CN110739159A - Preparation method of nanowire-shaped manganese dioxide/graphene aerogel composite materials for super capacitor - Google Patents

Preparation method of nanowire-shaped manganese dioxide/graphene aerogel composite materials for super capacitor Download PDF

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CN110739159A
CN110739159A CN201910977550.1A CN201910977550A CN110739159A CN 110739159 A CN110739159 A CN 110739159A CN 201910977550 A CN201910977550 A CN 201910977550A CN 110739159 A CN110739159 A CN 110739159A
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刘晓林
刘艳生
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Beijing University of Chemical Technology
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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
    • H01G11/30—Electrodes characterised by their material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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    • C01B32/19—Preparation by exfoliation
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    • C01G45/02—Oxides; Hydroxides
    • H—ELECTRICITY
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    • 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
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    • 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
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • 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
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    • 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

preparation method of nano linear manganese dioxide/graphene aerogel composite material for super capacitor, and the field of super capacitor energy storage materials, wherein the nano linear manganese dioxide is β -MnO2The nano-wires are formed of a plurality of nano-wires,the nano wire is a long strip sheet nano wire, the size of the nano wire in the width direction is about 10nm, the length of the nano wire is 2-5 mu m, and the β -MnO is2The nanowires are uniformly and vertically grown on the graphene nanoplatelets, thereby forming the composite material. The composite material integrates the advantages of high Faraday capacitance of manganese dioxide and good conductivity of graphene, and the electrochemical performance of the composite material is improved.

Description

Preparation method of nanowire-shaped manganese dioxide/graphene aerogel composite materials for super capacitor
Technical Field
The invention relates to the field of super capacitor energy storage materials, in particular to a preparation method of nano linear manganese dioxide/graphene aerogel composite materials, which enables manganese dioxide nanowires to vertically grow on graphene and improves electrochemical performance by utilizing the synergistic effect between the manganese dioxide nanowires and the graphene.
Background
The development of renewable energy sources such as solar and wind energy has been greatly advanced today due to the exhaustion of conventional fossil fuels and the aggravation of environmental pollution, and the development of clean and sustainable energy sources is important, however, these energy sources are limited by natural conditions and have characteristics of discontinuity and instability, and therefore, the development of stable and efficient energy storage systems has become more and more urgent and important.
However, the manganese dioxide has poor conductivity, so that the capacitance performance of the manganese dioxide is not high, and the application of the manganese dioxide in the advanced step in the field of supercapacitors is limited.
Disclosure of Invention
The invention aims to provide nano linear manganese dioxide/graphene aerogel composite materials and a preparation method thereof, wherein the nano linear manganese dioxide is β -MnO2The nanowire is a long strip-shaped sheet nanowire, the dimension of the nanowire in the width direction is about 10nm, the length of the nanowire is 2-5 mu m, and the β -MnO is2The nanowires are uniformly and vertically grown on the graphene nanoplatelets, thereby forming the composite material. The composite material integrates high Faraday capacitance of manganese dioxide and good conductivity of grapheneIts advantages are high electrochemical performance.
The invention provides messenger β -MnO2The preparation method for the nano-wires to uniformly and vertically grow on the graphene nano-sheets comprises the following specific implementation steps:
(1)、β-MnO2process for preparing nanowires
The method particularly preferably comprises the following steps:
① under magnetic stirring, dissolving amounts of Sodium Dodecyl Benzene Sulfonate (SDBS) and polyvinylpyrrolidone (PVP, preferably 10000) in deionized water until all dissolved, and marking as solution 1;
② dropping Mn (NO) with fixed volume by a dropper3)2(50 wt%) solution and KMnO4(0.2mol/L) solution is respectively dripped into the solution 1, magnetic stirring is continuously carried out in the period, and stirring is continuously carried out for 30min after all dripping is finished, so as to obtain a mixed solution 2;
③, transferring all the mixed solution 2 into a hydrothermal kettle, carrying out hydrothermal treatment at 180 ℃ for 4-6 h, taking out the hydrothermal kettle, naturally cooling to room temperature, washing with deionized water for multiple times, washing to remove SDBS and PVP, washing with absolute ethyl alcohol, removing residual water, and drying to obtain MnOOH precursor powder;
④ weighing parts of MnOOH powder, uniformly dispersing in NaOH (preferably 2mol/L) solution to obtain solution 3;
⑤ transferring the solution 3 into a hydrothermal kettle, carrying out hydrothermal treatment at 180 ℃ for 24-48 h, taking out the hydrothermal kettle, naturally cooling to room temperature, washing with deionized water for multiple times until the solution is neutral, then washing with absolute ethyl alcohol, removing residual water, drying, and calcining at 300 ℃ for 2h to obtain β -MnO2And (3) nano-wire powder.
sodium dodecylbenzene sulfonate (SDBS), polyvinylpyrrolidone (PVP, 10000), and Mn (NO) are preferable3)2、KMnO4The mass ratio of (1.5-2): (0.7-1.2): (0.3-0.8): (0.2-0.7). The mass percentage concentration of the Sodium Dodecyl Benzene Sulfonate (SDBS) in the solution 1 is 0.5-5%.
The dosage relation of the MnOOH powder and the NaOH solution is 10-20ml of NaOH solution per 10mg of MnOOH powder.
(2) Preparation process of nanowire-shaped manganese dioxide/graphene aerogel composite material
① first, graphite, (NaNO)3) Potassium permanganate (KMnO)4) Concentrated sulfuric acid (H)2SO4) Hydrogen peroxide (H)2O2) Preparing graphite oxide by using hydrochloric acid (HCl) as a raw material and an improved Hummers method, and then obtaining a uniform graphene oxide dispersion liquid through ultrasonic treatment;
② quantification of amount of β -MnO prepared in step (1)2Dispersing the nanowires into the graphene oxide dispersion liquid, stirring for 4-8 h, and then carrying out ultrasonic treatment on the mixed liquid for 1-2 h, β -MnO2The mass ratio range of the nano wire to the graphite oxide is 0.5: 1-2: 1;
③ transferring the mixed solution after ultrasonic treatment to a hydrothermal kettle, and carrying out hydrothermal treatment for 12h at 100-150 ℃ to obtain nano linear manganese dioxide/graphene hydrogel;
④, putting the hydrogel into a freeze dryer, and freeze-drying for 24h to obtain the nano linear manganese dioxide/graphene aerogel composite material.
The nano linear manganese dioxide/graphene aerogel composite material is characterized by comprising β -MnO2The nano-wires grow uniformly and vertically on the graphene nano-sheets to form the composite material with a stable structure.
The nano linear manganese dioxide/graphene aerogel composite material prepared by the method can be used for a supercapacitor electrode, and the electrochemical performance of the supercapacitor electrode is improved.
The method for performing electrochemical test by using the composite material as the supercapacitor electrode comprises the following steps: the test adopts a three-electrode test system and uses 1mol/L NaSO4The solution is electrolyte, and the test voltage window is 0-0.8V. Firstly, preparing a working electrode, mixing the upper composite material with acetylene black and PVDF according to a mass ratio of 80:15:5, uniformly mixing with ethanol, adding a proper amount of NMP, uniformly coating the mixture on foamed nickel, drying in vacuum at 70 ℃ for 12h, and finally tabletting to obtain the working electrode, wherein a saturated calomel electrode is used as a reference electrodeAnd the graphite rod is a counter electrode. Before testing, the working electrode is soaked in the electrolyte for 2 hours, so that the electrode material is fully contacted with the electrolyte.
The invention adopts a hydrothermal method for making β -MnO for the first time2The nano wires uniformly and vertically grow on the graphene nanosheets, and the nano linear manganese dioxide/graphene aerogel composite material with a stable structure is obtained. The composite material prepared by the preparation method has larger specific surface area and good conductivity, and when the composite material is used as a super capacitor electrode, the electrolyte ion transmission rate and the electron transfer rate in the charge and discharge process are increased, so that the electrochemical performance of the composite material is improved.
β -MnO for preparing composite material by using said invention2The mass ratio of the nano wire to the graphite oxide is 0.5: 1-2: 1, wherein the composite material has excellent performance when the mass ratio is 1:1, the specific capacity of the composite material under the current density of 1A/g reaches 204F/g and exceeds pure β -MnO2The nanowire is 123F/g, which is improved by 80F/g.
Drawings
FIG. 1 shows β -MnO of example 12Electron microscope photographs of nanowires, graphene and nanowire-like manganese dioxide/graphene aerogel composites;
FIG. 2 shows β -MnO of example 12XRD spectrograms of the nanowire, graphene and nanowire-shaped manganese dioxide/graphene aerogel composite material;
FIG. 3 shows β -MnO of example 12XPS spectra of nanowires, graphene and nanowire-like manganese dioxide/graphene aerogel composite materials;
FIG. 4 shows β -MnO of examples 1 and 22The current density and voltage (CV) curves of the nanowire, graphene and nanowire-shaped manganese dioxide/graphene aerogel composite material at a scanning rate of 10 mV/S;
FIG. 5 shows β -MnO of examples 1 and 22A constant current charge and discharge (GCD) curve of the nanowire, graphene and nanowire-shaped manganese dioxide/graphene aerogel composite material at a current density of 1A/g;
FIG. 6 shows β -MnO of examples 1 and 22Nanowire, graphene, and nanowire-likeManganese oxide/graphene aerogel composite impedance (EIS) curves.
Detailed Description
The present invention will be further illustrated at with reference to the following examples, but the present invention is not limited to the following examples.
Example 1 (composite amount 1:1)
Preparation method
, β -MnO2Process for preparing nanowires
① under magnetic stirring, 0.769g of SDBS (sodium dodecyl benzene sulfonate) and 0.4446g of PVP (polyvinylpyrrolidone, molecular weight 10000) are respectively dissolved in a beaker filled with 70ml of deionized water until all are dissolved, and the solution is marked as solution 1;
② measuring 2.4ml Mn (NO) with dropper3)2(50 wt%) solution and 4ml KMnO4(0.2mol/L) solution is respectively dripped into the solution 1, magnetic stirring is continuously carried out in the period, and stirring is continuously carried out for 30min after all dripping is finished, so as to obtain a mixed solution 2;
③ transferring all the mixed solution 2 into a 100ml hydrothermal kettle, carrying out hydrothermal treatment in an oven at 180 ℃ for 5h, taking out the hydrothermal kettle, naturally cooling to room temperature, washing with deionized water for multiple times, washing to remove SDBS and PVP, washing with absolute ethyl alcohol to remove residual water, and drying at 60 ℃ for 6h to obtain MnOOH precursor powder;
④ weighing 50mg of the MnOOH powder, and uniformly dispersing the MnOOH powder in 60ml of NaOH (2mol/L) solution to obtain solution 3;
⑤ transferring the solution 3 to 100ml hydrothermal kettle, carrying out hydrothermal treatment at 180 deg.C for 24h, taking out the hydrothermal kettle, naturally cooling to room temperature, washing with deionized water for several times to neutrality, washing with anhydrous ethanol to remove residual deionized water, drying at 60 deg.C for 6h, and calcining at 300 deg.C for 2h to obtain β -MnO2And (3) nano-wire powder.
Second, preparation process of nano linear manganese dioxide/graphene aerogel composite material
① first, with NaNO3、KMnO4Concentrated H2SO4,H2O2Preparing graphite oxide by adopting an improved Hummers method as a raw material, and then obtaining 0.2 graphene oxide dispersion liquid by an ultrasonic method;
② quantification of amount of β -MnO prepared in step 2Dispersing the nanowires into the graphene oxide dispersion liquid, stirring for 6 hours (the mass ratio of the nanowires to the graphene oxide dispersion liquid is 1:1), and then carrying out ultrasonic treatment on the mixed liquid for 1.5 hours;
③ transferring the mixed solution after ultrasonic treatment to a 25ml hydrothermal kettle, and carrying out hydrothermal treatment for 12h at 120 ℃ to obtain nano linear manganese dioxide/graphene hydrogel;
④, putting the hydrogel into a freeze dryer, and freeze-drying for 24h to obtain the nano linear manganese dioxide/graphene aerogel composite material.
The electrochemical test method of the supercapacitor electrode comprises the following steps: using a three-electrode test system with 1mol/L NaSO4The solution is electrolyte, and the test voltage window is 0-0.8V. Firstly, preparing a working electrode, mixing the upper composite material with acetylene black and PVDF according to a mass ratio of 80:15:5, uniformly mixing with ethanol, adding a proper amount of NMP, uniformly coating the mixture on foamed nickel, drying in vacuum at 70 ℃ for 12h, and finally tabletting to obtain the working electrode, wherein a saturated calomel electrode is used as a reference electrode, and a graphite rod is used as a counter electrode. Before testing, the working electrode is soaked in the electrolyte for 2 hours, so that the electrode material is fully contacted with the electrolyte.
The composite material is used as a super capacitor material, and when the current density is 1A/g, the specific capacitance reaches 204F/g, and when the current density is amplified to 5A/g, the specific capacitance still reaches 159.4F/g.
Data documentation and analysis:
FIG. 1 is an electron micrograph of the nanowire manganese dioxide/graphene aerogel composite material of example 1, a is a scanning electron micrograph of the composite material, and β -MnO can be observed2The nanowires are very uniformly and vertically grown on the graphene nanoplatelets, b is a transmission electron micrograph, from which β -MnO can be seen2The nanowire and the graphene are closely compounded, and the structure is favorable for the transmission of electrolyte ions and the transfer of electrons, so that the specific capacitance is improved.
FIG. 2 is an XRD pattern of the nanowire-shaped manganese dioxide/graphene aerogel composite material in example 1. by analyzing the XRD pattern of the composite material, we found β -MnO2Nanowires and graphene are well complexed at .
Fig. 3 is an XPS spectrum of manganese dioxide/graphene aerogel composite of example 1, a is the total peak, b is the Mn2p peak, and c is the O1s peak. close association of the two is demonstrated by further , which is consistent with previous analysis at .
FIGS. 4, 5 and 6 are 1 β -MnO in EXAMPLE 12The area of a composite curve surrounded by the composite material is obviously larger than that of pure phase β -MnO according to the CV curve2And graphene, calculated from the GCD curve, β -MnO2When the mass ratio of the nano wire to the graphene is 1:1, the specific volume is 204F/g and is larger than that of pure phase β -MnO2123F/g for the nanowire and 83F/g for the graphene, and it can be seen from the EIS curve that the conductivity of the nanomaterial after recombination is improved, which is consistent with the result of .
Example 2(β -MnO in Material)2The mass ratio of the nanowire to the graphene was changed, and the other conditions were the same as in example 1)
① Change β -MnO2The mass ratio of the nanowires to the graphene is 2:1, and other conditions are the same as in example 1.
② β -MnO obtained in step 12The composite material with the mass ratio of the nano wire to the graphene being 2:1 is used as an active material to be manufactured into a working electrode, a saturated calomel electrode is used as a reference electrode, a graphite rod is used as a counter electrode, and electrochemical performance tests are carried out on an electrochemical workstation, so that β -MnO can be found2The specific capacitance still increases after the nanowire and graphene are compounded.
③ electrochemical test of the working electrode made of the composite material, the specific volume reaches 170F/g, still better than that of pure phase β -MnO2123F/g of nanowires, and stone83F/g for graphene.
The results of example 1 and example 2 show that the prepared nano linear manganese dioxide/graphene aerogel composite material is used as an electrode material of a supercapacitor, the transmission rate of electrolyte ions and the transfer rate of electrons are increased through the synergistic effect between the nano linear manganese dioxide/graphene aerogel composite material and the electrode material, so that the electrochemical performance of the electrode material is improved, the composite method is simple to operate, and feasible schemes are provided for uniform vertical growth of linear nano materials on graphene sheets.

Claims (6)

1, nanometer linear manganese dioxide/graphene aerogel composite materials, characterized in that, β -MnO2The nano wires are uniformly and vertically grown on the graphene nano-sheets, and the nano wires are strip-shaped flaky nano-wires.
2. The nanowire-shaped manganese dioxide/graphene aerogel composites as claimed in claim 1, wherein the nanowires have a dimension of about 10nm in width direction and a length of 2-5 μm.
3. The nanofilament manganese dioxide/graphene aerogel composites of claim 1, wherein β -MnO2The mass ratio range of the nano wire to the graphite oxide is 0.5: 1-2: 1.
4. the nanofilament manganese dioxide/graphene aerogel composites of claim 1, wherein β -MnO2The mass ratio of the nano wire to the graphite oxide is 1: 1.
5. a method of preparing the nanofilament manganese dioxide/graphene aerogel composite of any of claims 1-4, comprising the steps of:
(1)、β-MnO2process for preparing nanowires
The method particularly preferably comprises the following steps:
① under magnetic stirring, dissolving amounts of Sodium Dodecyl Benzene Sulfonate (SDBS) and polyvinylpyrrolidone (PVP, preferably 10000) in deionized water until all dissolved, and marking as solution 1;
② dropping Mn (NO) with fixed volume by a dropper3)2(50 wt%) solution and KMnO4(0.2mol/L) solution is respectively dripped into the solution 1, magnetic stirring is continuously carried out in the period, and stirring is continuously carried out for 30min after all dripping is finished, so as to obtain a mixed solution 2;
③, transferring all the mixed solution 2 into a hydrothermal kettle, carrying out hydrothermal treatment at 180 ℃ for 4-6 h, taking out the hydrothermal kettle, naturally cooling to room temperature, washing with deionized water for multiple times, washing to remove SDBS and PVP, washing with absolute ethyl alcohol, removing residual water, and drying to obtain MnOOH precursor powder;
④ weighing parts of MnOOH powder, uniformly dispersing in NaOH (preferably 2mol/L) solution to obtain solution 3;
⑤ transferring the solution 3 into a hydrothermal kettle, carrying out hydrothermal treatment at 180 ℃ for 24-48 h, taking out the hydrothermal kettle, naturally cooling to room temperature, washing with deionized water for multiple times until the solution is neutral, then washing with absolute ethyl alcohol, removing residual water, drying, and calcining at 300 ℃ for 2h to obtain β -MnO2Nano-wire powder;
sodium dodecylbenzene sulfonate (SDBS), polyvinylpyrrolidone (PVP, 10000), and Mn (NO) are preferable3)2、KMnO4The mass ratio of (1.5-2): (0.7-1.2): (0.3-0.8): (0.2-0.7); the mass percent concentration of the Sodium Dodecyl Benzene Sulfonate (SDBS) in the solution 1 is 0.5-5%;
the dosage relation of the MnOOH powder and the NaOH solution is that 10-20ml of NaOH solution corresponds to each 10mg of MnOOH powder;
(2) preparation process of nanowire-shaped manganese dioxide/graphene aerogel composite material
① first, graphite, (NaNO)3) Potassium permanganate (KMnO)4) Concentrated sulfuric acid (H)2SO4) Hydrogen peroxide (H)2O2) And hydrochloric acid (HCl) is used as a raw material, an improved Hummers method is adopted to prepare graphite oxide, and then uniform graphene oxide dispersion is obtained through ultrasonic treatmentLiquid;
② quantification of amount of β -MnO prepared in step (1)2Dispersing the nanowires into the graphene oxide dispersion liquid, stirring for 4-8 h, and then carrying out ultrasonic treatment on the mixed liquid for 1-2 h, β -MnO2The mass ratio range of the nano wire to the graphite oxide is 0.5: 1-2: 1;
③ transferring the mixed solution after ultrasonic treatment to a hydrothermal kettle, and carrying out hydrothermal treatment for 12h at 100-150 ℃ to obtain nano linear manganese dioxide/graphene hydrogel;
④, putting the hydrogel into a freeze dryer, and freeze-drying for 24h to obtain the nano linear manganese dioxide/graphene aerogel composite material.
6. Use of the nanofilamented manganese dioxide/graphene aerogel composite of any of claims 1-4 as a supercapacitor electrode.
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CN113363086A (en) * 2021-05-31 2021-09-07 山东大学 MnO for supercapacitor2Nanobelt/nitrogen-doped graphene aerogel composite material and preparation method and application thereof

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