CN110627121B - Nano-sheet self-assembled vanadium pentoxide nano-rod and preparation method and application thereof - Google Patents
Nano-sheet self-assembled vanadium pentoxide nano-rod and preparation method and application thereof Download PDFInfo
- Publication number
- CN110627121B CN110627121B CN201910889288.5A CN201910889288A CN110627121B CN 110627121 B CN110627121 B CN 110627121B CN 201910889288 A CN201910889288 A CN 201910889288A CN 110627121 B CN110627121 B CN 110627121B
- Authority
- CN
- China
- Prior art keywords
- nano
- vanadium pentoxide
- assembled
- reaction kettle
- sheet
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
- C01G31/02—Oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a nano-sheet self-assembled vanadium pentoxide nano-rod as well as a preparation method and application thereof, wherein the nano-sheet self-assembled vanadium pentoxide nano-rod comprises the following steps: taking vanadium salt, hydrazine hydrate and ammonia water, and uniformly stirring in a container to obtain a mixed solution; pouring the mixed solution into a hydrothermal reaction kettle, sealing the hydrothermal reaction kettle, putting the hydrothermal reaction kettle into a thermostat, adjusting the reaction, and cooling the hydrothermal reaction kettle to room temperature; and cleaning and drying the sample to obtain the one-dimensional nano-sheet self-assembled vanadium pentoxide nano-rod. The prepared nano-sheet self-assembled vanadium pentoxide nanorod has the advantages of a two-dimensional nano-sheet and a one-dimensional nanorod: the nano-sheet increases the specific surface area of the material, simultaneously shortens the ion diffusion and transmission path, and the gaps between the sheets can also effectively store electrolyte and buffer the volume change of the material in the charging and discharging process, thereby improving the cycle of the battery and improving the charging and discharging capacity; the nano-rod can exert the advantages of a one-dimensional structure, is beneficial to the transmission of electrons, and improves the conductive effect so as to improve the cycle and rate performance of the battery.
Description
Technical Field
The invention belongs to the technical field of electrochemical energy storage-sodium ion batteries, and particularly relates to a nano-sheet self-assembled vanadium pentoxide nanorod and a preparation method and application thereof.
Background
As a more mature commercial technology, lithium ion batteries have been widely used in portable electronic devices due to their higher energy density, and are now being developed and applied to electric vehicles and large-scale energy storage applications [ Guo S, et al. energy environ.sci.2016,9, 2978-; armand M, et al. Nature 2008,451, 652-; kovalenko I, et al.science 2011,334, 75-79; ji X.L, et al Nat. Mater.2009,8, 500-); dunn B, et al, science 2011,334, 928-935; wang F, et al. energy environ. Sci.2016,9, 3666-; yang J, et al. adv.mater.2017,29,1604108; song J, et al. adv. Funct. Mater.2014,24, 1243-1250.). However, due to the limited nature of lithium resources and the worldwide maldistribution, it is predicted that the cost of lithium ion batteries will increase dramatically in the near future and that the price will rise [ Liu J, et at. energy environ. sci.,2015,8, 3531-3538; wang H.G, et at. energy environ. sci.,2015,8, 1660-; goodenough J.B, et at.J.am.chem.Soc.,2013,135, 1167-; song J, et al nano lett, 2014,14, 6329-; zhu Y, et al acs Nano,2015,9, 3254-. Recently, sodium ion batteries have been considered as one of the most promising alternatives to lithium ion batteries due to the abundant storage of sodium, lower price and close physicochemical properties to lithium [ Jiang Y, et al. energy environ.sci.,2016,9, 1430-1438; yang C, et al. energy environ. Sci.,2017,10, 107-113; liu Z, et al, energy environ, sci, 2016,9, 2314-. Recent efforts in sodium ion batteries have focused primarily on research in electrode materials, which have demonstrated relatively satisfactory rate and cycling performance. However, there are still great challenges to develop sodium ion batteries with more excellent performance. These challenges are mainly due to the fact that the radius of sodium ions is much larger than that of lithium ions, thus making it impossible to simply and directly adopt the knowledge and accumulated strategy gained from the development of high-performance lithium ion batteries. For example, the most widely economical graphite in the negative electrode materials of commercial lithium ion batteries, when used as the negative electrode of sodium ion batteries, exhibits only a specific capacity of 30-35mAh/g, because the small interlamellar spacing structure of graphite is not sufficient to effectively achieve reversible intercalation and deintercalation of sodium ions and stretching of carbon-carbon bonds during sodium modification, which renders the sodium-graphite intercalation compound thermodynamically unstable [ Liu S, et al. energy environ.sci.10(2017) 1222; luo W, et al.Acc.chem.Res.49(2016) 231-240; cao Y, et al nano lett, 2012,12, 3783-; wen Y, et al. nat. commun.,2014,5, 10; su D, et al adv. energy mater, 2015,5,1401205 ]. Although this is an example of a negative electrode material, experimental results and theoretical calculations indicate that a minimum interlayer spacing of 0.37nm is a condition that must be met for the host material in order to enable reversible intercalation and deintercalation of sodium ions in the host material. [ ZHao X, et al. adv. energy mater.2019, 1803648; cao Y, et al nano lett.12(2012) 3783-3787; wen Y, et al. nat. commun.5(2014) 4033; xiong X, et al sci. re.5(2015) 9254), therefore, it is a prerequisite for all jobs to consider the interlayer spacing, whether it is the choice of negative or positive material.
Currently, in the research on the positive electrode material of the sodium-ion battery, the lithium-ion battery mainly comprises layered transition metal oxide [ Berthelot, r.et al.nat.mater.2011,10, 74-80; xia, x.et al.electrochem.solid-State lett.2012,15, a1-a 4; su, D, et al chem. Eur.J.2013,19, 10884-; lee, K.T, et al chem.mater.2011,23, 3593-; jian, Z, et al, adv, energy mater.2013,3,156-160 ], wherein, the layered vanadium pentoxide attracts the attention of researchers due to its unique crystal structure and larger interlayer spacing, and is widely researched as a sodium-ion battery anode material, and certain achievements are obtained [ Tepavcevic S, et al, acs Nano,2012,6,530 ]; su D, et al ACS Nano,2013,7,11218, Raju V, et al Nano Lett, 2014,14, 4119-; su D, et al.j.mater.chem.a,2014,2, 11185; li H, et al. journal of Power Sources 285(2015) 418-424. Su et al prepared single-crystal double-layer vanadium pentoxide nanoribbons by a simple solvothermal method, the larger (001) interplanar spacing of the single-crystal double-layer vanadium pentoxide nanoribbons enables the single-crystal double-layer vanadium pentoxide nanoribbons to adapt to the intercalation and deintercalation of sodium ions, and the single-crystal double-layer vanadium pentoxide nanoribbons show a high capacity of 231.4mAh/g at a current density of 80mA/g [ Su D, et al. Tepavcevic and the like adopt an electrochemical method to prepare double-layer vanadium pentoxide with a Nano structure as a sodium-ion battery anode, circulate under the multiplying power of C/8 and have high power of 1200W/kg [ Tepavcevic S, et al. Raju et al prepare a composite structure of vanadium pentoxide coated nanoporous carbon by hydrolytic deposition in air, and the battery quality specific capacity is as high as 276mAh/g [ Raju V, et al. Su et al prepared hierarchical vanadium pentoxide hollow nanospheres by a polyol-induced solvothermal method, as sodium ion battery anodes, exhibited specific discharge capacity of 150mAh/g [ Su D, et al.J.Mater.chem.A., 2014,2,11185 ]. Li and the like grow a nano-crystalline vanadium pentoxide double-layer structure in situ on a stainless steel substrate, the optimized battery capacity is as high as 220mAh/g, and the capacity retention rate is as high as 92% after 500 cycles [ Li H, et al.
In summary, the research reported so far can improve the capacity of vanadium pentoxide as the positive electrode of sodium ion battery and improve the cycle performance to some extent, but the rate performance of the electrode based on vanadium pentoxide is still to be improved due to the inherent poor conductivity of the metal oxide. It is reported that the composite material is compounded with a carbon material with good conductivity, and although the composite material is beneficial to improving the rate capability, the addition of the carbon material reduces the specific capacity of the battery and the energy density. Therefore, on the premise of not losing the energy density of the battery, how to further improve the rate capability of the vanadium pentoxide electrode is still an important consideration for the current research on vanadium pentoxide materials.
Disclosure of Invention
One of the purposes of the invention is to provide a preparation method of a nano-sheet self-assembled vanadium pentoxide nano-rod, which realizes the synthesis of the nano-sheet self-assembled vanadium pentoxide nano-rod by controlling the preparation conditions, and comprises the controllable adjustment of the thickness and height of the nano-sheet, the diameter and the length of the nano-rod. The nano-sheet self-assembled vanadium pentoxide nano-rod prepared by the method has the advantages of a two-dimensional nano-sheet and a one-dimensional nano-rod.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a nano-sheet self-assembled vanadium pentoxide nano-rod comprises the following steps:
(1) uniformly stirring vanadium salt, hydrazine hydrate and ammonia water in a container to obtain a mixed solution, wherein the dosage ratio of the vanadium salt to the hydrazine hydrate to the ammonia water is 80% (w/w) to 25% (w/w) to 0.1-1 g: 1-10 mL: 1-30 mL;
(2) pouring the mixed solution into a hydrothermal reaction kettle, sealing the hydrothermal reaction kettle, putting the hydrothermal reaction kettle into a thermostat, adjusting the reaction temperature to 190-250 ℃ for 8-24 hours, and cooling the hydrothermal reaction kettle to room temperature after reaction;
(3) and taking out the sample in the reaction vessel, cleaning and drying to obtain the one-dimensional self-assembled nano-sheet vanadium pentoxide nanorod.
In some embodiments, the method further comprises calcining at 480 ℃ and 430 ℃ for 1-3 hours.
In some of these examples, the reaction temperature in step (2) is preferably 220 ℃ to 240 ℃ and the reaction time is 22 to 24 hours.
In some embodiments, in the step (1), the ratio of the vanadium salt to 80% (w/w) hydrazine hydrate to 25% (w/w)) ammonia water is more preferably 0.4-0.6 g: 2-4 mL: 25-30 mL.
In some embodiments, the vanadium salt in step (1) is one or more of ammonium metavanadate, sodium metavanadate, vanadium acetylacetonate, potassium metavanadate, triisopropoxytrianadate, bismuth vanadate, cyclopentadienyl vanadium dichloride and vanadyl sulfate, and more preferably sodium vanadate.
In some of the examples, the stirring time in step (1) of the present invention is 5min to 1h, more preferably 20min to 40 min.
In some embodiments, the closed hydrothermal reaction kettle used in step (2) of the present invention is a high temperature high pressure reaction kettle, the high pressure reaction kettle has a metal shell, a closed plastic or glass liner is arranged in the metal shell, wherein the plastic is polytetrafluoroethylene.
In some embodiments, the washing in step (3) of the present invention is performed several times by using deionized water and absolute ethyl alcohol sequentially.
In some embodiments, the temperature for drying in the step (3) is 50-70 ℃, and the drying time is 5-48 h.
The invention also aims to provide the one-dimensional nano sheet self-assembled vanadium pentoxide nano rod obtained by the preparation method.
The invention also aims to provide the application of the one-dimensional nano sheet self-assembled vanadium pentoxide nano rod as the anode in the preparation of the sodium-ion battery.
The invention also aims to provide a sodium ion battery, and the positive electrode of the sodium ion battery is made of the one-dimensional nano sheet self-assembled vanadium pentoxide nano rod.
According to the preparation method of the one-dimensional nano-sheet self-assembled vanadium pentoxide nanorod, the core reagents used in the preparation method are ammonia water and hydrazine hydrate, the ammonia water and the hydrazine hydrate are used as a solvent and a reducing agent to dissolve and reduce vanadium salt to obtain low-valence vanadium oxide under the synergistic effect of hydrothermal conditions, the proportion of the ammonia water and the hydrazine hydrate and the reducing agent as well as the reaction temperature and time are regulated and controlled, the structure of the one-dimensional nano-sheet self-assembled is further optimized and prepared, and the one-dimensional nano-sheet self-assembled vanadium pentoxide nanorod with good crystallization is further obtained through calcination in a muffle furnace.
Compared with the prior art, the invention has the advantages that:
the one-dimensional nano-sheet self-assembled vanadium pentoxide nanorod prepared by the method for preparing the one-dimensional nano-sheet self-assembled vanadium pentoxide nanorod has the advantages of a two-dimensional nano-sheet and a one-dimensional nanorod: the nano-sheet increases the specific surface area of the material, simultaneously shortens the ion diffusion and transmission path, and the gaps between the sheets can also effectively store electrolyte and buffer the volume change of the material in the charging and discharging process, thereby improving the cycle of the battery and improving the charging and discharging capacity; the nano-rod can exert the advantages of a one-dimensional structure, is beneficial to the transmission of electrons, and improves the conductive effect so as to improve the cycle and rate performance of the battery.
The method for preparing the one-dimensional nano sheet self-assembled vanadium pentoxide nano rod has the advantages of simple operation, high yield and short time consumption by adopting a simple hydrothermal method, and is different from relatively complex electrochemical methods adopted in reports such as electro-reduction, electroplating and the like, so that the preparation efficiency can be greatly improved.
Drawings
FIG. 1 is a scanning electron microscope photograph of a one-dimensional nano-sheet self-assembled vanadium pentoxide nanorod in embodiment 1 of the present invention: (a) a low magnification photograph; (b) high magnification photograph.
FIG. 2 is an X-ray diffraction pattern of a one-dimensional nano-sheet self-assembled vanadium pentoxide nanorod in embodiment 1 of the present invention.
Fig. 3 is a first charge-discharge curve of the battery when the one-dimensional nano-sheet self-assembled vanadium pentoxide nanorod prepared in embodiment 1 of the invention is used as the positive electrode of the sodium-ion battery.
Fig. 4 is a cycle curve of the battery for the first 10 times when the one-dimensional nano sheet self-assembled vanadium pentoxide nanorod prepared in the embodiment 1 of the invention is used as the positive electrode of the sodium ion battery.
FIG. 5 is a scanning electron micrograph of vanadium pentoxide prepared in example 2 of the present invention: (a) a low magnification photograph; (b) high magnification photograph.
FIG. 6 is a scanning electron micrograph of vanadium pentoxide prepared in example 3 of the present invention: (a) a low magnification photograph; (b) high magnification photograph.
FIG. 7 is a scanning electron micrograph of vanadium pentoxide prepared in example 4 of the present invention: (a) a low magnification photograph; (b) high magnification photograph.
FIG. 8 is a scanning electron micrograph of vanadium pentoxide prepared in example 5 of the present invention: (a) a low magnification photograph; (b) high magnification photograph.
FIG. 9 is a scanning electron micrograph of vanadium pentoxide prepared in example 6 of the present invention: (a) a low magnification photograph; (b) high magnification photograph.
FIG. 10 is a scanning electron micrograph of vanadium pentoxide prepared in example 7 of the present invention: (a) a low magnification photograph; (b) high magnification photograph.
Detailed Description
The practice of the present invention will employ, unless otherwise indicated, conventional techniques of materials science, inorganic chemistry and the like, which are within the skill of the art. See, e.g., Sambrook, Fritsch and maniotis, molecular cloning, a laboratory manual, 3 rd edition (2002). The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out under conventional conditions or conditions recommended by the manufacturers. The various chemicals used in the examples are commercially available.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The present invention will be further illustrated with reference to the following examples. It is to be understood that the following examples are given for illustrative purposes only and are not intended to limit the scope of the present invention. Various modifications and alterations of this invention will become apparent to those skilled in the art without departing from the spirit and scope of this invention.
Example 1
(1) Respectively measuring 0.5 g of sodium metavanadate, 30ml of ammonia water (with the concentration of 25w/w percent in the market), 3 ml of hydrazine hydrate (with the concentration of 80w/w percent in the market) and stirring the mixture for 30 minutes by strong magnetic force, and then putting the mixture into a reaction kettle, wherein the reaction kettle is a high-temperature high-pressure reaction kettle and is provided with a metal shell, and a sealed polytetrafluoroethylene or glass lining is arranged in the metal shell;
(2) screwing the reaction kettle, putting the reaction kettle into a constant temperature box, setting the reaction temperature to be 230 ℃, setting the reaction time to be 24 hours, and naturally cooling the reaction kettle to room temperature after the reaction is finished;
(3) opening the reaction kettle in the step (2), taking out a sample, washing the sample for 3 times by using deionized water and absolute ethyl alcohol, and drying the sample in a thermostat at 60 ℃ for 24 hours; and further placing the dried sample in a muffle furnace for 2 hours at 450 ℃ to calcine to obtain a final sample.
FIG. 1 is a scanning electron microscope picture of the obtained one-dimensional nano-sheet self-assembled vanadium pentoxide nanorod: as can be seen from the low-power scanning electron microscope image, products with one-dimensional structures are uniformly distributed in a large area, and the length of the products is measured to be 50-200 micrometers; the high-power scanning electron microscope image shows that the nano-sheets are staggered to form a one-dimensional nano-rod structure, the thickness of the nano-sheets is about 50nm, and the diameter of the nano-rods is 9 microns. FIG. 2 is an X-ray diffraction pattern of the prepared one-dimensional nano-sheet self-assembled vanadium pentoxide nanorod, and peaks of labeled diffraction surfaces correspond to 72-0433 of vanadium pentoxide standard PDF card JCPDF, which shows that the product prepared by the experiment has good crystallization. FIG. 3 is a first charge-discharge curve obtained by assembling a sodium ion battery by using a one-dimensional nano-sheet self-assembled vanadium pentoxide nanorod as a positive electrode and a sodium sheet as a counter electrode. Fig. 4 is a previous 20-time circulation curve of the battery, and it can be seen that the capacity of the battery is relatively stable, the first discharge specific capacity is 125.6mAh/g, and the capacity is 140.2mAh/g after 10-time circulation, which indicates that the vanadium pentoxide nanorod electrode based on the one-dimensional self-assembly nano sheet has good circulation stability, and illustrates the potential application prospect of the one-dimensional self-assembly nano sheet vanadium pentoxide nanorod as the positive electrode of the sodium ion battery.
Example 2
(1) Respectively measuring 0.2g of sodium metavanadate, 30ml of ammonia water (with the concentration of 25w/w percent in the market), 3 ml of hydrazine hydrate (with the concentration of 80w/w percent in the market) and stirring the mixture for 30 minutes by strong magnetic force, and then putting the mixture into a reaction kettle, wherein the reaction kettle is a high-temperature high-pressure reaction kettle and is provided with a metal shell, and a sealed polytetrafluoroethylene or glass lining is arranged in the metal shell;
(2) screwing the reaction kettle, putting the reaction kettle into a constant temperature box, setting the reaction temperature to be 230 ℃, setting the reaction time to be 24 hours, and naturally cooling the reaction kettle to room temperature after the reaction is finished;
(3) and (3) opening the reaction kettle in the step (2), taking out the sample, washing the sample for 3 times by using deionized water and absolute ethyl alcohol, and drying the sample in a thermostat for 24 hours at the temperature of 60 ℃. Fig. 5 is a scanning electron microscope picture of a product obtained by reducing the amount of sodium metavanadate to 0.2g, and it can be seen from fig. 1 that the nano-sheet and the one-dimensional nano-rod structure disappear and an open hollow structure is substituted for the nano-sheet and the one-dimensional nano-rod structure, and comparative example 1 shows that the amount of sodium metavanadate has a crucial influence on the final structure.
Example 3
(1) Respectively measuring 0.5 g of sodium metavanadate, 0.3g of hexamethylenetetramine, 30ml of ammonia water (sold on the market, the concentration is 25w/w percent), 3 ml of hydrazine hydrate (sold on the market, the concentration is 80w/w percent) and stirring for 30 minutes by strong magnetic force, and then putting the mixture into a reaction kettle, wherein the reaction kettle is a high-temperature high-pressure reaction kettle and is provided with a metal shell, and a sealed polytetrafluoroethylene or glass lining is arranged in the metal shell;
(2) screwing the reaction kettle, putting the reaction kettle into a constant temperature box, setting the reaction temperature to be 230 ℃, setting the reaction time to be 24 hours, and naturally cooling the reaction kettle to room temperature after the reaction is finished;
(3) and (3) opening the reaction kettle in the step (2), taking out the sample, washing the sample for 3 times by using deionized water and absolute ethyl alcohol, and drying the sample in a thermostat for 24 hours at the temperature of 60 ℃. Fig. 6 is a scanning electron microscope picture of a product obtained by a reaction after 0.3g of surfactant hexamethylenetetramine is added, from fig. 6, it can be seen that the one-dimensional nanorod structure disappears, and instead, an irregular particle structure appears, but a small piece similar to a wrinkle exists on the surface of the particle, comparative example 1 shows that the addition of hexamethylenetetramine affects the formation of the one-dimensional structure on one hand, and also limits the growth of the nanosheet on the other hand, which shows that the hexamethylenetetramine has a crucial effect on the final structure.
Example 4
(1) Respectively measuring 0.5 g of sodium metavanadate, 30ml of ammonia water (with the concentration of 25w/w percent in the market), 3 ml of hydrazine hydrate (with the concentration of 80w/w percent in the market) and stirring the mixture for 30 minutes by strong magnetic force, and then putting the mixture into a reaction kettle, wherein the reaction kettle is a high-temperature high-pressure reaction kettle and is provided with a metal shell, and a sealed polytetrafluoroethylene or glass lining is arranged in the metal shell;
(2) screwing the reaction kettle, putting the reaction kettle into a constant temperature box, setting the reaction temperature to be 230 ℃, setting the reaction time to be 18 hours, and naturally cooling the reaction kettle to room temperature after the reaction is finished;
(3) and (3) opening the reaction kettle in the step (2), taking out the sample, washing the sample for 3 times by using deionized water and absolute ethyl alcohol, and drying the sample in a thermostat for 24 hours at the temperature of 60 ℃. Fig. 7 is a scanning electron microscope picture of a product obtained by the reaction after the reaction time is shortened to 18 hours, and it can be seen from fig. 7 that the one-dimensional nanorod structure disappears and an irregular particle structure appears instead, but small nanosheets exist on the surface of the particle, as compared with example 1, it is shown that shortening the reaction time affects the formation of the one-dimensional structure on one hand, and further growth of the nanosheets is also limited on the other hand, which indicates that the reaction time has a crucial influence on the final structure.
Example 5
(1) Respectively measuring 0.5 g of sodium metavanadate, 0.3g of hexamethylenetetramine, 30ml of ammonia water (sold on the market, the concentration is 25w/w percent), 3 ml of hydrazine hydrate (sold on the market, the concentration is 80w/w percent) and stirring for 30 minutes by strong magnetic force, and then putting the mixture into a reaction kettle, wherein the reaction kettle is a high-temperature high-pressure reaction kettle and is provided with a metal shell, and a sealed polytetrafluoroethylene or glass lining is arranged in the metal shell;
(2) screwing the reaction kettle, putting the reaction kettle into a constant temperature box, setting the reaction temperature to be 230 ℃, setting the reaction time to be 18 hours, and naturally cooling the reaction kettle to room temperature after the reaction is finished;
(3) and (3) opening the reaction kettle in the step (2), taking out the sample, washing the sample for 3 times by using deionized water and absolute ethyl alcohol, and drying the sample in a thermostat for 24 hours at the temperature of 60 ℃. FIG. 8 is a scanning electron microscope picture of a product obtained by adding 0.3g of hexamethylenetetramine as a surfactant and shortening the reaction time to 18 hours, from FIG. 8, it can be seen that the one-dimensional morphology of the product disappears, mainly irregular hollow particles are formed, but nanosheets with smaller sizes are grown on the surface of the particles.
Example 6
(1) Respectively measuring 0.3g of sodium metavanadate, 55 ml of ammonia water (commercially available, with the concentration of 25 w/w%) and 5 ml of hydrazine hydrate (commercially available, with the concentration of 80 w/w%) and stirring the mixture for 30 minutes by strong magnetic force, and then putting the mixture into a reaction kettle, wherein the reaction kettle is a high-temperature high-pressure reaction kettle and is provided with a metal shell, and a sealed polytetrafluoroethylene or glass lining is arranged in the metal shell;
(2) screwing the reaction kettle, putting the reaction kettle into a constant temperature box, setting the reaction temperature to be 230 ℃, setting the reaction time to be 24 hours, and naturally cooling the reaction kettle to room temperature after the reaction is finished;
(3) and (3) opening the reaction kettle in the step (2), taking out the sample, washing the sample for 3 times by using deionized water and absolute ethyl alcohol, and drying the sample in a thermostat for 24 hours at the temperature of 60 ℃. Fig. 9 is a scanning electron microscope picture of a product obtained after reaction by reducing the vanadium salt dosage and simultaneously increasing ammonia water and hydrazine hydrate, and it can be seen from the picture that the product is no longer a one-dimensional structure, but a large number of particles with different sizes appear, and meanwhile, although wrinkles exist on the particle surface, the size of the nanosheet is obviously reduced.
Example 7
(1) Respectively measuring 0.3g of sodium metavanadate, 55 ml of ammonia water (commercially available, with the concentration of 25 w/w%) and 5 ml of hydrazine hydrate (commercially available, with the concentration of 80 w/w%) and stirring the mixture for 30 minutes by strong magnetic force, and then putting the mixture into a reaction kettle, wherein the reaction kettle is a high-temperature high-pressure reaction kettle and is provided with a metal shell, and a sealed polytetrafluoroethylene or glass lining is arranged in the metal shell;
(2) screwing the reaction kettle, putting the reaction kettle into a constant temperature box, setting the reaction temperature to be 230 ℃, setting the reaction time to be 8 hours, and naturally cooling the reaction kettle to room temperature after the reaction is finished;
(3) and (3) opening the reaction kettle in the step (2), taking out the sample, washing the sample for 3 times by using deionized water and absolute ethyl alcohol, and drying the sample in a thermostat for 24 hours at the temperature of 60 ℃. Fig. 10 is a scanning electron microscope picture of a product obtained after reaction by reducing the vanadium salt dosage, increasing ammonia water and hydrazine hydrate and simultaneously shortening the reaction time to 18 hours, and it can be seen from the picture that the product is no longer a one-dimensional structure, but a large number of particles with different sizes appear, and at the same time, although wrinkles exist on the particle surface, the size of the nanosheet is obviously reduced.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A preparation method of a nano-sheet self-assembled vanadium pentoxide nano-rod is characterized by comprising the following steps:
(1) taking vanadium salt, hydrazine hydrate and ammonia water, and uniformly stirring in a container to obtain a mixed solution; when the concentration of hydrazine hydrate is 80% w/w and the concentration of ammonia water is 25% w/w, the dosage ratio of the vanadium salt, the hydrazine hydrate and the ammonia water is 0.4-0.6 g: 2-4 mL: 25-30 mL;
(2) pouring the mixed solution into a hydrothermal reaction kettle, sealing the hydrothermal reaction kettle, putting the hydrothermal reaction kettle into a thermostat, adjusting the reaction temperature to be 220-240 ℃, reacting for 22-24 hours, and cooling the hydrothermal reaction kettle to room temperature after reaction;
(3) and taking out the sample in the reaction vessel, cleaning and drying to obtain the one-dimensional self-assembled nano-sheet vanadium pentoxide nanorod.
2. The method for preparing self-assembled nano-sheet vanadium pentoxide nanorods according to claim 1, characterized in that the method further comprises calcining at 480 ℃ and 430 ℃ for 1-3 hours after drying in step (3).
3. The method for preparing nano-sheet self-assembled vanadium pentoxide nano-rods according to claim 1, wherein the vanadium salt in step (1) is one or more of ammonium metavanadate, sodium metavanadate, vanadium acetylacetonate, potassium metavanadate, triisopropoxytrianise, bismuth vanadate, cyclopentadienyl vanadium dichloride and vanadyl sulfate.
4. The preparation method of the nano-sheet self-assembled vanadium pentoxide nanorod according to claim 1, wherein the stirring time in the step (1) is 5 min-1 h.
5. The preparation method of the nano-sheet self-assembled vanadium pentoxide nanorod according to claim 4, wherein the stirring time in the step (1) is 20-40 min.
6. The method for preparing nano-sheet self-assembled vanadium pentoxide nano-rods according to claim 1, wherein the water in step (2) is heated in a high-temperature high-pressure reactor, the high-pressure reactor has a metal shell, and a closed plastic or glass liner is arranged in the metal shell, wherein the plastic is polytetrafluoroethylene.
7. The preparation method of the nano-sheet self-assembled vanadium pentoxide nanorod according to any one of claims 1-4, wherein the washing in the step (3) is performed by sequentially washing with deionized water and absolute ethyl alcohol for 1-3 times; and/or the temperature for drying in the step (3) is 50-70 ℃, and the drying time is 5-48 h.
8. Nanosheet self-assembled vanadium pentoxide nanorods obtained by the preparation method according to any one of claims 1 to 7.
9. The use of nano-sheet self-assembled vanadium pentoxide nanorods according to claim 8 in the preparation of sodium-ion batteries.
10. A sodium-ion battery, characterized in that the positive electrode of the sodium-ion battery is made of the nano-sheet self-assembled vanadium pentoxide nano-rods of claim 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910889288.5A CN110627121B (en) | 2019-09-19 | 2019-09-19 | Nano-sheet self-assembled vanadium pentoxide nano-rod and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910889288.5A CN110627121B (en) | 2019-09-19 | 2019-09-19 | Nano-sheet self-assembled vanadium pentoxide nano-rod and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110627121A CN110627121A (en) | 2019-12-31 |
| CN110627121B true CN110627121B (en) | 2022-02-18 |
Family
ID=68971769
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910889288.5A Active CN110627121B (en) | 2019-09-19 | 2019-09-19 | Nano-sheet self-assembled vanadium pentoxide nano-rod and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110627121B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101700909A (en) * | 2009-11-25 | 2010-05-05 | 中国科学技术大学 | Method of preparing intelligent energy-saving vanadium dioxide by hydrothermal method |
| CN104261472A (en) * | 2014-09-22 | 2015-01-07 | 安徽工业大学 | Vanadium pentoxide nanobelt, and room-temperature synthesis method and application of vanadium pentoxide nanobelt |
| CN104577087A (en) * | 2014-12-29 | 2015-04-29 | 中国工程物理研究院化工材料研究所 | VO2(B) nanobelt, preparation method thereof, and lithium battery assembled with VO2(B) nanobelt |
| CN106904653A (en) * | 2017-01-22 | 2017-06-30 | 重庆大学 | The preparation method of vanadium dioxide nano material and applied in magnesium chargeable battery |
| CN107069020A (en) * | 2017-02-17 | 2017-08-18 | 武汉理工大学 | A kind of preparation method of lithium ion battery nickel doping vanadic anhydride nano-sheet positive electrode |
| CN109205674A (en) * | 2018-11-19 | 2019-01-15 | 北京科技大学 | A method of preparing vanadic anhydride base nanometer sheet |
| CN109775759A (en) * | 2019-01-10 | 2019-05-21 | 广东工业大学 | A kind of vanadium dioxide anode material of lithium-ion battery and preparation method thereof |
| CN110078121A (en) * | 2019-05-21 | 2019-08-02 | 上海交通大学 | A kind of preparation method and application of Magnesium ion battery vanadic anhydride positive electrode |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150380732A1 (en) * | 2014-06-30 | 2015-12-31 | Indiana University Research And Technology Corporation | Novel vanadium oxide cathode material |
-
2019
- 2019-09-19 CN CN201910889288.5A patent/CN110627121B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101700909A (en) * | 2009-11-25 | 2010-05-05 | 中国科学技术大学 | Method of preparing intelligent energy-saving vanadium dioxide by hydrothermal method |
| CN104261472A (en) * | 2014-09-22 | 2015-01-07 | 安徽工业大学 | Vanadium pentoxide nanobelt, and room-temperature synthesis method and application of vanadium pentoxide nanobelt |
| CN104577087A (en) * | 2014-12-29 | 2015-04-29 | 中国工程物理研究院化工材料研究所 | VO2(B) nanobelt, preparation method thereof, and lithium battery assembled with VO2(B) nanobelt |
| CN106904653A (en) * | 2017-01-22 | 2017-06-30 | 重庆大学 | The preparation method of vanadium dioxide nano material and applied in magnesium chargeable battery |
| CN107069020A (en) * | 2017-02-17 | 2017-08-18 | 武汉理工大学 | A kind of preparation method of lithium ion battery nickel doping vanadic anhydride nano-sheet positive electrode |
| CN109205674A (en) * | 2018-11-19 | 2019-01-15 | 北京科技大学 | A method of preparing vanadic anhydride base nanometer sheet |
| CN109775759A (en) * | 2019-01-10 | 2019-05-21 | 广东工业大学 | A kind of vanadium dioxide anode material of lithium-ion battery and preparation method thereof |
| CN110078121A (en) * | 2019-05-21 | 2019-08-02 | 上海交通大学 | A kind of preparation method and application of Magnesium ion battery vanadic anhydride positive electrode |
Non-Patent Citations (3)
| Title |
|---|
| Facile hydrothermal growth of VO2 nanowire,nanorod and nanosheet arrays as binder free cathode materials for sodium batteries;Hongkuan Wang et al.;《RSC Advances》;20160128;第6卷;第14314-14320页 * |
| Hydrothermal Synthesis of Nanostructured Vanadium Oxides;Jacques Livage;《Materials》;20100802;第3卷;第4175-4195页 * |
| V2O5 self-assembled nanosheets as high stable cathodes for Lithium-ion batteries;Jianfeng Huang et al.;《Electrochimica Acta》;20160113;第191卷;第158-164页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110627121A (en) | 2019-12-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105742602B (en) | A kind of sodium-ion battery cathode Sn/MoS2/ C composite and preparation method thereof | |
| CN107611404B (en) | Prussian white composite material and preparation method and application thereof | |
| CN109286009B (en) | Preparation method of nano-sheet self-assembled three-dimensional nano-flower tin sulfide/graphitized carbon nitride lithium ion battery cathode material | |
| CN108658119B (en) | Method for preparing copper sulfide nanosheet and compound thereof by low-temperature vulcanization technology and application | |
| CN109473650B (en) | MoO (MoO)2/rGO composite material and preparation method and application thereof | |
| CN108155353B (en) | Graphitized carbon coated electrode material, preparation method thereof and application of graphitized carbon coated electrode material as energy storage device electrode material | |
| CN109346688B (en) | Yolk-shell structure negative electrode material, preparation method thereof and lithium ion battery | |
| CN104900861B (en) | A kind of lithium hydrogentitanate Li H Ti O material and preparation method thereof | |
| CN107123794B (en) | A kind of preparation method of carbon coating manganese monoxide/N doping redox graphene lithium ion battery negative material | |
| CN109301204B (en) | Preparation method of hollow sphere structure tin sulfide/tin oxide lithium ion battery anode material | |
| CN110880589B (en) | Carbon nanotube @ titanium dioxide nanocrystal @ carbon composite material and preparation method and application thereof | |
| CN109755515B (en) | Silicon/carbon cathode composite material of lithium ion battery and preparation method thereof | |
| CN110416530B (en) | Flower-like manganese dioxide/carbon composite material and preparation method and application thereof | |
| CN110683522A (en) | Transition metal chalcogen family carbon-based heterostructure composite material with regular morphology and preparation method and application thereof | |
| CN104577072A (en) | Preparation method of graphene-oxide-based MoO2 high-performance electrode material of lithium/sodium ion battery | |
| WO2022032747A1 (en) | Method for preparing sulfur-doped rese2/mxene composite material | |
| CN112786865A (en) | MoS2Preparation method and application of quasi-quantum dot/nitrogen-sulfur co-doped biomass carbon composite nano material | |
| CN109830657A (en) | A kind of MoS2/MoO2The preparation method of/three-dimensional carbon lithium ion battery negative material | |
| CN110233251A (en) | A kind of preparation method and applications of porous silicon/carbon composite material | |
| CN105826522A (en) | Method for preparing in-situ carbon coated manganese carbonate for negative electrode of lithium ion battery | |
| CN106920957B (en) | A kind of molybdenum dioxide nano particle and preparation method thereof for lithium ion battery negative material | |
| CN108281620A (en) | A kind of preparation method of anode material of lithium-ion battery titanium dioxide | |
| CN109449440B (en) | Microporous ultrathin soft carbon nanosheet and preparation method and application thereof | |
| CN112331845A (en) | Preparation method of cobaltosic oxide nanowire array negative electrode material | |
| CN110627121B (en) | Nano-sheet self-assembled vanadium pentoxide nano-rod and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |