CN113363086A - MnO for supercapacitor2Nanobelt/nitrogen-doped graphene aerogel composite material and preparation method and application thereof - Google Patents
MnO for supercapacitor2Nanobelt/nitrogen-doped graphene aerogel composite material and preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 194
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 161
- 239000004964 aerogel Substances 0.000 title claims abstract description 127
- 239000002131 composite material Substances 0.000 title claims abstract description 109
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000002127 nanobelt Substances 0.000 claims abstract description 91
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 15
- 239000003990 capacitor Substances 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 claims abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
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- 238000006243 chemical reaction Methods 0.000 claims description 11
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 8
- 238000004108 freeze drying Methods 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 claims description 7
- 239000007853 buffer solution Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229960003638 dopamine Drugs 0.000 claims description 5
- 238000001179 sorption measurement Methods 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 3
- 238000011065 in-situ storage Methods 0.000 claims description 3
- 229910003144 α-MnO2 Inorganic materials 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 229920001661 Chitosan Polymers 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 239000010405 anode material Substances 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
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- 238000007710 freezing Methods 0.000 claims description 2
- 230000008014 freezing Effects 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 22
- 239000002074 nanoribbon Substances 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 7
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- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 230000001351 cycling effect Effects 0.000 abstract description 4
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract 1
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- 238000012360 testing method Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000463 material Substances 0.000 description 8
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- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 4
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- 125000004122 cyclic group Chemical group 0.000 description 3
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- 230000014759 maintenance of location Effects 0.000 description 3
- 229920001690 polydopamine Polymers 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
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- 229910018648 Mn—N Inorganic materials 0.000 description 1
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- 229910021607 Silver chloride Inorganic materials 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
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- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
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- 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
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Abstract
The invention provides MnO for a super capacitor2Provided are a nanobelt/nitrogen-doped graphene aerogel composite material and a preparation method and application thereof. The method prepares the nitrogen-doped graphene aerogel with a large specific surface and a hierarchical pore structure through hydrothermal reaction, and then adsorbs KMnO4Adding MnSO4Reduction of KMnO adsorbed on nitrogen-doped graphene aerogel4To obtain MnO with high surface unit cell exposure ratio2A nanoribbon. MnO2Nanobelt and nitrogen-doped graphene gasStrong chemical bonding between gels improves structural stability and cycling stability; but also is beneficial to the rapid transmission of electrons and improves the electrochemical performance. MnO with protected carbon skeleton2The nanobelt/nitrogen-doped graphene aerogel composite material has excellent supercapacitor performances such as specific capacitance, specific energy, specific power and cycling stability.
Description
Technical Field
The invention relates to a super capacitorMnO for device2A nanobelt/nitrogen-doped graphene aerogel composite material and a preparation method and application thereof belong to the technical field of super capacitor energy storage materials.
Background
As a novel energy storage device, the super capacitor has the advantages of high energy density, long cycle life, short charging time and the like, and has wide application prospects in the fields of consumer electronics, new energy automobiles, motion control, smart power grids, industrial energy conservation and emission reduction, military weaponry and the like.
MnO2Has large theoretical specific capacitance (1370.0F g)-1) The electrochemical performance is excellent, the cost is low, and the like, and the method is widely applied to electrode materials of super capacitors. However, MnO2Poor conductivity, resulting in low capacitive performance, limiting its further applications in the field of supercapacitors. The graphene has the advantages of good conductivity and large theoretical specific surface, and the nitrogen doping can provide p electrons for a pi electron system of the graphene, so that the pseudo-capacitance performance of the graphene is endowed, and particularly, the graphene aerogel also has the structural advantage of rich pore structure and is beneficial to mass transfer. Mixing graphene with MnO2The composite material is compounded, so that the conductivity of the composite material is improved, the specific surface area of the composite material is increased, and the transmission efficiency of electrons and electrolyte ions is improved. Thus, based on MnO2Pseudo-capacitance and double layer capacitance of graphene, MnO2The/graphene composite material is often used for a supercapacitor.
Currently, MnO for supercapacitors2The preparation method of the graphene composite material mainly comprises the following steps: 1. by KMnO4Reduction by the reducing carbon skeleton of graphene to MnO2Preparing a composite material, for example: chinese patent documents CN111463020A, CN110534355A, CN109390161A, CN110581028A, CN109192529A, CN108172408A, and the like all use a reduced carbon skeleton of graphene to convert KMnO into KMnO4Reduction to MnO2To obtain MnO2The method is characterized in that the integrity of a graphene carbon skeleton structure is damaged in the reduction process, so that the conductivity and the structural stability of the composite material are damaged; 2. passing MnO2Nano materialMixing with graphene directly to prepare composite materials, for example: chinese patent documents CN110739159A, CN111653435A, CN111732095A, CN107026026A, CN109065367A, CN107887179A and CN108455573A, but MnO is used in the above method2Strong chemical bonding with graphene is lacked, so that the advantages of the graphene cannot be fully exerted, and the obtained composite material has poor conductivity and structural stability; 3. the composite material is prepared by an electrochemical deposition method, for example: the MnO is formed by electrochemical deposition method in Chinese patent documents CN111710534A, CN110970234A, CN107316752A and the like2Deposited on graphene materials, but the electrodeposition method cannot ensure MnO2The nano material has uniform dispersion, and an electro-deposition device is needed, so that the popularization of the preparation method is restricted.
Therefore, a new MnO was developed2The preparation method of the graphene composite material has important significance in obtaining the supercapacitor electrode material with high conductivity, large specific capacitance and high cycle stability.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides MnO for a supercapacitor2Provided are a nanobelt/nitrogen-doped graphene aerogel composite material and a preparation method and application thereof. The method of the invention firstly adopts KMnO4Uniformly performing characteristic chemical adsorption on three-dimensional nitrogen-doped graphene aerogel with good conductivity, large specific surface and rich hierarchical pore structure, and introducing reducing agent to replace reductive carbon skeleton of graphene for reduction of KMnO4Formation of MnO2Thereby obtaining MnO2The nanobelt/nitrogen-doped graphene aerogel composite material. The method disclosed by the invention not only protects the structural integrity of the graphene carbon skeleton, but also protects the good conductivity of the graphene carbon skeleton; simultaneously, horizontally-oriented uniform-growth chemical bonding MnO is induced by large-area C ═ C region2Nanobelt of MnO2The surface crystal cell is fully exposed, and the structural stability and the performance stability of the surface crystal cell are improved, so that the performance of the supercapacitor is effectively improved, and MnO is endowed2More closely approaching the theoretical advantage of capacitance.
The technical scheme of the invention is as follows:
MnO for supercapacitor2Nanobelt/nitrogen-doped graphene aerogel composite material having MnO therein2The nanobelts are uniformly and horizontally grown in situ on the nitrogen-doped graphene aerogel, and the MnO is2Is alpha-MnO2Said MnO being2The nanobelt has a length of 400 to 600nm, a width of 40 to 50nm, and a thickness of 8 to 12 nm.
According to the invention, preferably, MnO is contained in the composite material2The loading amount of (A) is 3-10 wt%.
According to the invention, the MnO for supercapacitor2The preparation method of the nanobelt/nitrogen-doped graphene aerogel composite material comprises the following steps:
(1) adding a Tris-HCl buffer solution into the graphene oxide dispersion liquid, then adding a nitrogen source, uniformly mixing, and carrying out hydrothermal reaction; after the reaction is finished, washing, freeze-drying and heat-treating to obtain the nitrogen-doped graphene aerogel;
(2) adding nitrogen-doped graphene aerogel into KMnO4Adsorbing in solution, washing to obtain KMnO adsorbed4The nitrogen-doped graphene aerogel of (a);
(3) will adsorb KMnO4Adding MnSO into the nitrogen-doped graphene aerogel4In the solution, carrying out reaction; washing, freezing and drying to obtain MnO2The nanobelt/nitrogen-doped graphene aerogel composite material.
According to the invention, the concentration of the graphene oxide dispersion liquid in the step (1) is preferably 4-20 mg mL-1More preferably 5 to 7mg mL-1(ii) a The graphene oxide is prepared by an improved Hummers method, and the preparation method is referred to in the literature (Xie, B.; Zhang, Y.; Zhang, R.Pure nitro-processed graphene aerogel with rich micropores high ORR performances. materials Science and Engineering: B2019, 242, 1-5).
According to the invention, the concentration of the Tris-HCl buffer solution in the step (1) is 0.1mol L-1The pH is 8.5; the volume ratio of the Tris-HCl buffer solution to the graphene oxide dispersion liquid is 1-9: 1.
According to the invention, the nitrogen source in the step (1) is one or more of dopamine, melamine, chitosan, urea and ammonia water, and is further preferably dopamine; the mass ratio of the nitrogen source to the graphene oxide is 1: 1-3.
According to the invention, the hydrothermal reaction temperature in the step (1) is preferably 150-200 ℃, and the hydrothermal reaction time is preferably 5-20 h.
According to the invention, the washing in the step (1) is preferably 3 to 10 times by using pure water.
According to the invention, the freeze drying in the step (1) is preferably carried out at-60 to-70 ℃ for 48 to 84 hours.
According to the invention, the heat treatment temperature in the step (1) is preferably 500-800 ℃, and the heat treatment time is preferably 3-6 h; the heat treatment atmosphere is Ar gas.
According to the invention, the KMnO in the step (2)4The concentration of the solution is 1-5 mg mL-1More preferably 2 to 3mg mL-1。
According to the invention, the KMnO in the step (2)4KMnO in solution4The mass ratio of the nitrogen-doped graphene aerogel to the nitrogen-doped graphene aerogel is 4-5: 1.
According to the invention, the adsorption in the step (2) is preferably carried out for 40-80 min under the vacuum condition of-0.08 to-0.09 MPa.
According to the invention, the washing in step (2) is preferably carried out using pure water until the filtrate is colorless.
According to the invention, the MnSO in the step (3) is preferable4The concentration of the solution is 3-4 mg mL-1(ii) a The MnSO4MnSO in solution4And KMnO4KMnO in solution4The mass ratio of (A) to (B) is 1.2-1.5: 1.
According to the invention, the reaction temperature in the step (3) is preferably 40-90 ℃, and more preferably 60-80 ℃; the reaction time is 10 to 30min, and more preferably 14 to 28 min.
Preferably, the washing in the step (3) is washing 3-10 times by using pure water; the freeze drying is carried out at the temperature of-60 to-70 ℃ for 10 to 24 hours.
According to the invention, the MnO mentioned above2The application of the nanobelt/nitrogen-doped graphene aerogel composite material is used for a super capacitor anode material.
The invention has the following technical characteristics and beneficial effects:
1. the method of the invention firstly adopts KMnO4Uniformly performing characteristic chemical adsorption on three-dimensional nitrogen-doped graphene aerogel with good conductivity, large specific surface and rich hierarchical pore structure, and introducing MnSO4Reduction of KMnO that has been specifically chemisorbed onto nitrogen-doped graphene aerogel4Thereby preparing MnO2The nanobelt/nitrogen-doped graphene aerogel composite material. The method disclosed by the invention not only protects the structural integrity of the nitrogen-doped graphene aerogel carbon skeleton, but also protects the good conductivity of the nitrogen-doped graphene aerogel carbon skeleton; and in-situ uniformly growing horizontally oriented MnO on the surface of the nitrogen-doped graphene aerogel through chemical bonding2The nanobelt improves the structural stability and the electrochemical performance stability of the composite material, is favorable for the rapid transmission of electrons, and improves the electrochemical performance.
2. MnO prepared by the invention2The nanobelt/nitrogen-doped graphene aerogel composite material has a large specific surface, a hierarchical pore structure and MnO2The high surface unit cell exposure ratio is beneficial to the full exposure of active sites, the electrochemical performance is improved, and the excellent performance of the super capacitor is shown; MnO prepared by the invention2MnO in nanobelt/nitrogen-doped graphene aerogel composite material2Specific capacitance of (2) compared with MnO obtained by the prior art method2The nano material is closer to MnO2Theoretical specific capacitance.
3. MnO prepared by the invention2The nanobelt/nitrogen-doped graphene aerogel composite material is used for a super capacitor, and the prepared super capacitor has high specific capacitance, high specific energy, high specific power and good cycle stability; the preparation method is simple and suitable for large-scale production.
Drawings
FIG. 1 shows MnO prepared in example 12Nanoribbon/nitrogen dopingA scanning electron microscope image of the hybrid graphene aerogel composite material, specifically a scanning electron microscope image (a) with low magnification and a scanning electron microscope image (b) with high magnification.
FIG. 2 shows MnO prepared in example 12Atomic force microscopy of nanoribbon/nitrogen doped graphene aerogel composites.
FIG. 3 shows MnO prepared in example 12Thermogravimetric plot of nanoribbon/nitrogen doped graphene aerogel composite.
FIG. 4 shows MnO prepared in example 12An X-ray diffraction pattern of the nanobelt/nitrogen-doped graphene aerogel composite.
FIG. 5 shows MnO prepared in example 12N of nanobelt/nitrogen-doped graphene aerogel composite material2Adsorption/desorption isotherms and pore size distribution maps, wherein the lower right hand insert is the pore size distribution map.
FIG. 6 shows MnO prepared in example 12An X-ray photoelectron spectroscopy (XPS) diagram of the nanobelt/nitrogen-doped graphene aerogel composite material, specifically an N1s XPS spectrum (a), an O1 s XPS spectrum (b) and an Mn 2p XPS spectrum (c).
FIG. 7 shows MnO prepared in example 12The specific capacitance of the nanobelt/nitrogen-doped graphene aerogel composite material and the nitrogen-doped graphene aerogel material in a three-electrode system changes with current density according to a graph (a) and a cyclic stability graph (b).
FIG. 8 is a graph of specific capacitance as a function of current density for MNRs/NGA// AC ASC prepared in example 1 (a), a Ragon plot (b) and a cycling stability plot (c).
FIG. 9 shows MnO prepared in example 2(a), example 3(b), example 4(c), example 5(d), and example 6(e)2Scanning electron microscope images of the nanobelt/nitrogen-doped graphene aerogel composite.
Detailed Description
The present invention will be further described with reference to the following examples, but is not limited thereto, in conjunction with the accompanying drawings.
The graphene oxide used in the examples was prepared according to the literature (Xie, B.; Zhang, Y.; Zhang, R.Pure nitro-oriented graphene aerogel with rich micropores optics high ORR performance. materials Science and Engineering: B2019, 242,1-5), and the obtained graphene oxide had a transverse dimension of 0.04 to 0.90 μm and a thickness of 0.7 to 0.9 nm. The rest raw materials are conventional raw materials and are commercial products.
Example 1
MnO for supercapacitor2The preparation method of the nanobelt/nitrogen-doped graphene aerogel composite material comprises the following steps:
(1) to a concentration of 5.3mg mL in 7.5mL-1Adding 12.5mL of Tris-HCl buffer solution (with a concentration of 0.1mol L) into the graphene oxide dispersion liquid-1pH is 8.5), stirring fully and mixing uniformly, then adding 20mg of dopamine, carrying out ultrasonic treatment for 40min, shaking for 10min, mixing uniformly, transferring the obtained mixture to a 50mL high-pressure reaction kettle, and reacting for 12h at 180 ℃; and after the reaction is finished, obtaining polydopamine-reduced graphene oxide hydrogel, washing the polydopamine-reduced graphene oxide hydrogel with pure water for 5 times, freeze-drying the polydopamine-reduced graphene oxide hydrogel for 72 hours at the temperature of-65 ℃, and then performing heat treatment for 3 hours at the temperature of 800 ℃ in an Ar atmosphere to obtain the nitrogen-doped graphene aerogel, which is recorded as NGA.
(2) Adding 30.0mg of nitrogen-doped graphene aerogel obtained in the step (1) into 50mL of nitrogen-doped graphene aerogel with the concentration of 2.6mg mL-1KMnO of4Adsorbing in the solution under-0.09 MPa for 60min, washing with pure water until the filtrate is colorless to obtain a solution with KMnO adsorbed thereon4The nitrogen-doped graphene aerogel of (a).
(3) Adsorbing KMnO obtained in the step (2)450mL of nitrogen-doped graphene aerogel with the concentration of 3.8mg mL is added-1MnSO of4Reacting in the solution at 80 ℃ for 28 min; washing with pure water for 5 times, and freeze-drying at-65 deg.C for 12 hr to obtain MnO2The nanobelt/nitrogen-doped graphene aerogel composite material is marked as MNRs/NGA.
MnO obtained in this example2The scanning electron microscope image of the nanobelt/nitrogen-doped graphene aerogel composite material is shown in fig. 1, and as can be seen from fig. 1, the obtained material is three-dimensional porous aerogel, MnO2The nanobelts are uniformly distributed on the nitrogen-doped graphene aerogel and MnO is2The nanoribbon has a length of 500nm and a width of 50nm, and has atomic forceThe micromirror is illustrated in FIG. 2. As can be seen from FIG. 2, MnO2The thickness of the nanobelt was 11.1 nm.
MnO obtained in this example2The thermogravimetric graph of the nanobelt/nitrogen-doped graphene aerogel composite material is shown in fig. 3, and it can be seen from fig. 3 that MnO is obtained2MnO in nanobelt/nitrogen-doped graphene aerogel composite material2The loading was 5.3 wt%; the X-ray diffraction pattern thereof is shown in FIG. 4, and it can be seen from FIG. 4 that MnO was obtained2The crystal form of the nanobelt is alpha-MnO2(ii) a And MnO in the resulting composite2The surface unit cell exposure ratio of the nanoribbons was 35.6%.
MnO obtained in this example2N of nanobelt/nitrogen-doped graphene aerogel composite material2The absorption/desorption isotherms and pore size distributions are shown in FIG. 5, and from FIG. 5, MnO can be seen2The specific surface area of the nanobelt/nitrogen-doped graphene aerogel composite material is 777.5m2 g-1And has a hierarchical pore structure.
MnO obtained in this example2The X-ray photoelectron spectrum of the nanobelt/nitrogen-doped graphene aerogel composite material is shown in FIG. 6, and MnO can be seen from FIG. 62The nanobelts and the nitrogen-doped graphene aerogel are subjected to strong chemical bonding through Mn-N and Mn-O-C bonds.
MnO prepared in this example2The electrochemical performance test is carried out on the nanobelt/nitrogen-doped graphene aerogel composite material, and the composite material is assembled into a solid Asymmetric Supercapacitor (ASC) for carrying out the performance test, and the specific steps are as follows:
preparing an electrode:
MnO prepared in this example2Mixing the nanobelt/nitrogen-doped graphene aerogel composite material, Ketjen black and PVDF according to the mass ratio of 5:4:1, uniformly grinding, adding NMP, grinding into fine paste, uniformly coating on foamed nickel, wherein the coating area is 1cm multiplied by 1cm, and MnO is added2The coating amount of the nanobelt/nitrogen-doped graphene aerogel composite material is 0.5mg cm-2And then dried at 60 ℃ for 12 h. Compacting the dried electrode plate by an oil press under the pressure of 10MPaObtaining MNRs/NGA electrode, putting the MNRs/NGA electrode into 1mol L-1Na of (2)2SO4And soaking in the electrolyte for 12h to be tested. Activated Carbon (AC) electrodes were prepared in the same manner as MNRs/NGA electrodes.
(II) three-electrode test:
using MNRs/NGA electrode as positive electrode, Pt sheet as counter electrode, Ag/AgCl as reference electrode and 1mol L-1Na of (2)2SO4The solution is used as electrolyte, and electrochemical properties of the MNRs/NGA composite material, such as CV, GCD and the like, are researched by utilizing an electrochemical workstation. The scanning rate of CV is 2.5-100.0 mV s-1The current density of GCD is 0.5-20.0A g-1。
(III) assembling the solid ASC:
MNRs/NGA electrode and AC electrode are placed in Na2SO4And fully soaking in PVA gel electrolyte, assembling, curing at room temperature, and packaging to obtain MNRs/NGA// AC ASC.
And the electrochemical performance of the nitrogen-doped graphene aerogel prepared in this example was tested by the same method.
MnO prepared in this example2The specific capacitance change graph and the cyclic stability graph of the nanobelt/nitrogen-doped graphene aerogel composite material and the nitrogen-doped graphene aerogel material in the three-electrode system are respectively shown in fig. 7a and 7b, and as can be seen from fig. 7a, the specific capacitance change graph and the cyclic stability graph are 0.5A g-1At current density, MnO2The specific capacitance of the nanobelt/nitrogen-doped graphene aerogel composite material is 658.1F g-1The specific capacitance of the nitrogen-doped graphene aerogel material is 619.3F g-1MnO obtained2MnO in nanobelt/nitrogen-doped graphene aerogel composite material2The specific capacitance of the contribution is 1351.4F gMnO2 -1Near MnO of2Theoretical specific capacitance (1370.0F g)-1) (ii) a As can be seen from FIG. 7b, MnO2The nano-belt/nitrogen-doped graphene aerogel composite material is 10.0A g-1After 5000 cycles of current density, the capacitance retention rate is 93.5%, which is superior to that of the nitrogen-doped graphene aerogel material (the capacitance retention rate is 83.8%).
The specific capacitance of the prepared MNRs/NGA// AC ASC is dependent on the currentThe density profile, the Ragon profile and the cycling stability profile are shown in FIG. 8a, FIG. 8b and FIG. 8c, respectively, and it can be seen from FIG. 8a that the value is 0.5A g-1Current density, corresponding to a specific capacitance of up to 167.3F g-1(ii) a As can be seen from FIG. 8b, at 500.0W kg-1When the specific power is used, the corresponding specific energy is up to 92.9W h kg-1(ii) a As can be seen in FIG. 8c, the MNRs/NGA// AC ASC is at 5.0A g-1After the current density is cycled for 5000 times, the capacity retention rate is as high as 91.4%.
Example 2
MnO for supercapacitor2The preparation method of the nanobelt/nitrogen-doped graphene aerogel composite material is as described in example 1, except that: the reaction time in step (3) was 21 min.
MnO obtained in this example2The scanning electron micrograph of the nanobelt/nitrogen-doped graphene aerogel composite material is shown in fig. 9a, and as can be seen from fig. 9a, MnO2The nanoribbons were grown uniformly on nitrogen-doped graphene aerogel.
MnO prepared in this example2Electrochemical performance testing was performed on the nanobelt/nitrogen-doped graphene aerogel composite, and the composite was assembled into a solid-state ASC for performance testing, according to the method described in example 1.
In a three-electrode system, at 0.5A g-1Current density, MnO2The specific capacitance of the nanobelt/nitrogen-doped graphene aerogel composite material is 647.5F g-1. MNRs/NGA// AC ASC at 0.5A g-1The specific capacitance corresponding to the current density is 158.2F g-1. At 500.0W kg-1When the specific power is high, the corresponding specific energy is 87.9W h kg-1。
Example 3
MnO for supercapacitor2The preparation method of the nanobelt/nitrogen-doped graphene aerogel composite material is as described in example 1, except that: the reaction time in step (3) was 14 min.
MnO obtained in this example2The scanning electron micrograph of the nanobelt/nitrogen-doped graphene aerogel composite material is shown in FIG. 9b, and from FIG. 9b, MnO can be seen2Nanobelt ofUniformly growing on the nitrogen-doped graphene aerogel.
MnO prepared in this example2Electrochemical performance testing was performed on the nanobelt/nitrogen-doped graphene aerogel composite, and the composite was assembled into a solid-state ASC for performance testing, according to the method described in example 1.
In a three-electrode system, at 0.5A g-1Current density, MnO2The specific capacitance of the nanobelt/nitrogen-doped graphene aerogel composite material is 643.1F g-1. MNRs/NGA// AC ASC at 0.5A g-1The specific capacitance corresponding to the current density was 155.3F g-1. At 500.0W kg-1When the specific power is high, the corresponding specific energy is 86.3W h kg-1。
Example 4
MnO for supercapacitor2The preparation method of the nanobelt/nitrogen-doped graphene aerogel composite material is as described in example 1, except that: the reaction temperature in step (3) was 60 ℃.
MnO obtained in this example2The scanning electron micrograph of the nanobelt/nitrogen-doped graphene aerogel composite material is shown in fig. 9c, and from fig. 9c, it can be seen that MnO is present2The nanoribbons were grown uniformly on nitrogen-doped graphene aerogel.
MnO prepared in this example2Electrochemical performance testing was performed on the nanobelt/nitrogen-doped graphene aerogel composite, and the composite was assembled into a solid-state ASC for performance testing, according to the method described in example 1.
In a three-electrode system, at 0.5A g-1Current density, MnO2The specific capacitance of the nanobelt/nitrogen-doped graphene aerogel composite material is 652.3F g-1. MNRs/NGA// AC ASC at 0.5A g-1The specific capacitance corresponding to the current density is 161.8F g-1. At 500.0W kg-1When the specific power is higher than the reference value, the corresponding specific energy is 89.9W h kg-1。
Example 5
MnO for supercapacitor2The preparation method of the nanobelt/nitrogen-doped graphene aerogel composite material is as described in example 1, except that: reaction temperature in step (3)The reaction time was 21min at 60 ℃.
MnO obtained in this example2The scanning electron micrograph of the nanobelt/nitrogen-doped graphene aerogel composite material is shown in fig. 9d, and as can be seen from fig. 9d, MnO2The nanoribbons were grown uniformly on nitrogen-doped graphene aerogel.
MnO prepared in this example2Electrochemical performance testing was performed on the nanobelt/nitrogen-doped graphene aerogel composite, and the composite was assembled into a solid-state ASC for performance testing, according to the method described in example 1.
In a three-electrode system, at 0.5A g-1Current density, MnO2The specific capacitance of the nanobelt/nitrogen-doped graphene aerogel composite material is 646.5F g-1. MNRs/NGA// AC ASC at 0.5A g-1The specific capacitance corresponding to the current density is 157.6F g-1. At 500.0W kg-1When the specific power is high, the corresponding specific energy is 87.6W h kg-1。
Example 6
MnO for supercapacitor2The preparation method of the nanobelt/nitrogen-doped graphene aerogel composite material is as described in example 1, except that: in the step (3), the reaction temperature is 60 ℃, and the reaction time is 14 min.
MnO obtained in this example2The scanning electron micrograph of the nanobelt/nitrogen-doped graphene aerogel composite material is shown in fig. 9e, and as can be seen from fig. 9e, MnO is present2The nanoribbons were grown uniformly on nitrogen-doped graphene aerogel.
MnO prepared in this example2Electrochemical performance testing was performed on the nanobelt/nitrogen-doped graphene aerogel composite, and the composite was assembled into a solid-state ASC for performance testing, according to the method described in example 1.
In a three-electrode system, at 0.5A g-1Current density, MnO2The specific capacitance of the nanobelt/nitrogen-doped graphene aerogel composite material is 642.7F g-1. MNRs/NGA// AC ASC at 0.5A g-1The specific capacitance corresponding to the current density was 154.5F g-1. At 500.0W kg-1At a specific power of (D), the corresponding specific energy is85.8W h kg-1。
Comparative example 1
MnO for supercapacitor2The preparation method of the nanobelt/nitrogen-doped graphene aerogel composite material is as described in example 1, except that: MnSO in step (3)4The concentration of the solution was 4.8mg mL-1。
MnO prepared in this comparative example2Electrochemical performance testing was performed on the nanobelt/nitrogen-doped graphene aerogel composite, and the composite was assembled into a solid-state ASC for performance testing, according to the method described in example 1.
In a three-electrode system, at 0.5A g-1Current density, MnO2The specific capacitance of the nanobelt/nitrogen-doped graphene aerogel composite material is 637.5F g-1. MNRs/NGA// AC ASC at 0.5A g-1The specific capacitance corresponding to the current density is 137.8F g-1. At 500.0W kg-1When the specific power is higher than the reference value, the corresponding specific energy is 76.6W h kg-1. In this comparative example, MnSO4Too high a concentration of (i.e. MnSO)4And KMnO4Too large a proportion of (B) to obtain MnO2Electrochemical performance of nanobelt/nitrogen-doped graphene aerogel composite material and MnO prepared by using same2The performance of the solid ASC prepared from the nanobelt/nitrogen-doped graphene aerogel composite material is lower than that of the solid ASC prepared from the embodiment of the invention.
Comparative example 2
MnO for supercapacitor2The preparation method of the nanobelt/nitrogen-doped graphene aerogel composite material is as described in example 1, except that: MnSO in step (3)4The concentration of the solution was 2.1mg mL-1。
MnO prepared in this comparative example2Electrochemical performance testing was performed on the nanobelt/nitrogen-doped graphene aerogel composite, and the composite was assembled into a solid-state ASC for performance testing, according to the method described in example 1.
In a three-electrode system, at 0.5A g-1Current density, MnO2The specific capacitance of the nanobelt/nitrogen-doped graphene aerogel composite material is 631.2F g-1. MNRs/NGA// AC ASC at 0.5A g-1The specific capacitance corresponding to the current density is 132.5F g-1. At 500.0W kg-1When the specific power is higher than the reference power, the corresponding specific energy is 73.6W h kg-1. In this comparative example, MnSO4Too low a concentration of (i.e. MnSO)4And KMnO4Too small a proportion of (B) to obtain MnO2Electrochemical performance of nanobelt/nitrogen-doped graphene aerogel composite material and MnO prepared by using same2The performance of the solid ASC prepared from the nanobelt/nitrogen-doped graphene aerogel composite material is lower than that of the solid ASC prepared from the embodiment of the invention.
Comparative example 3
MnO for supercapacitor2The preparation method of the nanobelt/nitrogen-doped graphene aerogel composite material is as described in example 1, except that: in the step (3), KMnO is adsorbed4The nitrogen-doped graphene aerogel of (a) was added to 50mL of water.
MnO prepared in this comparative example2Electrochemical performance testing was performed on the nanobelt/nitrogen-doped graphene aerogel composite, and the composite was assembled into a solid-state ASC for performance testing, according to the method described in example 1.
In a three-electrode system, at 0.5A g-1Current density, MnO2The specific capacitance of the nanobelt/nitrogen-doped graphene aerogel composite material is 629.0F g-1. MNRs/NGA// AC ASC at 0.5A g-1The specific capacitance corresponding to the current density is 113.4F g-1. At 500.0W kg-1When the specific power is higher than the reference value, the corresponding specific energy is 63.0W h kg-1. In this comparative example, MnSO was not added4MnO obtained2Electrochemical performance of nanobelt/nitrogen-doped graphene aerogel composite material and MnO prepared by using same2The performance of the solid-state ASC prepared from the nanobelt/nitrogen-doped graphene aerogel composite material is lower than that of the embodiment of the invention, and is lower than that of the comparative examples 1 and 2.
Claims (10)
1. MnO for supercapacitor2The nanobelt/nitrogen-doped graphene aerogel composite material is characterized in that MnO in the composite material2The nanobelts are uniformly and horizontally grown in situ on the nitrogen-doped graphene aerogelMnO2Is alpha-MnO2Said MnO being2The nanobelt has a length of 400 to 600nm, a width of 40 to 50nm, and a thickness of 8 to 12 nm.
2. The MnO for supercapacitor of claim 12The preparation method of the nanobelt/nitrogen-doped graphene aerogel composite material comprises the following steps:
(1) adding a Tris-HCl buffer solution into the graphene oxide dispersion liquid, then adding a nitrogen source, uniformly mixing, and carrying out hydrothermal reaction; after the reaction is finished, washing, freeze-drying and heat-treating to obtain the nitrogen-doped graphene aerogel;
(2) adding nitrogen-doped graphene aerogel into KMnO4Adsorbing in solution, washing to obtain KMnO adsorbed4The nitrogen-doped graphene aerogel of (a);
(3) will adsorb KMnO4Adding MnSO into the nitrogen-doped graphene aerogel4In the solution, carrying out reaction; washing, freezing and drying to obtain MnO2The nanobelt/nitrogen-doped graphene aerogel composite material.
3. The MnO of claim 22The preparation method of the nanobelt/nitrogen-doped graphene aerogel composite material is characterized in that the concentration of the graphene oxide dispersion liquid in the step (1) is 4-20 mg mL-1Preferably 5 to 7mg mL-1(ii) a The concentration of the Tris-HCl buffer solution is 0.1mol L-1The pH is 8.5; the volume ratio of the Tris-HCl buffer solution to the graphene oxide dispersion liquid is 1-9: 1.
4. The MnO of claim 22The preparation method of the nanobelt/nitrogen-doped graphene aerogel composite material is characterized in that the nitrogen source in the step (1) is one or more of dopamine, melamine, chitosan, urea and ammonia water, preferably dopamine; the mass ratio of the nitrogen source to the graphene oxide is 1: 1-3.
5. According to the rightThe MnO of claim 22The preparation method of the nanobelt/nitrogen-doped graphene aerogel composite material is characterized in that the hydrothermal reaction temperature in the step (1) is 150-200 ℃, and the hydrothermal reaction time is 5-20 hours; the washing is carried out for 3-10 times by using pure water; the freeze drying is carried out for 48-84 h at the temperature of-60 to-70 ℃; the heat treatment temperature is 500-800 ℃, the heat treatment time is 3-6 h, and the heat treatment atmosphere is Ar gas.
6. The MnO of claim 22The preparation method of the nanobelt/nitrogen-doped graphene aerogel composite material is characterized in that the KMnO in the step (2)4The concentration of the solution is 1-5 mg mL-1Preferably 2 to 3mg mL-1(ii) a The KMnO4KMnO in solution4The mass ratio of the nitrogen-doped graphene aerogel to the nitrogen-doped graphene aerogel is 4-5: 1.
7. The MnO of claim 22The preparation method of the nanobelt/nitrogen-doped graphene aerogel composite material is characterized in that the adsorption in the step (2) is carried out for 40-80 min under the vacuum-pumping condition of-0.08 to-0.09 MPa; the washing is carried out by using pure water until the filtrate is colorless.
8. The MnO of claim 22The preparation method of the nanobelt/nitrogen-doped graphene aerogel composite material is characterized in that the MnSO in the step (3)4The concentration of the solution is 3-4 mg mL-1(ii) a The MnSO4MnSO in solution4And KMnO4KMnO in solution4The mass ratio of (A) to (B) is 1.2-1.5: 1.
9. The MnO of claim 22The preparation method of the nanobelt/nitrogen-doped graphene aerogel composite material is characterized in that the reaction temperature in the step (3) is 40-90 ℃, and preferably 60-80 ℃; the reaction time is 10-30 min, preferably 14-28 min;
the washing is carried out for 3-10 times by using pure water; the freeze drying is carried out at the temperature of-60 to-70 ℃ for 10 to 24 hours.
10. The MnO of claim 12The application of the nanobelt/nitrogen-doped graphene aerogel composite material is used for a super capacitor anode material.
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