CN113363086B - MnO for supercapacitor 2 Nanobelt/nitrogen-doped graphene aerogel composite material and preparation method and application thereof - Google Patents
MnO for supercapacitor 2 Nanobelt/nitrogen-doped graphene aerogel composite material and preparation method and application thereof Download PDFInfo
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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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Abstract
The invention provides MnO for a super capacitor 2 Provided 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 KMnO 4 Adding MnSO 4 Reduction of KMnO adsorbed on nitrogen-doped graphene aerogel 4 To obtain MnO with high surface unit cell exposure ratio 2 A nanoribbon. MnO 2 The strong chemical bonding between the nanobelts and the nitrogen-doped graphene aerogel improves the structural stability and the cycling stability; but also is beneficial to the rapid transmission of electrons and improves the electrochemical performance. MnO with protected carbon skeleton 2 The 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 MnO for a super capacitor 2 A 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.
MnO 2 Has 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, mnO 2 Poor 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 MnO 2 The 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 MnO 2 Pseudo-capacitance and double layer capacitance of graphene, mnO 2 The/graphene composite material is often used for a supercapacitor.
At present, mnO for super capacitor 2 The preparation method of the graphene composite material mainly comprises the following steps: 1. by KMnO 4 Reduction by the reducing carbon skeleton of graphene to MnO 2 Preparing a composite material, for example: chinese patent documents CN111463020A, CN110534355A, CN109390161A, CN110581028A, CN109192529A, CN108172408A and the like all use a reducing carbon skeleton of graphene to convert KMnO 4 Reduction to MnO 2 To obtain MnO 2 The 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 MnO 2 The nano material and graphene are directly mixed to prepare the composite material, for example: chinese patent document CN110739159A, CN111653435A, CN111732095A, CN107026026A, CN109065367A, CN107887179A, CN108455573A, but MnO in the above method 2 The graphene is lack of strong chemical bonding with graphene, 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: chinese patent document CN111710534A, CN110970234A, CN107316752A et al use electrochemical deposition to remove MnO 2 Deposited on graphene materials, but the electrodeposition method cannot ensure MnO 2 The 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 developed 2 The 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 supercapacitor 2 Provided are a nanobelt/nitrogen-doped graphene aerogel composite material and a preparation method and application thereof. The method of the invention firstly adopts KMnO 4 Uniformly 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 KMnO 4 Formation of MnO 2 Thereby obtaining MnO 2 The 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, chemical bonding MnO is uniformly grown in horizontal orientation due to large-area C = C area induction 2 Nanobelt of MnO 2 The 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 endowed 2 More closely approaching the theoretical advantage of capacitance.
The technical scheme of the invention is as follows:
MnO for supercapacitor 2 Nanobelt/nitrogen-doped graphene aerogel composite material having MnO therein 2 Nanobelts are uniformly and horizontally grown in situ on a nitrogen-doped graphene aerogel, the MnO 2 Is alpha-MnO 2 Said MnO being 2 The length of the nano-belt is 400-600 nm, the width is 40-50 nm, and the thickness is 8-12 nm.
According to the invention, preferably, mnO is contained in the composite material 2 The loading amount of (B) is 3-10 wt%.
According to the invention, the MnO for supercapacitor 2 The 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 KMnO 4 Adsorbing in solution, washing to obtain KMnO adsorbed 4 The nitrogen-doped graphene aerogel of (a);
(3) Will adsorb KMnO 4 Adding MnSO into the nitrogen-doped graphene aerogel 4 In the solution, carrying out reaction; washing, freezing and drying to obtain MnO 2 Provided is a 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 -1 More 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 -1 The 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 150-200 ℃, and the hydrothermal reaction time is 5-20 h.
According to the present invention, the washing in step (1) is preferably 3 to 10 times washing with 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 500-800 ℃, and the heat treatment time is 3-6 h; the heat treatment atmosphere is Ar gas.
According to the invention, the KMnO in the step (2) 4 The concentration of the solution is 1-5 mg mL -1 More preferably 2 to 3mg mL -1 。
According to the invention, the KMnO in the step (2) 4 KMnO in solution 4 The 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 preferable 4 The concentration of the solution is 3-4 mg mL -1 (ii) a The MnSO 4 MnSO in solution 4 And KMnO 4 KMnO in solution 4 The mass ratio of (A) to (B) is 1.2 to 1.5.
According to the present invention, the reaction temperature in the step (3) is preferably 40 to 90 ℃, and more preferably 60 to 80 ℃; the reaction time is 10 to 30min, and more preferably 14 to 28min.
Preferably, according to the present invention, the washing in step (3) is washing 3 to 10 times with pure water; the freeze drying is carried out for 10 to 24 hours at a temperature of between 60 ℃ below zero and 70 ℃ below zero.
According to the invention, the MnO mentioned above 2 The 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 firstly adopts KMnO 4 In the structure with good conductivity, large specific surface and rich hierarchical poresUniformly performing characteristic chemical adsorption on the three-dimensional nitrogen-doped graphene aerogel by introducing MnSO 4 Reduction of KMnO which has been characteristic of chemisorption on nitrogen-doped graphene aerogel 4 Thereby preparing MnO 2 The 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 bonding 2 The 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 invention 2 The nanobelt/nitrogen-doped graphene aerogel composite material has a large specific surface, a hierarchical pore structure and MnO 2 The 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 invention 2 MnO in nanobelt/nitrogen-doped graphene aerogel composite material 2 Specific capacitance of (2) compared with MnO obtained by the prior art method 2 The nano material is closer to MnO 2 Theoretical specific capacitance.
3. MnO prepared by the invention 2 The 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 1 2 Scanning electron microscope images of the nanobelt/nitrogen-doped graphene aerogel composite material, specifically a low-magnification scanning electron microscope image (a) and a high-magnification scanning electron microscope image (b).
FIG. 2 shows MnO prepared in example 1 2 Atomic force microscopy of nanoribbon/nitrogen doped graphene aerogel composites.
FIG. 3 shows MnO prepared in example 1 2 Thermogravimetric plot of nanoribbon/nitrogen doped graphene aerogel composite.
FIG. 4 shows MnO prepared in example 1 2 An X-ray diffraction pattern of the nanobelt/nitrogen-doped graphene aerogel composite.
FIG. 5 shows MnO prepared in example 1 2 N of nanobelt/nitrogen-doped graphene aerogel composite material 2 Adsorption/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 1 2 An 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 1 2 The 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) 2 Scanning 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 aeogel 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 0.9nm. The rest raw materials are conventional raw materials and are commercial products.
Example 1
MnO for supercapacitor 2 The 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 -1 The dispersion of graphene oxide of (2) was added with 12.5mL of Tris-HCl buffer solution (concentration: 0.1mol L) -1 pH 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 -1 KMnO of 4 Adsorbing in the solution under-0.09 MPa for 60min, washing with pure water until the filtrate is colorless to obtain KMnO 4 The nitrogen-doped graphene aerogel of (a).
(3) Adsorbing KMnO obtained in the step (2) 4 50mL of nitrogen-doped graphene aerogel with the concentration of 3.8mg mL is added -1 MnSO of 4 Reacting in the solution at 80 ℃ for 28min; washing with pure water for 5 times, and freeze-drying at-65 deg.C for 12 hr to obtain MnO 2 The nanobelt/nitrogen-doped graphene aerogel composite material is marked as MNRs/NGA.
MnO obtained in this example 2 The 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, mnO 2 The nanobelts are uniformly distributed on the nitrogen-doped graphene aerogel and MnO is 2 The nanobelts have a length of 500nm and a width of 50nm, and an atomic force microscope image thereof is shown in FIG. 2, from which it can be seen that MnO is 2 The thickness of the nanobelt was 11.1nm.
MnO obtained in this example 2 The thermogravimetric graph of the nanobelt/nitrogen-doped graphene aerogel composite material is shown in fig. 3, and as can be seen from fig. 3, the obtained MnO is 2 MnO in nanobelt/nitrogen-doped graphene aerogel composite material 2 The loading was 5.3wt%; the X-ray diffraction pattern is shown in FIG. 4. As can be seen from FIG. 4, the obtainedMnO 2 The crystal form of the nanobelt is alpha-MnO 2 (ii) a And MnO in the obtained composite material 2 The surface unit cell exposure ratio of the nanoribbons was 35.6%.
MnO obtained in this example 2 N of nanobelt/nitrogen-doped graphene aerogel composite 2 The absorption/desorption isotherms and pore size distributions are shown in FIG. 5, and from FIG. 5, mnO can be seen 2 The specific surface area of the nanobelt/nitrogen-doped graphene aerogel composite material is 777.5m 2 g -1 And has a hierarchical pore structure.
MnO obtained in this example 2 The 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. 6 2 The 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 example 2 The method comprises the following steps of carrying out electrochemical performance test on the nanobelt/nitrogen-doped graphene aerogel composite material, and carrying out performance test on an assembled solid-state Asymmetric Supercapacitor (ASC), wherein the method comprises the following specific steps:
preparing an electrode:
MnO prepared in this example 2 Mixing the nanobelt/nitrogen-doped graphene aerogel composite material, ketjen black and PVDF according to the mass ratio of 5 2 The coating amount of the nanobelt/nitrogen-doped graphene aerogel composite material is 0.5mg cm -2 And then dried at 60 ℃ for 12h. Compacting the dried electrode slice with oil hydraulic press under 10MPa to obtain MNRs/NGA electrode, and placing the MNRs/NGA electrode into 1mol L -1 Na of (2) 2 SO 4 And 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 -1 Na of (2) 2 SO 4 Using solution as electrolyte and working electrochemicallyThe electrochemical properties of CV, GCD and the like of the MNRs/NGA composite material are researched. The scanning rate of CV is 2.5-100.0 mV s -1 The 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 Na 2 SO 4 And 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 example 2 The 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 respectively shown in 0.5A g -1 At current density, mnO 2 The specific capacitance of the nanobelt/nitrogen-doped graphene aerogel composite material is 658.1F g -1 The specific capacitance of the nitrogen-doped graphene aerogel material is 619.3F g -1 MnO obtained 2 MnO in nanobelt/nitrogen-doped graphene aerogel composite material 2 The specific capacitance contributed is 1351.4F g MnO2 -1 Near MnO of 2 Theoretical specific capacitance of (1370.0F g) -1 ) (ii) a As can be seen from FIG. 7b, mnO 2 The nano-belt/nitrogen-doped graphene aerogel composite material is prepared in a proportion of 10.0A g -1 After 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 obtained MNRs/NGA// AC ASC specific capacitance variation graph, ragon graph and cycling stability graph are respectively shown in FIG. 8a, FIG. 8b and FIG. 8c, and can be seen from FIG. 8a to be 0.5A g -1 The current density and the corresponding specific capacitance are up to 167.3F g -1 (ii) a As can be seen from FIG. 8b, at 500.0W kg -1 When 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 5.0A g -1 After the current density is cycled for 5000 times, the capacity retention rate is as high as 91.4%.
Example 2
MnO for supercapacitor 2 The 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 21min.
MnO obtained in this example 2 The 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, mnO 2 The nanoribbons were grown uniformly on nitrogen-doped graphene aerogel.
MnO prepared in this example 2 Electrochemical 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, the voltage is 0.5A g -1 Current density, mnO 2 The specific capacitance of the nanobelt/nitrogen-doped graphene aerogel composite material is 647.5F g -1 . MNRs/NGA// AC ASC is 0.5A g -1 The specific capacitance corresponding to the current density is 158.2F g -1 . At 500.0W kg -1 At a specific power of 87.9W-h kg, the corresponding specific energy -1 。
Example 3
MnO for supercapacitor 2 The 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 14min.
MnO obtained in this example 2 The scanning electron micrograph of the nanobelt/nitrogen-doped graphene aerogel composite material is shown in FIG. 9b, and from FIG. 9b, mnO can be seen 2 The nanoribbons were grown uniformly on nitrogen-doped graphene aerogel.
MnO prepared in this example 2 Electrochemical 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, the voltage is 0.5A g -1 Current density, mnO 2 Ratio of nanoribbon/nitrogen-doped graphene aerogel compositeThe capacitance is 643.1F g -1 . MNRs/NGA// AC ASC is 0.5A g -1 The specific capacitance corresponding to the current density is 155.3F g -1 . At 500.0W kg -1 When the specific power is high, the corresponding specific energy is 86.3W h kg -1 。
Example 4
MnO for supercapacitor 2 The 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 example 2 The 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 present 2 The nanoribbons were grown uniformly on nitrogen-doped graphene aerogel.
MnO prepared in this example 2 Electrochemical 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 -1 Current density, mnO 2 The specific capacitance of the nanobelt/nitrogen-doped graphene aerogel composite material is 652.3F g -1 . MNRs/NGA// AC ASC is 0.5A g -1 The specific capacitance corresponding to the current density is 161.8F g -1 . At 500.0W kg -1 When the specific power is higher than the reference value, the corresponding specific energy is 89.9W h kg -1 。
Example 5
MnO for supercapacitor 2 The 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 21min.
MnO obtained in this example 2 The scanning electron micrograph of the nanobelt/nitrogen-doped graphene aerogel composite is shown in fig. 9d, and as can be seen from fig. 9d, mnO is present 2 The nanoribbons were grown uniformly on nitrogen-doped graphene aerogel.
MnO prepared in this example 2 Electrochemical performance of nanobelt/nitrogen-doped graphene aerogel composite materialThe test was performed and the assembled solid ASC was subjected to performance testing as described in example 1.
In a three-electrode system, the voltage is 0.5A g -1 Current density, mnO 2 The specific capacitance of the nanobelt/nitrogen-doped graphene aerogel composite material is 646.5F g -1 . MNRs/NGA// AC ASC is 0.5A g -1 The specific capacitance corresponding to the current density is 157.6F g -1 . At 500.0W kg -1 When the specific power is high, the corresponding specific energy is 87.6W h kg -1 。
Example 6
MnO for supercapacitor 2 The 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 14min.
MnO obtained in this example 2 The 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 present 2 The nanoribbons were grown uniformly on nitrogen-doped graphene aerogel.
MnO prepared in this example 2 Electrochemical 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, the voltage is 0.5A g -1 Current density, mnO 2 The specific capacitance of the nanobelt/nitrogen-doped graphene aerogel composite material is 642.7F g -1 . MNRs/NGA// AC ASC is 0.5A g -1 The specific capacitance corresponding to the current density is 154.5F g -1 . At 500.0W kg -1 When the specific power of (2) is higher, the corresponding specific energy is 85.8W h kg -1 。
Comparative example 1
MnO for supercapacitor 2 The preparation method of the nanobelt/nitrogen-doped graphene aerogel composite material is as described in example 1, except that: mnSO in step (3) 4 The concentration of the solution was 4.8mg mL -1 。
MnO prepared by this comparative example 2 Nanobelt/nitrogen-doped graphene aerogel compositeThe materials were tested for electrochemical performance and assembled into solid state ASCs for performance testing as described in example 1.
In a three-electrode system, the voltage is 0.5A g -1 Current density, mnO 2 The specific capacitance of the nanobelt/nitrogen-doped graphene aerogel composite material is 637.5F g -1 . MNRs/NGA// AC ASC is 0.5A g -1 The specific capacitance corresponding to the current density is 137.8F g -1 . At 500.0W kg -1 When the specific power is higher than the reference value, the corresponding specific energy is 76.6W h kg -1 . In this comparative example, mnSO 4 Too high a concentration of (i.e. MnSO) 4 With KMnO 4 Too large a proportion of (B) to obtain MnO 2 Electrochemical performance of nanobelt/nitrogen-doped graphene aerogel composite material and MnO prepared by using same 2 The 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 supercapacitor 2 The preparation method of the nanobelt/nitrogen-doped graphene aerogel composite material is as described in example 1, except that: mnSO in step (3) 4 The concentration of the solution was 2.1mg mL -1 。
MnO prepared in this comparative example 2 Electrochemical 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, the voltage is 0.5A g -1 Current density, mnO 2 The specific capacitance of the nanobelt/nitrogen-doped graphene aerogel composite material is 631.2F g -1 . MNRs/NGA// AC ASC is 0.5A g -1 The specific capacitance corresponding to the current density is 132.5F g -1 . At 500.0W kg -1 When the specific power is higher than the reference power, the corresponding specific energy is 73.6W h kg -1 . In this comparative example, mnSO 4 Too low a concentration of (i.e. MnSO) 4 With KMnO 4 Too small a proportion of (B) to obtain MnO 2 Electrochemical performance of nanobelt/nitrogen-doped graphene aerogel composite material and MnO prepared by using same 2 Solid-state prepared from nanobelt/nitrogen-doped graphene aerogel composite materialThe performance of the ASCs is lower than the examples of the present invention.
Comparative example 3
MnO for supercapacitor 2 The 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 adsorbed 4 The nitrogen-doped graphene aerogel of (a) was added to 50mL of water.
MnO prepared by this comparative example 2 Electrochemical performance tests were performed on the nanobelt/nitrogen-doped graphene aerogel composite, and the nanobelt/nitrogen-doped graphene aerogel composite was assembled into a solid-state ASC for performance tests, according to the method described in example 1.
In a three-electrode system, the voltage is 0.5A g -1 Current density, mnO 2 The specific capacitance of the nanobelt/nitrogen-doped graphene aerogel composite material is 629.0F g -1 . MNRs/NGA// AC ASC is 0.5A g -1 The specific capacitance corresponding to the current density is 113.4F g -1 . At 500.0W kg -1 At a specific power of 63.0W-hr kg -1 . In this comparative example, mnSO was not added 4 MnO obtained 2 Electrochemical performance of nanobelt/nitrogen-doped graphene aerogel composite material and MnO prepared by using same 2 The 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 (9)
1. MnO for supercapacitor 2 The preparation method of the nanobelt/nitrogen-doped graphene aerogel composite material is characterized in that MnO in the composite material 2 The nanobelts are uniformly and horizontally grown in situ on the nitrogen-doped graphene aerogel, and the MnO is 2 Is alpha-MnO 2 The MnO being 2 The length of the nanobelt is 400 to 600nm, the width of the nanobelt is 40 to 50nm, and the thickness of the nanobelt is 8 to 12 nm;
the preparation method 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 KMnO 4 Adsorbing in solution, washing to obtain KMnO adsorbed 4 The nitrogen-doped graphene aerogel of (a); the KMnO 4 The concentration of the solution is 2 to 5mg mL -1 (ii) a The KMnO 4 KMnO in solution 4 The mass ratio of the nitrogen-doped graphene aerogel to the nitrogen-doped graphene aerogel is 4 to 5;
(3) Will adsorb KMnO 4 Adding MnSO into the nitrogen-doped graphene aerogel 4 In the solution, carrying out reaction; washing, freezing and drying to obtain MnO 2 A nanoribbon/nitrogen-doped graphene aerogel composite; the MnSO 4 The concentration of the solution is 3 to 4mg mL -1 (ii) a The MnSO 4 MnSO in solution 4 And KMnO 4 KMnO in solution 4 The mass ratio of (A) to (B) is 1.2 to 1.5; the reaction temperature is 40 to 90 ℃; the reaction time is 10 to 30 min.
2. The MnO of claim 1 2 The 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 -1 (ii) a The concentration of the Tris-HCl buffer solution is 0.1mol L -1 The pH is 8.5; the volume ratio of the Tris-HCl buffer solution to the graphene oxide dispersion liquid is 1 to 9.
3. The MnO of claim 2 2 The 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 5-7 mg mL -1 。
4. The MnO of claim 1 2 The 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; the mass ratio of the nitrogen source to the graphene oxide is 1 to 1.
5. The MnO of claim 1 2 The preparation method of the nanobelt/nitrogen-doped graphene aerogel composite material is characterized in that the nitrogen source in the step (1) is dopamine.
6. The MnO of claim 1 2 The 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 to 200 ℃, and the hydrothermal reaction time is 5 to 20 hours; the washing is carried out for 3 to 10 times by using pure water; the freeze drying is carried out at the temperature of-60 to-70 ℃ for 48 to 84 hours; the heat treatment temperature is 500-800 ℃, the heat treatment time is 3-6 h, and the heat treatment atmosphere is Ar gas.
7. The MnO of claim 1 2 The 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 to 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 1 2 The preparation method of the nanobelt/nitrogen-doped graphene aerogel composite material is characterized in that the reaction temperature in the step (3) is 60 to 80 ℃; the reaction time is 14 to 28min;
the washing is carried out for 3 to 10 times by using pure water; the freeze drying is carried out at the temperature of-60 to-70 ℃ for 10 to 24 hours.
9. MnO obtainable by the process of claim 1 2 The application of the nanobelt/nitrogen-doped graphene aerogel composite material is used for a super capacitor anode material.
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| CN110739159A (en) * | 2019-10-14 | 2020-01-31 | 北京化工大学 | Preparation method of nanowire-shaped manganese dioxide/graphene aerogel composite materials for super capacitor |
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