CN109994325B - Preparation method of bismuth oxide/nitrogen-doped carbon dot hollow porous microsphere negative electrode material - Google Patents

Preparation method of bismuth oxide/nitrogen-doped carbon dot hollow porous microsphere negative electrode material Download PDF

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CN109994325B
CN109994325B CN201910249229.1A CN201910249229A CN109994325B CN 109994325 B CN109994325 B CN 109994325B CN 201910249229 A CN201910249229 A CN 201910249229A CN 109994325 B CN109994325 B CN 109994325B
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nitrogen
doped carbon
preparation
bismuth oxide
hollow porous
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CN109994325A (en
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季振源
戴文瑶
沈小平
刘锴
朱国兴
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Jiangsu 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
    • H01G11/32—Carbon-based
    • 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 belongs to the field of nano composite material preparation, and particularly relates to a preparation method of a bismuth oxide/nitrogen-doped carbon point hollow porous microsphere negative electrode material. The bismuth oxide/nitrogen-doped carbon point hollow porous microsphere anode material is prepared by taking bismuth nitrate and nitrogen-doped carbon points as raw materials through a solvothermal-calcination two-step method. The bismuth oxide and the nitrogen-doped carbon dots in the composite material have a synergistic effect, so that the capacitance performance of a single material can be improved. As a super capacitor cathode material, the specific capacitance is as high as 1046F/g at 1A/g, and the super capacitor cathode material shows high electrochemical performance.

Description

Preparation method of bismuth oxide/nitrogen-doped carbon dot hollow porous microsphere negative electrode material
Technical Field
The invention belongs to the field of nano composite material preparation, and particularly relates to a preparation method of a bismuth oxide/nitrogen-doped carbon point hollow porous microsphere negative electrode material.
Technical Field
Recently, with the rapid development of smart grids, hybrid cars and portable electronic devices, the extensive research on the construction of advanced energy storage devices by researchers has been greatly stimulated. Among them, the super capacitor is the most promising energy storage device due to its fast charge and discharge capability, high power density and excellent cycle stability. The electrode material is used as a core part of energy storage of the super capacitor, and material selection and modification of the electrode material are always hot topics of research. The carbon material is widely applied to the cathode material of the supercapacitor due to the large specific surface area, the excellent conductivity and the good cycling stability. However, carbon-based materials tend to have a lower specific capacitance, which greatly limits the development of supercapacitors. Therefore, it is important to search for other negative electrode materials with high specific capacitance. At present, some transition metal oxides, such as Mn3O4，Fe2O3And Bi2O3Etc. have attracted the attention of researchers. Wherein, Bi2O3Has the advantages of low cost, rich content, and high theoretical specific capacitance (1370F g)-1) Etc. but with respect to Bi2O3Reports of negative electrode materials are less, and prepared Bi2O3The specific capacitance of the material is much lower than the theoretical capacitance, and the capacitance still needs to be further improved.
The carbon dots are a novel zero-dimensional carbon-based nano material with the size less than 10 nanometers, can accommodate various elements (such as N, O, S and the like) and functional groups (such as hydroxyl, carboxyl and carbonyl) on the surface of the carbon dots, and also have the advantages of good dispersibility, excellent conductivity, larger specific surface area, easiness in preparation and the like. At present, carbon dots have wide application in a plurality of fields such as photocatalysis, biological imaging, sensors, electrocatalysis, supercapacitors and the like.
Researches show that the carbon dots can improve the wettability of the electrode material and an electrolyte and improve the specific capacitance and the cycling stability of the electrode material. However, the research on the bismuth oxide/carbon dot composite anode material is rarely reported in the literature.
Disclosure of Invention
The bismuth oxide/nitrogen-doped carbon point hollow porous microsphere anode material is prepared by taking bismuth nitrate and nitrogen-doped carbon points as raw materials through a solvothermal-calcination two-step method. The bismuth oxide and the nitrogen-doped carbon dots in the composite material have a synergistic effect, so that the capacitance performance of a single material can be improved. As a super capacitor cathode material, the specific capacitance is as high as 1046F/g at 1A/g, and the super capacitor cathode material shows high electrochemical performance.
The invention aims to provide a preparation method of a bismuth oxide/nitrogen-doped carbon dot hollow porous microsphere negative electrode material, which adopts the following technical scheme:
(1) dispersing bismuth nitrate pentahydrate and nitrogen-doped carbon dots in a mixed solution of ethanol and acetic acid.
(2) Putting the solution obtained in the step (1) into a reaction kettle, and reacting for 20-24 h at 170-190 ℃; and after the reaction is finished, cooling, separating and washing the solid sample, drying to obtain a precursor, heating to 400-500 ℃ at a heating rate of 2 ℃/min in an inert atmosphere, and calcining for 3-4 h to obtain the bismuth oxide/nitrogen-doped carbon-point supercapacitor negative electrode material.
In the step (1), the nitrogen-doped carbon dots are prepared by using citric acid and ethylenediamine as raw materials and adopting a hydrothermal method. The method specifically comprises the following steps: dissolving 1.05g of citric acid and 335 mu L of ethylenediamine in 10mL of deionized water, transferring the mixed solution into a reaction kettle, and reacting at 220 ℃ for 12 hours to obtain the nitrogen-doped carbon dots.
In the step (1), the concentration of the pentahydrate bismuth nitrate is 0.02-0.03mol/L, the concentration of the nitrogen-doped carbon dots is 0.125-0.375 g/L, and the volume ratio of ethanol to acetic acid is 3: 1.
The invention has the beneficial effects that:
(1) the method has the advantages of simple and easy operation process, easily obtained raw materials and easy industrial implementation.
(2) The bismuth oxide/nitrogen-doped carbon dot hollow porous microsphere negative electrode material prepared by the method has excellent capacitance performance and good application prospect.
Drawings
Fig. 1 is an X-ray diffraction (XRD) pattern of the bismuth oxide/nitrogen-doped carbon dot hollow porous microsphere anode material prepared in example 1 of the present invention.
Fig. 2 is a Scanning Electron Microscope (SEM) photograph (10 μm scale) of the bismuth oxide/nitrogen-doped carbon dot hollow porous microsphere negative electrode material prepared in example 1 of the present invention.
Fig. 3 is a Scanning Electron Microscope (SEM) photograph (scale 1 μm) of the bismuth oxide/nitrogen-doped carbon dot hollow porous microsphere negative electrode material prepared in example 1 of the present invention.
Fig. 4 is an energy spectrum analysis (EDS) of the bismuth oxide/nitrogen-doped carbon dot hollow porous microsphere anode material prepared in example 1 of the present invention.
Fig. 5 is a charge-discharge curve of the bismuth oxide/nitrogen-doped carbon dot hollow porous microsphere negative electrode material prepared in example 1 in a 3M KOH electrolyte test.
The specific implementation mode is as follows:
embodiments of the present invention will be described in detail below with reference to the drawings, but the scope of the present invention is not limited to these embodiments.
Example 1:
dissolving 1.05g of citric acid and 335 mu L of ethylenediamine in 10mL of deionized water, transferring the mixed solution into a reaction kettle, and reacting at 220 ℃ for 12 hours to obtain the nitrogen-doped carbon dots.
Ultrasonically dispersing 0.5mmol of bismuth nitrate pentahydrate and 5mg of nitrogen-doped carbon quantum dots in 15mL of ethanol and 5mL of acetic acid, and then transferring the mixed system into a reaction kettle to react for 20 hours at 180 ℃. And after cooling, washing with deionized water and ethanol, drying to obtain a precursor, heating to 400 ℃ at a heating rate of 2 ℃/min in an Ar atmosphere, and keeping for 3h to obtain a final sample.
FIG. 1 is an XRD pattern of the composite material, and it can be seen that bismuth oxide in the composite material corresponds to tetragonal system Bi2O3(PDF78-1793) and monoclinic Bi2O3(PDF 71-2274)。
Fig. 2 and 3 are SEM images of the bismuth oxide/nitrogen-doped carbon dot composite material, and it can be clearly seen that the composite material has a hollow porous structure.
Fig. 4 is an EDS plot of the composite material, and it can be seen that the composite material is composed of C, N, O, Bi elements, indicating that the nitrogen-doped carbon dots were successfully composited with bismuth oxide.
FIG. 5 is a charge-discharge curve of the composite material in 3M KOH electrolyte, using a mercury/mercury oxide electrode as a reference electrode for testing. When the voltage range is between-1 and 0V, the charge and discharge curves are 15A/g, 10A/g, 5A/g, 2A/g and 1A/g from left to right in sequence, the composite material shows excellent capacitance performance, and the specific capacitance is up to 1046F/g at 1A/g.
Example 2:
ultrasonically dispersing 0.4mmol of bismuth nitrate pentahydrate and 5mg of nitrogen-doped carbon quantum dots in 15mL of ethanol and 5mL of acetic acid, and then transferring the mixed system into a reaction kettle to react for 20 hours at 180 ℃. And after cooling, washing with deionized water and ethanol, drying to obtain a precursor, heating to 400 ℃ at a heating rate of 2 ℃/min in an Ar atmosphere, and keeping for 3h to obtain a final sample.
Example 3:
ultrasonically dispersing 0.6mmol of bismuth nitrate pentahydrate and 5mg of nitrogen-doped carbon quantum dots in 15mL of ethanol and 5mL of acetic acid, and then transferring the mixed system into a reaction kettle to react for 20 hours at 180 ℃. And after cooling, washing with deionized water and ethanol, drying to obtain a precursor, heating to 400 ℃ at a heating rate of 2 ℃/min in an Ar atmosphere, and keeping for 3h to obtain a final sample.
Example 4:
ultrasonically dispersing 0.5mmol of bismuth nitrate pentahydrate and 2.5mg of nitrogen-doped carbon quantum dots in 15mL of ethanol and 5mL of acetic acid, and then transferring the mixed system into a reaction kettle to react for 20 hours at 180 ℃. And after cooling, washing with deionized water and ethanol, drying to obtain a precursor, heating to 400 ℃ at a heating rate of 2 ℃/min in an Ar atmosphere, and keeping for 3h to obtain a final sample.
Example 5:
ultrasonically dispersing 0.5mmol of bismuth nitrate pentahydrate and 7.5mg of nitrogen-doped carbon quantum dots in 15mL of ethanol and 5mL of acetic acid, and then transferring the mixed system into a reaction kettle to react for 20 hours at 180 ℃. And after cooling, washing with deionized water and ethanol, drying to obtain a precursor, heating to 400 ℃ at a heating rate of 2 ℃/min in an Ar atmosphere, and keeping for 3h to obtain a final sample.
Example 6:
ultrasonically dispersing 0.5mmol of bismuth nitrate pentahydrate and 5mg of nitrogen-doped carbon quantum dots in 15mL of ethanol and 5mL of acetic acid, and then transferring the mixed system into a reaction kettle to react for 20 hours at 170 ℃. And after cooling, washing with deionized water and ethanol, drying to obtain a precursor, heating to 400 ℃ at a heating rate of 2 ℃/min in an Ar atmosphere, and keeping for 3h to obtain a final sample.
Example 7:
ultrasonically dispersing 0.5mmol of bismuth nitrate pentahydrate and 5mg of nitrogen-doped carbon quantum dots in 15mL of ethanol and 5mL of acetic acid, and then transferring the mixed system into a reaction kettle to react for 20 hours at 190 ℃. And after cooling, washing with deionized water and ethanol, drying to obtain a precursor, heating to 400 ℃ at a heating rate of 2 ℃/min in an Ar atmosphere, and keeping for 3h to obtain a final sample.
Example 8:
ultrasonically dispersing 0.5mmol of bismuth nitrate pentahydrate and 5mg of nitrogen-doped carbon quantum dots in 15mL of ethanol and 5mL of acetic acid, and then transferring the mixed system into a reaction kettle to react for 24 hours at 180 ℃. And after cooling, washing with deionized water and ethanol, drying to obtain a precursor, heating to 400 ℃ at a heating rate of 2 ℃/min in an Ar atmosphere, and keeping for 3h to obtain a final sample.
Example 9:
ultrasonically dispersing 0.5mmol of bismuth nitrate pentahydrate and 5mg of nitrogen-doped carbon quantum dots in 15mL of ethanol and 5mL of acetic acid, and then transferring the mixed system into a reaction kettle to react for 20 hours at 180 ℃. And after cooling, washing with deionized water and ethanol, drying to obtain a precursor, heating to 500 ℃ at a heating rate of 2 ℃/min in an Ar atmosphere, and keeping for 4h to obtain a final sample.

Claims (3)

1. A preparation method of a bismuth oxide/nitrogen-doped carbon dot hollow porous microsphere negative electrode material is characterized by comprising the following steps of: the method comprises the following steps:
(1) dispersing bismuth nitrate pentahydrate and nitrogen-doped carbon dots in a mixed solution of ethanol and acetic acid; wherein the concentration of the pentahydrate bismuth nitrate is 0.02-0.03mol/L, the concentration of the nitrogen-doped carbon dots is 0.125-0.375 g/L, and the volume ratio of ethanol to acetic acid is 3: 1;
(2) putting the solution obtained in the step (1) into a reaction kettle, and heating and reacting for 20-24 hours at 170-190 ℃; and after the reaction is finished, cooling, separating, washing and drying the solid sample to obtain a precursor, heating the precursor to the calcination temperature of 400-500 ℃ in an inert atmosphere, and calcining for 3-4 h to obtain the bismuth oxide/nitrogen-doped carbon-point supercapacitor negative electrode material.
2. The preparation method of the bismuth oxide/nitrogen-doped carbon dot hollow porous microsphere anode material as claimed in claim 1, wherein the preparation method comprises the following steps: in the step (1), the nitrogen-doped carbon dots are prepared by using citric acid and ethylenediamine as raw materials and adopting a hydrothermal method; the method specifically comprises the following steps: dissolving 1.05g of citric acid and 335 mu L of ethylenediamine in 10mL of deionized water, transferring the mixed solution into a reaction kettle, and reacting at 220 ℃ for 12 hours to obtain the nitrogen-doped carbon dots.
3. The preparation method of the bismuth oxide/nitrogen-doped carbon dot hollow porous microsphere anode material as claimed in claim 1, wherein the preparation method comprises the following steps: the temperature rise rate of the temperature programming is 2 ℃/min.
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