CN110556249A - Preparation method of alpha-MnO 2 nanorod array - Google Patents

Preparation method of alpha-MnO 2 nanorod array Download PDF

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Publication number
CN110556249A
CN110556249A CN201810556726.1A CN201810556726A CN110556249A CN 110556249 A CN110556249 A CN 110556249A CN 201810556726 A CN201810556726 A CN 201810556726A CN 110556249 A CN110556249 A CN 110556249A
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mno
alpha
preparation
nanorod array
reaction
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夏晖
林宝伟
房灵哲
徐璟
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Nanjing Tech University
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Nanjing Tech University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/46—Metal oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • 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
    • Y02E60/13—Energy storage using capacitors

Abstract

The invention discloses a preparation method of an alpha-MnO 2 nanorod array, which is characterized in that KMnO 4 is dissolved in water, the PH is adjusted to 1-3 by dilute H 2 SO 4, a substrate material is added, hydrothermal reaction is carried out at 100-140 ℃, after the reaction is finished, washing and drying are carried out to obtain the alpha-MnO 2 nanorod array.

Description

Preparation method of alpha-MnO 2 nanorod array
Technical Field
The invention belongs to the technical field of nano material preparation, relates to a preparation method of MnO 2, and particularly relates to a preparation method of an alpha-MnO 2 nanorod array.
Background
2Super Capacitors (Supercapacitors), also called Electrochemical Capacitors (Electrochemical Capacitors), generally have power density 1-2 orders of magnitude higher than that of lithium ion batteries, cycle life 2-3 orders of magnitude higher, energy density 3-4 orders of magnitude higher than that of conventional Capacitors, and the like, and have received extensive attention as a novel, practical, and efficient energy storage device.
MnO 2 forms a plurality of crystal forms including alpha, beta, gamma, delta and the like through different connection modes of MnO 6 octahedron, wherein the three have a pore structure (alpha-MnO 2 is a 2 x 2 large pore structure; beta-MnO 2 is a 1 x 1 pore structure; gamma-MnO 2 is a part of a 2 x 2 small pore structure and a 1 x 1 pore structure), and delta-MnO 2 is an open layered structure. alpha-MnO capacitance performance is the best, while beta-and gamma-MnO 2 are relatively poor. the regulation of morphology can effectively regulate the specific surface area of MnO 2. therefore, MnO 2 with different morphologies in recent years, such as nanorods (Wang, GS; porous absorption properties of Nano-MnO 2 nanoparticles and the applicable Nano electric composites; RSC Advances), Nano-tubes (Jan, S.v.ut; Sealf-sapphire and Nano additive films) can effectively regulate the specific surface area of MnO 2, while the conductivity of Nano particles can be regulated to obtain Nano particles with excellent conductivity and Nano particles (Nano particles) and Nano particles of Nano particles, thus the Nano particles can be synthesized by Nano particles of Nano particles.
Disclosure of Invention
In order to solve the problem of poor conductivity of alpha-MnO 2 prepared by the existing method, the invention provides a preparation method of an alpha-MnO 2 nanorod array.
The technical scheme of the invention is as follows:
The preparation method of the alpha-MnO 2 nanorod array comprises the following steps:
Dissolving KMnO 4 in water, adjusting the pH value to 1-3 by using dilute H 2 SO 4, adding a substrate material, carrying out hydrothermal reaction at 100-140 ℃, washing after the reaction is finished, and drying to obtain the alpha-MnO 2 nanorod array.
Preferably, the concentration of the KMnO 4 solution is 0.01-0.2M.
Preferably, the concentration of the dilute H 2 SO 4 is 1M.
Preferably, the pH value is adjusted to 1-2.
Preferably, the substrate material can be stainless steel sheet, titanium sheet, nickel mesh, gold foil, platinum foil, and carbon material such as carbon fiber and carbon nanotube.
Preferably, the hydrothermal reaction is carried out in a high-pressure reaction kettle, and the volume of the mixed solution is 75-85% of the volume of the reaction kettle.
Preferably, the hydrothermal reaction temperature is 110-130 ℃, and the reaction time is 0.5-2 h.
Compared with the prior art, the invention has the following advantages:
The invention synthesizes the alpha-MnO 2 material with the nanorod array morphology by a simple one-step hydrothermal method, has short synthesis time, low reaction energy consumption, simple process and controllable process, and the prepared alpha-MnO 2 grows on a substrate uniformly and has uniform morphology without agglomeration.
Drawings
FIG. 1 is an XRD pattern of an α -MnO 2 nanorod array prepared in example 2.
FIG. 2 is a high power SEM image of the α -MnO 2 nanorod array prepared in example 2.
FIG. 3 is a low magnification SEM image of an α -MnO 2 nanorod array prepared in example 2.
Fig. 4 is an SEM image of MnO 2 prepared in comparative example 1.
Fig. 5 is an SEM image of MnO 2 prepared in comparative example 2.
Fig. 6 is an SEM image of MnO 2 prepared in comparative example 3.
Detailed Description
The present invention will be described in further detail with reference to the following examples and the accompanying drawings.
Example 1
dissolving 1mmol of KMnO 4 in 40ml of deionized water, adjusting the pH to 1 with 1M H 2 SO 4, adding 3cm by 3cm of carbon cloth as a substrate material, carrying out hydrothermal reaction at 100 ℃ for 0.5h, after the reaction is finished, washing the product with the deionized water, and drying in a 60 ℃ oven to obtain the alpha-MnO 2 nanorod array.
Example 2
Dissolving 2mmol of KMnO 4 in 40ml of deionized water, adjusting the pH to 1 by using 1M H 2 SO 4, adding 3cm by 3cm of carbon cloth as a substrate material, carrying out hydrothermal reaction at 120 ℃ for 0.5h, after the reaction is finished, washing the product with the deionized water, and drying in a 60 ℃ oven to obtain the alpha-MnO 2 nanorod array.
example 3
Dissolving 4mmol of KMnO 4 in 40ml of deionized water, adjusting the pH value to 1 by using 1M H 2 SO 4, adding 3cm by 3cm of carbon cloth as a substrate material, carrying out hydrothermal reaction at 140 ℃ for 0.5h, after the reaction is finished, washing the product with the deionized water, and drying in a 60 ℃ oven to obtain the alpha-MnO 2 nanorod array.
Example 4
dissolving 2mmol of KMnO 4 in 40ml of deionized water, adjusting the pH to 2 with 1M H 2 SO 4, adding 3cm by 3cm of carbon cloth as a substrate material, carrying out hydrothermal reaction at 120 ℃ for 1h, after the reaction is finished, washing the product with the deionized water, and drying in a 60 ℃ oven to obtain the alpha-MnO 2 nanorod array.
Example 5
Dissolving 2mmol of KMnO 4 in 40ml of deionized water, adjusting the pH to 3 by using 1M H 2 SO 4, adding 3cm by 3cm of carbon cloth as a substrate material, carrying out hydrothermal reaction at 120 ℃ for 2h, after the reaction is finished, washing the product with the deionized water, and drying in a 60 ℃ oven to obtain the alpha-MnO 2 nanorod array.
As shown in figure 1, the XRD pattern of the prepared alpha-MnO 2 with the nanorod array morphology is completely consistent with the standard card bar No.72-1982 in a database, which indicates that the crystal phase composition of the product is alpha-MnO 2, and in addition, the peak type of a visible ray diffraction peak is sharp, the peak intensity is high, and the crystal form development is good.
As shown in FIGS. 2 and 3, SEM images of the prepared alpha-MnO 2 with nanorod array morphology show that alpha-MnO 2 is in an array shape, and the array structure is formed by assembling nanorods.
comparative example 1
This comparative example is essentially the same as example 2, except that H 2 SO 4 was replaced with hcl-as can be seen from a comparison of fig. 2 and 4, the product with H 2 SO 4 was rod-shaped, while the product with HCI was ribbon-shaped, indicating that the presence of H 2 SO 4 is an important factor in the formation of a rod-shaped structure.
Comparative example 2
This comparative example is essentially the same as example 2, except that no H 2 SO 4 was added, it can be seen from a comparison of FIGS. 3 and 5 that the product with the addition of H 2 SO 4 was in the form of a higher loading rod, whereas the product without the addition of H 2 SO 4 had only a few needles on the substrate, indicating that the presence of H 2 SO 4 is an important factor in accelerating the progress of the reaction.
Comparative example 3
This comparative example is essentially the same as example 2, except that no H 2 SO 4 was added and the reaction time was extended to 10H-as can be seen from a comparison of fig. 2, fig. 3 and fig. 6, the product with H 2 SO 4 added was rod-like at higher loading, whereas the product without H 2 SO 4 had only a few needles on the substrate, and after greatly extending the reaction time, the product without H 2 SO 4 was less flaky, further illustrating that the presence of H 2 SO 4 is an important factor in accelerating the progress of the reaction and in forming the rod-like structure.

Claims (7)

1. The preparation method of the alpha-MnO 2 nanorod array is characterized by comprising the following steps of:
Dissolving KMnO 4 in water, adjusting the pH value to 1-3 by using dilute H 2 SO 4, adding a substrate material, carrying out hydrothermal reaction at 100-140 ℃, washing after the reaction is finished, and drying to obtain the alpha-MnO 2 nanorod array.
2. The preparation method according to claim 1, wherein the concentration of the KMnO 4 solution is 0.01-0.2M.
3. The method as claimed in claim 1, wherein the dilute H 2 SO 4 is at a concentration of 1M.
4. The method according to claim 1, wherein the pH is adjusted to 1 to 2.
5. The method according to claim 1, wherein the substrate material is selected from the group consisting of stainless steel sheet, titanium sheet, nickel mesh, gold foil, platinum foil, carbon fiber, and carbon nanotube.
6. The preparation method according to claim 1, wherein the hydrothermal reaction is carried out in an autoclave, and the volume of the mixed solution is 75 to 85% of the volume of the autoclave.
7. The preparation method according to claim 1, wherein the hydrothermal reaction temperature is 110 ℃ to 130 ℃ and the reaction time is 0.5h to 2 h.
CN201810556726.1A 2018-06-01 2018-06-01 Preparation method of alpha-MnO 2 nanorod array Pending CN110556249A (en)

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Publication number Priority date Publication date Assignee Title
CN112981453A (en) * 2021-02-05 2021-06-18 常熟理工学院 Method for preparing water oxidation electrode by using waste stainless steel as base material

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CN112981453A (en) * 2021-02-05 2021-06-18 常熟理工学院 Method for preparing water oxidation electrode by using waste stainless steel as base material

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