1, wherein the ammonium polyvanadate is mixed with the acid solution in a mass ratio of (0.2-20) to 100, and the concentration of the acid solution is 2-200 g/L.
3. The method according to claim 2, wherein the ammonium polyvanadate is mixed with the acid solution, preferably in a mass ratio of (1-10) to 100, and the concentration of the acid solution is 10-100 g/L.
4. The method of claim 1, wherein mixing and agitating the ammonium polyvanadate with the acid solution comprises: and mixing, shearing and stirring the ammonium polyvanadate and the acid solution at normal temperature and normal pressure.
5. The method according to claim 1, wherein the ammonium polyvanadate comprises technical grade ammonium polyvanadate, and the acid solution comprises any one selected from the group consisting of nitric acid, hydrochloric acid, sulfuric acid, oxalic acid, phosphoric acid, and acetic acid.
6. The method of claim 1, wherein the separating the vanadium intermediate nanofiber dispersion comprises: and carrying out suction filtration on the vanadium intermediate nanofiber dispersion liquid to obtain a vanadium intermediate nanofiber membrane, washing, drying and calcining the vanadium intermediate nanofiber membrane to obtain a specially-shaped structure vanadium oxide nanofiber membrane, and crushing the specially-shaped structure vanadium oxide nanofiber membrane to obtain nanofiber particles or powder.
7. The method of claim 6, further comprising the steps of: and adjusting the calcining temperature to change the crystal form and the color of the vanadium oxide nanofiber membrane with the special-shaped structure.
8. The method of claim 1, wherein the separating the vanadium intermediate nanofiber dispersion comprises: and carrying out filter pressing on the vanadium intermediate nanofiber dispersion liquid to obtain a vanadium intermediate nanofiber block, washing, drying and calcining the vanadium intermediate nanofiber block to obtain a specially-shaped vanadium oxide nanofiber block, and crushing the specially-shaped vanadium oxide nanofiber block to obtain specially-shaped vanadium oxide nanofiber particles or powder.
9. The method of claim 1, wherein the separating the vanadium intermediate nanofiber dispersion comprises: and freeze-drying the vanadium intermediate nanofiber dispersion liquid to obtain vanadium intermediate nanofiber aerogel, and calcining the vanadium intermediate nanofiber aerogel to obtain the vanadium oxide nanofiber aerogel with the special-shaped structure.
10. A device for preparing vanadium oxide nanofibers with a special-shaped structure and aggregates thereof, characterized in that the device is configured to carry out the method of any one of claims 1 to 9.
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| CN116119713A (en) * | 2022-12-13 | 2023-05-16 | 攀钢集团研究院有限公司 | Preparation method of porous nano vanadium oxide, porous nano vanadium oxide and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107662946A (en) * | 2017-08-11 | 2018-02-06 | 攀枝花学院 | The preparation method of vanadium trioxide |
| CN113481656A (en) * | 2021-06-30 | 2021-10-08 | 攀钢集团研究院有限公司 | Preparation method of high-purity vanadium pentoxide nanofiber non-woven fabric |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107662946A (en) * | 2017-08-11 | 2018-02-06 | 攀枝花学院 | The preparation method of vanadium trioxide |
| CN113481656A (en) * | 2021-06-30 | 2021-10-08 | 攀钢集团研究院有限公司 | Preparation method of high-purity vanadium pentoxide nanofiber non-woven fabric |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116119713A (en) * | 2022-12-13 | 2023-05-16 | 攀钢集团研究院有限公司 | Preparation method of porous nano vanadium oxide, porous nano vanadium oxide and application |
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