CN114927354B - Nitrogen-doped manganese dioxide/graphene carbon nanotube electrode material and preparation method thereof - Google Patents
Nitrogen-doped manganese dioxide/graphene carbon nanotube electrode material and preparation method 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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- 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 discloses a nitrogen-doped manganese dioxide/graphene carbon nanotube electrode material and a preparation method thereof, and relates to the technical field of electrode materials. The electrode material is prepared by depositing MnO on the surface of nitrogen doped manganese dioxide/graphene carbon nano tube through constant-pressure electrochemical deposition 2 Nano sheet to obtain MnO 2 NGCF electrode material; then MnO is added 2 And (3) placing the NGCF electrode material in ammonia water for nitrogen doping, so as to obtain the nitrogen doped manganese dioxide/graphene carbon nanotube electrode material. The electrode material prepared by the invention has more excellent electrochemical performance.
Description
Technical Field
The invention relates to the technical field of electrode materials, in particular to a nitrogen-doped manganese dioxide/graphene carbon nanotube membrane electrode material and a preparation method thereof.
Background
Transition metal oxides and carbonaceous materials are the two main materials currently used in Supercapacitors (SCs). The related report shows that the electric double layer capacitor assembled by using the graphene carbon nano tube as an electrode material shows a narrow potential window and low specific capacitance in an acid/alkali electrolyte, so that the energy density of the electric double layer capacitor is low. The transition metal oxide is capable of undergoing a redox reaction based on single/multiple electrons, and thus canTo provide much greater capacitance than conventional carbon materials. In the transition metal oxide, manganese dioxide (MnO 2 ) Due to its abundant reserves, multiple cost, environmental friendliness and high theoretical capacity (308 mAh g) -1 Single electron based) and a wide potential window of 0-1.3V, show great potential as an electrode material for SCs, mnO applied to SCs 2 Various morphologies such as nanowires, nanoplatelets, nanoflower, etc. have been developed. However, the unmodified MnO mentioned above 2 The cyclic properties of tetravalent manganese ions are unsatisfactory because they dissolve, resulting in irreversible phase transition and structural collapse during charge and discharge. In addition, due to poor conductivity of the material, the capacitance utilization rate is low, mnO 2 The specific capacitance of (2) is still not ideal and is far smaller than the theoretical specific capacitance. Therefore, there is an urgent need to develop MnO with high specific capacitance, long lifetime and excellent performance 2 An electrode material.
Disclosure of Invention
In order to solve the problems, the invention provides a nitrogen-doped manganese dioxide/graphene carbon nanotube membrane electrode material and a preparation method thereof, wherein manganese dioxide is deposited on the surface of a nitrogen-doped manganese dioxide/graphene carbon nanotube, and then nitrogen doping is carried out on the manganese dioxide, so that N-MnO with high specific capacitance is finally prepared 2 NGCF electrode material.
The invention is realized by the following technical scheme:
(1) MnO is deposited on the surface of the nitrogen doped manganese dioxide/graphene carbon nano tube through constant-pressure electrochemical deposition 2 Nano sheet to obtain MnO 2 NGCF electrode material; the electrochemical deposition adopts a saturated calomel electrode as a reference electrode and a platinum sheet electrode as a counter electrode, and a nitrogen-doped manganese dioxide/graphene carbon nano tube as a working electrode, and the electrolyte for the electrochemical deposition is a mixed aqueous solution of manganese acetate and sodium acetate;
the preparation method of the nitrogen-doped manganese dioxide/graphene carbon nanotube (refer to Chinese patent CN 105225844A) comprises the following steps:
firstly, adding 1.5g of potassium permanganate into 100mL of graphene oxide with the concentration of 0.5mg/mL, stirring and reacting for 2 hours, then adding 250mL of hydrochloric acid with the mass fraction of 36.5% for stirring and reacting for 3 hours, and then adding 20mL of hydrogen peroxide with the mass fraction of 30% for stirring and reacting for 3 hours to obtain porous graphene;
secondly, placing the porous graphene in a dialysis bag, dialyzing in distilled water until the graphene is neutral (about 8-12 days), taking out, performing ultrasonic dispersion for 1h, and obtaining a porous graphene dispersion liquid, wherein the ultrasonic power is 20 kHz; then adding carbon nano tubes into the porous graphene dispersion liquid, wherein the mass ratio of the added carbon nano tubes to the porous graphene is 1:5-15, and carrying out suction filtration after continuing to carry out ultrasonic treatment for 2 hours to obtain a graphene film;
finally, the graphene film obtained by suction filtration is dried for 48 hours at normal temperature, 35mL of ammonia water with the concentration of 25% is added, and hydrothermal reaction is carried out at 180 ℃, so that the obtained product is the nitrogen-doped graphene/carbon nanotube material.
(2) MnO is added to 2 Placing the/NGCF electrode material in ammonia water for hydrothermal reaction, washing and drying after the reaction is finished to obtain N-MnO 2 NGCF electrode material;
preferably, the concentration of manganese acetate in the electrolyte is 0.0978mol/L, and the concentration of sodium acetate in the electrolyte is 0.0974mol/L.
Preferably, the electrochemical deposition voltage in the step (1) is 1.0V, and the deposition time is 300-900s.
Preferably, the temperature of the hydrothermal reaction in the step (2) is 180 ℃, and the time of the hydrothermal reaction is 25 hours.
Preferably, the concentration of the ammonia water in the step (2) is 25-28 wt%.
Next, the present invention also uses the above N-MnO 2 Use of/NGCF as an electrode for a supercapacitor.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a nitrogen-doped manganese dioxide/graphene carbon nanotube membrane electrode material, which takes porous nitrogen-doped graphene and carbon nanotubes as a framework, and MnO is loaded on the framework 2 A nano-sheet. The nano sheet deposited on the surface of the electrode material not only can reduce the empty area on the graphene and the carbon nano tube, but also can improve the actual contact area between the electrode and the electrolyte, thereby improving the electrodeThe efficiency of the material is reduced, the contact resistance is reduced, and the specific capacitance of the electrode material is improved.
Meanwhile, the electrode material has excellent flexibility, and the electrochemical performance of the electrode material is small in change after being bent into various angles.
Drawings
FIG. 1 shows MnO prepared in example 1 of the present invention 2 SEM image of NGCF;
FIG. 2 shows MnO prepared in example 1 of the present invention 2 TEM image of NGCF;
FIG. 3 shows MnO prepared in example 1 of the present invention 2 Charge-discharge curve graph of/NGCF;
FIG. 4 shows N-MnO prepared in example 2 of the present invention 2 SEM image of NGCF;
FIG. 5 shows N-MnO prepared in example 2 of the present invention 2 TEM image of NGCF;
FIG. 6 shows N-MnO prepared in example 2 of the present invention 2 Charge-discharge curve graph of/NGCF;
FIG. 7 shows MnO prepared in example 1 of the present invention 2 NGCF and N-MnO prepared in example 2 2 XRD pattern of NG CF;
FIG. 8 shows N-MnO prepared in example 2 of the present invention 2 Cyclic voltammogram of/NGCF;
FIG. 9 shows N-MnO prepared in example 2 of the present invention 2 Charge-discharge curve graph of/NGCF;
FIG. 10 shows N-MnO prepared in example 2 of the present invention 2 Cycle life graph of/NGCF;
Detailed Description
The single-walled carbon nanotubes used in the examples were purchased from Shenzhen nanoharbor Co., ltd (SWNT-2);
the natural crystalline flake graphite used in the examples was purchased from AlfaAcsar, usa;
dialysis bags were purchased from Biosharp corporation, 27mm dialysis bags, MW:14000.
the remaining reagents and materials were purchased commercially unless otherwise specified.
Example 1
MnO (MnO) 2 NGCF of/NGCFThe preparation method comprises the following specific steps:
(1) Dispersing 3g of natural crystalline flake graphite in 70mL of 98% concentrated sulfuric acid, adding 0.1g of sodium nitrate under ice bath condition, cooling, adding 9g of potassium permanganate, keeping the temperature below 20 ℃, and stirring at 400rpm for reaction for 1.5h; then the reactants are placed in a hot water bath at 40 ℃ and stirred at a speed of 400rpm for reaction for 30min; then taking out the reactant, putting the reactant in an ice-water bath again, adding distilled water into the reactant, standing for at least 2 hours, removing supernatant after layering the solution, centrifuging (13000 rpm) for 10 minutes, taking dark solution obtained by centrifugation, and performing ultrasonic treatment (20 kHz) for 10 minutes; then centrifuging (4000 rpm) for 10min again, wherein the upper yellow transparent liquid obtained after centrifugation is graphene oxide;
(2) Adjusting the concentration of the graphene oxide obtained in the step (1) to be 0.5mg/mL, taking 100mL of graphene oxide in a beaker, adding 1.5g of potassium permanganate, stirring at a speed of 400rpm for reaction for 2 hours, then adding 250mL of 36.5% by mass of concentrated hydrochloric acid, stirring at 400rpm for reaction for 3 hours, and then adding 20mL of 30% by mass of hydrogen peroxide for stirring for reaction for 3 hours to obtain porous graphene;
(3) Putting the porous graphene obtained in the step (2) into a dialysis bag, and putting the dialysis bag into distilled water for dialysis for 10 days, so that the dialyzed porous graphene is neutral; taking dialyzed porous graphene and carrying out ultrasonic treatment (20 kHz) for 1h to obtain porous graphene dispersion liquid; then adding carbon nano tubes with the mass ratio of 1:10 with porous graphene into the porous graphene dispersion liquid, carrying out ultrasonic mixing for 2 hours at 20kHz, and carrying out suction filtration on the solution to form a film, thus obtaining a graphene/carbon nano tube film material;
(4) Drying the membrane obtained by suction filtration at normal temperature for 48 hours, then adding 35mL of ammonia water with the concentration of 25% into a reaction kettle, and reacting for 24 hours at 180 ℃, wherein the obtained product is the nitrogen-doped graphene/carbon nano tube membrane material (NGCF);
(5) Sequentially weighing 1.2g of Mn (Ac) 2 And 0.4g NaAc was dissolved in 50mL deionized water and vigorously stirred for several minutes to form a homogeneous clear solution that was used as the deposition electrolyte. The three-electrode system is used in the deposition process, and comprises Saturated Calomel Electrode (SCE) as reference electrode and platinum sheet electrodeThe counter electrode, NGCF, serves as the working electrode. After deposition, the electrode is taken down and washed by deionized water for several times, and the electrode is dried in a blast oven at 60 ℃ for overnight, thus finally obtaining black flexible self-supporting MnO 2 /NGCF electrode.
MnO obtained in this example 2 SEM pictures of the surface of the NGCF are shown in FIG. 1, where a and b are MnO at 500nm and 5 μm scales, respectively, in FIG. 1 2 NGCF surface SEM image; it can be seen that MnO 2 The original morphology is that the extremely small compact nano-sheets are aggregated into the auricularia auricular nano-flowers, because the nano-sheets are too small, mnO 2 The nano sheets which are grown on the surface of the substrate and then lead to the later deposition process can not be continuously loaded on the surface to be stacked and covered, and finally the appearance of the nano flower clusters is presented.
FIG. 2 shows MnO prepared in this example 2 TEM image of NGCF, in FIG. 2, a, b are MnO 2 TEM image of NGCF. MnO can be found 2 In the form of nano-sheet, obviously MnO 2 The nanoplatelets are condensed and agglomerated into spheres, and cannot be fully stretched.
FIG. 3 shows MnO prepared in this example 2 Charging and discharging curve graph of NGCF under different current density, calculating 1Ag according to the curve -1 The mass specific capacitance of the material under the current density is 288.5F g -1 . See DX Gong, H Tong, JP Xiao, TT Li, J Liu, Y Wu, XD Chen, J Liu and XG Zhang. Ceramics International,2021,47 (23), 33020-33027. Electrochemical test section.
Example 2
The preparation method of the nitrogen-doped manganese dioxide/graphene carbon nanotube membrane electrode material comprises the following specific operations:
MnO prepared in example 1 2 The NGCF is put into ammonia water with the mass concentration of 26 percent, placed into a 50mL polytetrafluoroethylene lining, and the lining is put into a stainless steel high-temperature high-pressure reaction kettle for hydrothermal reaction for 25 hours at 180 ℃. Taking out the sample, washing with distilled water for 3 times, and drying at 60deg.C for 12 hr to obtain the N-MnO 2 /NGCF。
FIG. 4 shows N-MnO prepared in this example 2 SEM image of NGCF. FIGS. a and b are N-MnO at 500nm and 5 μm scales, respectively 2 Surface of NGCFSEM pictures, from FIG. 4, can be seen N-MnO 2 The morphology of the nano-meter is a nano-network formed by large and thin nano-sheets, the nano-sheets uniformly grow on a substrate, and stacking does not occur. The difference can be clearly seen by comparing fig. 1 (a) and (b), the shape of the original nanoflower clusters is changed by the hydrothermal method, the internal space which is originally covered by the nano sheet stack is released, the expansion of the contracted lamellar structure can be promoted under the airtight high-temperature ammonia-rich environment, the stacking condition of the nano sheets is changed, the utilization rate of a main material is improved, the reactive sites are increased, the ion diffusion rate in the electrolyte is accelerated, and therefore, higher charge storage capacity and multiplying power are obtained.
FIG. 5 shows N-MnO prepared in this example 2 TEM image of NGCF, panels a, b are N-MnO 2 TEM image of NGCF. N-MnO 2 The nano sheets are stretched to be obvious sheets, which indicates that the ammonia water and the hydrothermal energy inhibit the stacking of the sheets and promote the stretching of the sheets, and the nano sheets are consistent with the SEM observation result. The morphology and internal structure information of the material are obtained through the characterization of SEM and TEM, and mutual verification of several means proves that the hydrothermal reaction of ammonia water on epsilon-MnO 2 The lamination structure stacking is restrained, the wettable area of the electrolyte of the material is increased, and the electrochemical performance of the material is fully exerted.
FIG. 6 shows N-MnO prepared in this example 2 Charging and discharging curve graph of NGCF under different current density, calculating 1Ag according to the curve -1 The mass specific capacitance of the material under the current density is 358.4F g -1 。
FIG. 7 shows MnO 2 NGCF and N-MnO 2 XRD pattern of NGCF, as can be seen from the figure: except that a distinct peak (2θ=26.3°) is assigned to the NGCF substrate, the remaining peaks in the XRD pattern are substantially identical to standard cards (JCPDS No. 00-030-0820) and belong to the overpass crystal system epsilon-MnO 2 P63/mmc space group. The characteristic peak position is 2 theta=36.6 DEG, 41.8 DEG, 55.3 DEG, and the crystal face information of 66.6 DEG corresponds to epsilon-MnO respectively 2 The (100), (101), (102), (110) crystal planes of the phases. In addition, no other diffraction peaks were present, indicating that the resulting epsilon-MnO was electrochemically deposited 2 Is pure phase. epsilon-MnO 2 The characteristic peak-to-peak signal of (2) is weak and the peak width is large, indicating that the electrochemical deposition is carried outThe epsilon-MnO obtained 2 The crystallinity is poor. From the figure, it is clear that N-MnO 2 NGCF and MnO 2 The XRD patterns of the NGCF are highly consistent, which means that the lattice structure of manganese dioxide is not changed obviously after the hydrothermal treatment of ammonia water, and the structure of active substances is not damaged.
FIG. 8 shows N-MnO at different scan speeds 2 Cyclic voltammogram of/NGCF, potential window of-0-1.2V, scan rate of 2-200mV s -1 Is a CV curve of (c). CV curve shapes of different scanning rates are kept consistent, obvious polarization and oxygen inhalation phenomena do not occur along with the increase of the scanning speed, and the N-MnO is proved 2 The electrochemical behavior of/NGCF is highly reversible and structurally stable, see DX Gong, H Tong, JP Xao, TT Li, J Liu, Y Wu, X D Chen, J Liu and XG Zhang. Ceramics International,2021,47 (23), 33020-33027. Electrochemical test section.
N-MnO is shown in FIG. 9 2 Charge and discharge curves of/NGCF at different current densities (see DX Gong, H Tong, JP Xiao, TT Li, J Liu, Y Wu, X D Chen, J Liu and XG Zhang. Ceramics International 2021,47 (23), 33020-33027.) at current densities of 1,2,5, 10, 15, 20, 25 and 30A g -1 The mass ratio capacitances are 358.4, 334.6, 295.3, 267.6, 241.0, 222.7, 207.8 and 185.114F g respectively -1 . Even at a high current density of 30Ag -1 The capacity retention rate was still 51.7% of the initial capacity. According to example 1, mnO 2 NGCF at 1A g -1 Mass specific capacitance of 288.5F g -1 At 30A g -1 The lower capacity is only 24.5% of the initial capacity, i.e. 70.8F g -1 The nitrogen doping can improve the oxygen vacancy content of the material, shorten the electron and ion transmission distance, improve the conductivity of the material and be beneficial to improving the rate capability by adjusting the valence structure of the manganese metal.
FIG. 10 shows N-MnO prepared in this example 2 Cycle life graph of/NGCF composite, N-MnO 2 Once the NGCF has undergone about 1000 cycles of activation, a slow capacity fade is initiated, and even then after 10000 cycles the capacity retention is 121% of the initial capacity, showing excellent cycling stability and higher electricityCapacity due to the extended N-MnO 2 The NGCF nano-sheet has larger effective active area, can not only hold more electrolyte, but also endow the material with larger solution buffer capacity, so that the damage of ions to the material structure in the charge and discharge process is smaller, and longer cycle life is obtained.
As can be seen from FIGS. 8 to 10, N-MnO prepared in this example 2 the/NGCF can be used as an electrode and applied to a super capacitor.
The above examples are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred examples, it should be understood by those skilled in the art that modifications can be made to the technical solution of the present invention, but they are all included in the scope of the claims of the present invention.
Claims (6)
1. The preparation method of the nitrogen doped manganese dioxide/graphene carbon nanotube electrode material is characterized by comprising the following steps of:
MnO is deposited on the surface of the nitrogen doped manganese dioxide/graphene carbon nano tube through constant-pressure electrochemical deposition 2 Nano sheet to obtain MnO 2 NGCF electrode material; the electrochemical deposition adopts a saturated calomel electrode as a reference electrode and a platinum sheet electrode as a counter electrode, and a nitrogen-doped manganese dioxide/graphene carbon nano tube as a working electrode, and the electrolyte for the electrochemical deposition is a mixed aqueous solution of manganese acetate and sodium acetate;
MnO is added to 2 Placing the/NGCF electrode material in ammonia water for hydrothermal reaction, washing and drying after the reaction is finished to obtain N-MnO 2 NGCF electrode material;
the electrochemical deposition in step (1) was performed at a voltage of 1.0 and V for a deposition time of 300 ‒ 900,900, 900s.
2. The method for preparing the nitrogen-doped manganese dioxide/graphene carbon nanotube electrode material according to claim 1, wherein the electrolyte is prepared by adding 1.2g manganese acetate and 0.4g sodium acetate into 50mL deionized water.
3. The method for preparing the nitrogen-doped manganese dioxide/graphene carbon nanotube electrode material according to claim 1, wherein the temperature of the hydrothermal reaction in the step (2) is 180 ℃, and the time of the hydrothermal reaction is 25 hours.
4. The method for preparing the nitrogen-doped manganese dioxide/graphene carbon nanotube electrode material according to claim 1, wherein the ammonia water concentration in the step (2) is 25% ‒% by weight.
5. A nitrogen doped manganese dioxide/graphene carbon nanotube electrode material, characterized in that it is prepared by the method of any one of claims 1 to 4.
6. The use of the nitrogen-doped manganese dioxide/graphene carbon nanotube electrode material of claim 5 as an electrode for a supercapacitor.
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