CN110739159B - Preparation method of nanowire-shaped manganese dioxide/graphene aerogel composite material for supercapacitor - Google Patents
Preparation method of nanowire-shaped manganese dioxide/graphene aerogel composite material for supercapacitor Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 81
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 68
- 239000002131 composite material Substances 0.000 title claims abstract description 57
- 239000004964 aerogel Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000002070 nanowire Substances 0.000 claims abstract description 49
- 229910006648 β-MnO2 Inorganic materials 0.000 claims abstract description 21
- 239000000243 solution Substances 0.000 claims description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 20
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 20
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 16
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 229910003174 MnOOH Inorganic materials 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910002804 graphite Inorganic materials 0.000 claims description 11
- 239000010439 graphite Substances 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 238000010335 hydrothermal treatment Methods 0.000 claims description 9
- 239000012286 potassium permanganate Substances 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 7
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- 238000003760 magnetic stirring Methods 0.000 claims description 5
- 239000011572 manganese Substances 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000002135 nanosheet Substances 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 3
- 238000004108 freeze drying Methods 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims 2
- 235000010344 sodium nitrate Nutrition 0.000 claims 1
- 239000004317 sodium nitrate Substances 0.000 claims 1
- 239000003990 capacitor Substances 0.000 abstract description 6
- 238000004146 energy storage Methods 0.000 abstract description 4
- 239000002064 nanoplatelet Substances 0.000 abstract description 3
- 239000011232 storage material Substances 0.000 abstract description 2
- 239000003792 electrolyte Substances 0.000 description 10
- 239000007772 electrode material Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 3
- 238000000840 electrochemical analysis Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
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- 239000006230 acetylene black Substances 0.000 description 2
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
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Abstract
A preparation method of a nanowire-shaped manganese dioxide/graphene aerogel composite material for a super capacitor belongs to the field of energy storage materials of super capacitors. The nano linear manganese dioxide is beta-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 beta-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
Technical Field
The invention relates to the field of super capacitor energy storage materials, in particular to a preparation method of a nanowire-shaped manganese dioxide/graphene aerogel composite material.
Background
Nowadays, due to exhaustion of traditional fossil fuels and aggravation of environmental pollution, development of clean and sustainable energy is very important, so that development of renewable energy sources such as solar energy, wind energy and the like is greatly improved. However, these energy sources are limited by natural conditions, and are characterized by discontinuities and instabilities. Therefore, the development of stable and efficient energy storage systems is becoming more and more urgent and important. As a new energy storage device, supercapacitors have many significant characteristics, such as high power density, fast charge/discharge rates and long cycle life, with wide applications in electronics, hybrid electric vehicles and backup power systems. However, the low energy density of supercapacitors has greatly limited their further applications. Therefore, the development of electrode materials having a large specific surface area and high conductivity has been a research hotspot and difficulty.
The manganese dioxide nano material has the advantages of high theoretical specific volume, rich sources, environmental friendliness, low cost and the like, and is widely applied to electrode materials of super capacitors. However, manganese dioxide has poor conductivity, resulting in low capacitance performance, which limits its further application in the field of supercapacitors. Therefore, the manganese dioxide and the graphene with good conductivity are compounded, and the specific surface area of the composite material is increased through the synergistic effect of the manganese dioxide and the graphene, so that the transmission efficiency of electrons and electrolyte ions is improved, and the specific capacitance performance of the composite material is improved.
Disclosure of Invention
The invention aims to provide a nano linear manganese dioxide/graphene aerogel composite material and a preparation method thereof. Wherein the nanowire-shaped manganese dioxide is beta-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 beta-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.
The invention provides a method for making beta-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:
under the condition of magnetic stirring, respectively dissolving a certain amount of Sodium Dodecyl Benzene Sulfonate (SDBS) and polyvinylpyrrolidone (PVP, preferably 10000) in deionized water until all the sodium dodecyl benzene sulfonate and the polyvinylpyrrolidone are dissolved, and marking as solution 1;
② respectively measuring Mn (NO) with a certain volume by using 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;
thirdly, 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;
fourthly, weighing a certain amount of the MnOOH powder, uniformly dispersing the MnOOH powder in a NaOH (with the preferred concentration of 2mol/L) solution, and recording the solution as a solution 3;
fifthly, 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 beta-MnO2And (3) nano-wire powder.
Further preferred are Sodium Dodecylbenzenesulfonate (SDBS), polyvinylpyrrolidone (PVP, 10000), and Mn (NO)3)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
Firstly, graphite, (NaNO) is used3) 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 adding a certain amount of beta-MnO prepared in the step (1)2Dispersing the nanowires into the graphene oxide dispersion liquid, stirring for 4-8 hours, and then carrying out ultrasonic treatment on the mixed liquid for 1-2 hours; beta-MnO2The mass ratio range of the nano wire to the graphite oxide is 0.5: 1-2: 1;
thirdly, transferring the mixed liquid after ultrasonic treatment into a hydrothermal kettle, and carrying out hydrothermal treatment for 12 hours at the temperature of 100-150 ℃ to obtain nano linear manganese dioxide/graphene hydrogel;
and fourthly, putting the hydrogel into a freeze dryer, and freeze-drying for 24 hours to obtain the nano linear manganese dioxide/graphene aerogel composite material.
The nano linear manganese dioxide/graphene aerogel composite material is characterized by comprising beta-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 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 invention adopts a hydrothermal method to make beta-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.
The invention prepares beta-MnO of composite material2The mass ratio range of the nano wire to the graphite oxide is 0.5: 1-2: 1, wherein the mass ratio is 1: the performance of the composite material is better at 1 hour, the specific capacity of the composite material under the current density of 1A/g reaches 204F/g and exceeds that of pure beta-MnO2The nanowire is 123F/g, which is improved by 80F/g。
Drawings
FIG. 1 is a beta-MnO of example 12Electron microscope photographs of nanowires, graphene and nanowire-like manganese dioxide/graphene aerogel composites;
FIG. 2 is a beta-MnO of example 12XRD spectrograms of the nanowire, graphene and nanowire-shaped manganese dioxide/graphene aerogel composite material;
FIG. 3 is a beta-MnO of example 12XPS spectra of nanowires, graphene and nanowire-like manganese dioxide/graphene aerogel composite materials;
FIG. 4 is a beta-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 is a beta-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 is a beta-MnO of examples 1 and 22Nanowire, graphene, and nanowire-like manganese dioxide/graphene aerogel composite impedance (EIS) curves.
Detailed Description
The present invention will be further illustrated 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
Mono, beta-MnO2Process for preparing nanowires
Under the condition of magnetic stirring, respectively dissolving 0.769g of SDBS (sodium dodecyl benzene sulfonate) and 0.4446g of PVP (polyvinylpyrrolidone with molecular weight of 10000) in a beaker filled with 70ml of deionized water until all the SDBS and the PVP are dissolved, and marking as solution 1;
② measuring 2.4ml Mn (NO) by burette3)2(50 wt%) solution and 4ml KMnO4(0.2mol/L) solution is respectively dripped into the solution 1, magnetic stirring is continuously carried out during the process, and the solution is dripped completelyContinuing stirring for 30min after finishing to obtain a mixed solution 2;
thirdly, transferring all the mixed solution 2 into a 100ml hydrothermal kettle, carrying out hydrothermal treatment in a drying oven at 180 ℃ for 5h, taking out the hydrothermal kettle, naturally cooling to room temperature, washing for multiple times by using deionized water, washing to remove SDBS and PVP, washing by using absolute ethyl alcohol, removing residual water, and drying at 60 ℃ for 6h to obtain MnOOH precursor powder;
weighing 50mg of MnOOH powder, and uniformly dispersing the MnOOH powder in 60ml of NaOH (2mol/L) solution to be recorded as solution 3;
fifthly, transferring the solution 3 into a 100ml hydrothermal kettle, carrying out hydrothermal treatment at 180 ℃ for 24h, taking out the hydrothermal kettle, naturally cooling to room temperature, washing for multiple times with deionized water to be neutral, then washing with absolute ethyl alcohol to remove residual deionized water, drying at 60 ℃ for 6h, and then calcining at 300 ℃ for 2h to obtain beta-MnO2And (3) nano-wire powder.
Second, preparation process of nano linear manganese dioxide/graphene aerogel composite material
Firstly, NaNO is used3、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 a certain amount of beta-MnO prepared in the first step2Dispersing 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;
thirdly, transferring the mixed liquid after ultrasonic treatment into a 25ml hydrothermal kettle, and carrying out hydrothermal treatment for 12h at 120 ℃ to obtain nano linear manganese dioxide/graphene hydrogel;
and fourthly, putting the hydrogel into a freeze dryer, and freeze-drying for 24 hours 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. First, a working electrode is preparedMixing 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 a 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 a nanowire-like manganese dioxide/graphene aerogel composite of example 1; a is the scanning electron microscope picture of the composite material, and beta-MnO can be observed2The nanowires are vertically grown on the graphene nanoplatelets very uniformly. b is a transmission electron micrograph, from which it can be seen that beta-MnO2The 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-like manganese dioxide/graphene aerogel composite of example 1; by XRD pattern analysis of the composite material, we found that beta-MnO2Nanowires and graphene are well composited together.
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 the close association of the two was further demonstrated by spectroscopic analysis of the composite, consistent with previous analysis.
FIGS. 4, 5 and 6 are respectively the beta-MnO of example 12A current density and voltage (CV) curve of the nanowire, graphene and nanowire-shaped manganese dioxide/graphene aerogel composite material at a scanning rate of 10mV/s, a constant current charge and discharge (GCD) curve and an impedance (EIS) curve at a current density of 1A/g; as can be seen from the CV curve, the area of the composite curve surrounded by the composite material is obviously larger than that of pure phase beta-MnO2And graphene, by GCD curveCalculated to obtain beta-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 beta-MnO2123F/g for nanowires, and 83F/g for graphene, and it can be seen from the EIS curves that the conductivity of the nanomaterial after recombination is improved, which is consistent with the results of the invention.
Example 2 (. beta. -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)
Changing beta-MnO2The mass ratio of the nanowires to the graphene is 2:1, and other conditions are the same as in example 1.
② the beta-MnO obtained from step 12The composite material with the mass ratio of the nanowires to the graphene being 2:1 is used as an active material to manufacture a working electrode, a saturated calomel electrode is used as a reference electrode, and a graphite rod is used as a counter electrode. The electrochemical performance test is carried out on an electrochemical workstation, and the beta-MnO can be found2The specific capacitance still increases after the nanowire and graphene are compounded.
Thirdly, the working electrode made of the composite material is subjected to electrochemical test, the specific volume reaches 170F/g and is still superior to pure phase beta-MnO2123F/g for nanowires, and 83F/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, and 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 a feasible scheme is provided for uniform vertical growth of linear nano materials on graphene sheets.
Claims (2)
1. A preparation method of a nano linear manganese dioxide/graphene aerogel composite material is characterized in that the nano linear manganese dioxide/graphene aerogel composite material is beta-MnO2The nano wires are uniformly and vertically grown on the graphene nano-sheets, and the nano wires are strip-shaped flaky nano-wires; the dimension of the nanowire in the width direction is 10nm, and the length of the nanowire is 2-5 mu m;
the method comprises the following steps:
（1）、β-MnO2process for preparing nanowires
The method specifically comprises the following steps:
firstly, respectively dissolving a certain amount of Sodium Dodecyl Benzene Sulfonate (SDBS) and polyvinylpyrrolidone (PVP) in deionized water under the condition of magnetic stirring until the SDBS and the PVP are completely dissolved, and marking as solution 1;
② respectively measuring 50wt percent Mn (NO) with a certain volume by using a dropper3)2Solution and 0.2mol/L KMnO4Respectively dripping the solution into the solution 1, continuously stirring by magnetic force during the dripping, and continuously stirring for 30min after all the dripping is finished to obtain a mixed solution 2;
fourthly, weighing a certain amount of the MnOOH precursor powder, and uniformly dispersing the MnOOH precursor powder in a NaOH solution with the concentration of 2mol/L to be recorded as a solution 3;
fifthly, 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 beta-MnO2A nanowire;
sodium Dodecyl Benzene Sulfonate (SDBS), polyvinylpyrrolidone (PVP), Mn (NO)3)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 precursor powder and the NaOH solution is that 10-20ml of NaOH solution corresponds to each 10mg of MnOOH precursor powder;
(2) preparation process of nanowire-shaped manganese dioxide/graphene aerogel composite material
Firstly, graphite and sodium nitrate (NaNO) are used3) 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 adding a certain amount of beta-MnO prepared in the step (1)2Dispersing the nanowires into the graphene oxide dispersion liquid, stirring for 4-8 hours, and then carrying out ultrasonic treatment on the mixed liquid for 1-2 hours; beta-MnO2The mass ratio range of the nano wire to the graphite oxide is 0.5: 1-2: 1;
thirdly, transferring the mixed liquid after ultrasonic treatment into a hydrothermal kettle, and carrying out hydrothermal treatment for 12 hours at the temperature of 100-150 ℃ to obtain nano linear manganese dioxide/graphene hydrogel;
and fourthly, putting the hydrogel into a freeze dryer, and freeze-drying for 24 hours to obtain the nano linear manganese dioxide/graphene aerogel composite material.
2. Use of the nanowire-like manganese dioxide/graphene aerogel composite obtained by the method of claim 1 as a supercapacitor electrode.
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