CN104045114A - Preparation method of mesoporous self-assembled structural manganese oxide with large specific surface area - Google Patents
Preparation method of mesoporous self-assembled structural manganese oxide with large specific surface area Download PDFInfo
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- CN104045114A CN104045114A CN201410275473.2A CN201410275473A CN104045114A CN 104045114 A CN104045114 A CN 104045114A CN 201410275473 A CN201410275473 A CN 201410275473A CN 104045114 A CN104045114 A CN 104045114A
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Abstract
The invention discloses a preparation method of mesoporous self-assembled structural manganese oxide with a large specific surface area. The method comprises the following steps: carrying out slurry stripping on a layered manganese oxide nanolayer with the water content of 50% to 69% and evenly grinding with ammonium bisulfate; and calcining an obtained mixture in an air atmosphere, thereby preparing the mesoporous self-assembled structural manganese oxide with the large specific surface area. The method is moderate in reaction condition and low in production cost, wherein a template agent and a surfactant are not added. The specific surface area of the obtained product, ie., the mesoporous self-assembled structural Delta-type manganese oxide nanoparticles, is between 184m<2>.g<-1> and 456 184m<2>.g<-1>. Thus, the mesoporous self-assembled structural Delta-type manganese oxide nanoparticles can be taken as electrode materials for assembling a supercapacitor with high-energy density and high-power density.
Description
Technical field
The invention belongs to material technology field, be specifically related to the preparation method of the mesoporous self-assembled structures manganese oxide of bigger serface material.
Background technology
Manganese oxide, as a kind of important transition metal oxide, has shown wide application prospect because its unique physicochemical property make this type of material in fields such as catalysis, ion-exchange, molecular adsorption, biosensor, lithium ion battery and electric chemical super capacitors.Result of study shows, the capacitive properties of manganese oxide material is not only relevant with its pattern and microstructure, and in close relations with its specific surface area and pore size distribution.The mesoporous manganese oxide nano-electrode material with bigger serface can provide more redox reaction avtive spot, shortens ion diffusion time, improves reaction kinetics speed, makes it show higher faraday's electric capacity.
At present, the preparation method of bigger serface porous oxidation manganese material mainly contains electrodip process, thermal decomposition method and template etc.But it is few that electrodip process is prepared product, can not expand scale, thermal decomposition method temperature of reaction is higher, template not only preparation process is complicated, also there is very large limitation, the selection of Template Types in first reaction system, it two is that other impurity is removed thoroughly or introduced to template in last handling process.At present, the technology of preparing of bigger serface mesoporous manganese oxide material report is a lot, and specific surface area is generally 50～100m
2g
-1, the specific surface area maximum of preparing according to the literature material is no more than 340m
2g
-1, this has brought significant limitation to the application of preparing material.Therefore, exploitation crystalline phase and pattern is controlled, specific surface area is large and the manganese oxide nano-electrode material new preparation technology in mesoporous aperture is significant.
Summary of the invention
Technical problem to be solved by this invention is to provide the preparation method of the mesoporous self-assembled structures manganese oxide of a kind of bigger serface simple to operate, that production cost is low.
Solving the problems of the technologies described above adopted scheme is: the stratiform manganese oxide nanometer layer that is 50%～60% by water content peels off mud and monoammonium sulfate is 1: 0.25～2 abundant grindings evenly in mass ratio, in air atmosphere, calcine 1～5 hour for 120～175 ℃, naturally cool to room temperature, with deionized water wash to filtrate, be neutral, dry, be prepared into the mesoporous self-assembled structures manganese oxide of bigger serface.
Preferred water content of the present invention is that the mass ratio that 50%～60% stratiform manganese oxide nanometer layer is peeled off mud and monoammonium sulfate is 1: 1.0～1.5, and the best is 1: 1.5.
The present invention preferably in air atmosphere 175 ℃ calcining 5 hours.
Above-mentioned water content is that the preparation method that 50%～60% stratiform manganese oxide nanometer layer is peeled off mud is: the H that is 3% by massfraction
2o
2the aqueous solution mixes with the tetramethylammonium hydroxide aqueous solution of 0.6mol/L, and gained mixed solution adds the MnCl of 0.3mol/L under stirring at room condition
24H
2in the O aqueous solution, H wherein
2o
2the aqueous solution and tetramethylammonium hydroxide aqueous solution, MnCl
24H
2the volume ratio of the O aqueous solution is 1: 3: 2, stirring at room 24 hours, centrifugation, discard the unstripped mud of lower floor, the turbid liquid centrifuge washing in upper strata, to neutral, is discarded to supernatant liquid, dry lower floor mud, obtains water content and is 50%～60% stratiform manganese oxide nanometer layer and peel off mud.
It is that 50%～60% stratiform manganese oxide nanometer layer is peeled off mud and monoammonium sulfate calcination reaction is prepared mesoporous self-assembled structures manganese oxide that the present invention adopts water content.Reaction conditions of the present invention is gentle, production cost is low, do not add template and tensio-active agent, products therefrom adopts X-ray diffractometer, x-ray photoelectron power spectrum, field emission scanning electron microscope, transmission electron microscope, physical adsorption appearance and electrochemical workstation to characterize, result shows that product is mesoporous self-assembled structures δ type manganese oxide nano granule, and its specific surface area is 184～456m
2g
-1, can be used as the electrode materials of a kind of potential assembling high-energy-density and high power density ultracapacitor.
Accompanying drawing explanation
Fig. 1 is the X-ray diffractogram of the mesoporous self-assembled structures manganese oxide of bigger serface of embodiment 1 preparation.
Fig. 2 is the x-ray photoelectron energy spectrogram of Mn2p in the mesoporous self-assembled structures manganese oxide of bigger serface of embodiment 1 preparation.
Fig. 3 is the x-ray photoelectron energy spectrogram of Mn3s in the mesoporous self-assembled structures manganese oxide of bigger serface of embodiment 1 preparation.
Fig. 4 is the field emission scanning electron microscope photo of the mesoporous self-assembled structures manganese oxide of bigger serface of embodiment 1 preparation.
Fig. 5 is the transmission electron microscope photo of the mesoporous self-assembled structures manganese oxide of bigger serface of embodiment 1 preparation.
Fig. 6 is the N of the mesoporous self-assembled structures manganese oxide of bigger serface of embodiment 1 preparation
2adsorption-desorption isothermal map.
Fig. 7 is the cyclic voltammetry curve figure of the mesoporous self-assembled structures manganese oxide of bigger serface of embodiment 1 preparation.
Fig. 8 is the transmission electron microscope photo of the mesoporous self-assembled structures manganese oxide of bigger serface of embodiment 2 preparations.
Fig. 9 is the transmission electron microscope photo of the mesoporous self-assembled structures manganese oxide of bigger serface of embodiment 3 preparations.
Figure 10 is the transmission electron microscope photo of the mesoporous self-assembled structures manganese oxide of bigger serface of embodiment 4 preparations.
Figure 11 is the transmission electron microscope photo of the mesoporous self-assembled structures manganese oxide of bigger serface of embodiment 5 preparations.
Figure 12 is the transmission electron microscope photo of the mesoporous self-assembled structures manganese oxide of bigger serface of embodiment 6 preparations.
Figure 13 is the transmission electron microscope photo of the mesoporous self-assembled structures manganese oxide of bigger serface of embodiment 7 preparations.
Figure 14 is the transmission electron microscope photo of the mesoporous self-assembled structures manganese oxide of bigger serface of embodiment 8 preparations.
Figure 15 is the transmission electron microscope photo of the mesoporous self-assembled structures manganese oxide of bigger serface of embodiment 9 preparations.
Figure 16 is the transmission electron microscope photo of the mesoporous self-assembled structures manganese oxide of bigger serface of embodiment 10 preparations.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in more detail, but protection scope of the present invention is not limited only to these embodiment.
Embodiment 1
The H that is 3% by 50mL massfraction
2o
2the aqueous solution mixes with the tetramethylammonium hydroxide aqueous solution of 150mL0.6mol/L, and gained mixed solution adds the MnCl of 100mL0.3mol/L under stirring at room condition
24H
2in the O aqueous solution, stirring at room 24 hours, 8000 revs/min of gained suspension liquids are centrifugal 15 minutes, discard the unstripped mud of lower floor, the turbid liquid in upper strata 12000 revs/min of centrifuge washings 30 minutes until neutrality, discard supernatant liquid, by lower floor's mud 50 ℃ dry 2 hours, obtain water content and be 55% stratiform manganese oxide nanometer layer and peel off mud.The stratiform manganese oxide nanometer layer that is 55% by 2.0g water content peels off mud and 3.0g monoammonium sulfate adds in mortar, fully ground and mixed is even, manganese oxide nanometer layer peels off mud and monoammonium sulfate mass ratio is 1: 1.5, gained mixture is transferred to crucible and is built in retort furnace, under air atmosphere, calcine 5 hours for 175 ℃, naturally cool to room temperature, with deionized water filtering and washing to filtrate, be neutral, pressed powder is placed in 50 ℃, baking oven and is dried 12 hours, is prepared into the mesoporous self-assembled structures manganese oxide of bigger serface.
Prepared manganese oxide adopts X-ray diffractometer, x-ray photoelectron power spectrum, field emission scanning electron microscope, transmission electron microscope, physical adsorption appearance and electrochemical workstation to characterize and test, and the results are shown in Figure 1～7.As seen from Figure 1, products therefrom is δ type manganese oxide.From Fig. 2～3, the oxidation state of manganese is 3.55.As seen from Figure 4, prepared manganese oxide is particulate state.As seen from Figure 5, prepared product is formed by manganese oxide nano granule self-assembly.As seen from Figure 6, the manganese oxide that the nano particle self-assembly of preparation forms has mesoporous material feature, and its specific surface area is 456m
2g
-1, aperture is about 3.0nm, pore volume is about 0.68cm
3g
-1.As seen from Figure 7, the cyclic voltammetry curve of product presents good rectangular shape, and the capacitive properties that it has had is described, is sweeping speed for 10mVs
-1time, its specific discharge capacity is 316Fg
-1, can be used as the electrode materials of ultracapacitor.
Embodiment 2
The stratiform manganese oxide nanometer layer that is 55% by 2.0g water content peels off mud and 0.5g monoammonium sulfate adds in mortar, fully ground and mixed is even, manganese oxide nanometer layer peels off mud and monoammonium sulfate mass ratio is 1: 0.25, other steps are identical with embodiment 1, be prepared into the mesoporous self-assembled structures manganese oxide of bigger serface (seeing Fig. 8), its specific surface area is 184m
2g
-1, aperture is about 3.8nm, pore volume is about 0.42cm
3g
-1, sweeping speed for 10mVs
-1time, its specific discharge capacity is 206Fg
-1.
Embodiment 3
The stratiform manganese oxide nanometer layer that is 55% by 2.0g water content peels off mud and 1.0g monoammonium sulfate adds in mortar, fully ground and mixed is even, manganese oxide nanometer layer peels off mud and monoammonium sulfate mass ratio is 1: 0.5, other steps are identical with embodiment 1, be prepared into the mesoporous self-assembled structures manganese oxide of bigger serface (seeing Fig. 9), its specific surface area is 231m
2g
-1, aperture is about 3.5nm, pore volume is about 0.57cm
3g
-1, sweeping speed for 10mVs
-1time, its specific discharge capacity is 230Fg
-1.
Embodiment 4
The stratiform manganese oxide nanometer layer that is 55% by 2.0g water content peels off mud and 2.0g monoammonium sulfate adds in mortar, fully ground and mixed is even, manganese oxide nanometer layer peels off mud and monoammonium sulfate mass ratio is 1: 1.0, other steps are identical with embodiment 1, be prepared into the mesoporous self-assembled structures manganese oxide of bigger serface (seeing Figure 10), its specific surface area is 350m
2g
-1, aperture is about 3.5nm, pore volume is about 0.73cm
3g
-1, sweeping speed for 10mVs
-1time, its specific discharge capacity is 278Fg
-1.
Embodiment 5
The stratiform manganese oxide nanometer layer that is 55% by 2.0g water content peels off mud and 4.0g monoammonium sulfate adds in mortar, fully ground and mixed is even, manganese oxide nanometer layer peels off mud and monoammonium sulfate mass ratio is 1: 2, other steps are identical with embodiment 1, be prepared into the mesoporous self-assembled structures manganese oxide of bigger serface (seeing Figure 11), its specific surface area is 421m
2g
-1, aperture is about 3.5nm, pore volume is about 0.66cm
3g
-1, sweeping speed for 10mVs
-1time, its specific discharge capacity is 303Fg
-1.
Embodiment 6
In the present embodiment under air atmosphere 120 ℃ calcining 5 hours, other steps are identical with embodiment 1, are prepared into the mesoporous self-assembled structures manganese oxide of bigger serface (seeing Figure 12), its specific surface area is 282m
2g
-1, aperture is about 3.7nm, pore volume is about 0.46cm
3g
-1, sweeping speed for 10mVs
-1time, its specific discharge capacity is 242Fg
-1.
Embodiment 7
In the present embodiment under air atmosphere 150 ℃ calcining 5 hours, other steps are identical with embodiment 1, are prepared into the mesoporous self-assembled structures manganese oxide of bigger serface (seeing Figure 13), its specific surface area is 348m
2g
-1, aperture is about 3.4nm, pore volume is about 0.65cm
3g
-1, sweeping speed for 10mVs
-1time, its specific discharge capacity is 268Fg
-1.
Embodiment 8
In the present embodiment under air atmosphere 200 ℃ calcining 1 hour, other steps are identical with embodiment 1, are prepared into the mesoporous self-assembled structures manganese oxide of bigger serface (seeing Figure 14), its specific surface area is 269mg
-1, aperture is about 3.6nm, pore volume is about 0.40cm
3g
-1, sweeping speed for 10mVs
-1time, its specific discharge capacity is 236Fg
-1.
Embodiment 9
In the present embodiment under air atmosphere 175 ℃ calcining 1 hour, other steps are identical with embodiment 1, are prepared into the mesoporous self-assembled structures manganese oxide of bigger serface (seeing Figure 15), its specific surface area is 254m
2g
-1, aperture is about 3.6nm, pore volume is about 0.38cm
3g
-1, sweeping speed for 10mVs
-1time, its specific discharge capacity is 244Fg
-1.
Embodiment 10
In the present embodiment under air atmosphere 175 ℃ calcining 3 hours, other steps are identical with embodiment 1, are prepared into the mesoporous self-assembled structures manganese oxide of bigger serface (seeing Figure 16), its specific surface area is 305m
2g
-1, aperture is about 3.4nm, pore volume is about 0.59cm
3g
-1, sweeping speed for 10mVs
-1time, its specific discharge capacity is 298Fg
-1.
Claims (5)
1. the preparation method of the mesoporous self-assembled structures manganese oxide of bigger serface, it is characterized in that: the stratiform manganese oxide nanometer layer that is 50%～60% by water content peels off mud and monoammonium sulfate is 1: 0.25～2 abundant grindings evenly in mass ratio, in air atmosphere, calcine 1～5 hour for 120～175 ℃, naturally cool to room temperature, with deionized water wash to filtrate, be neutral, dry, be prepared into the mesoporous self-assembled structures manganese oxide of bigger serface.
2. the preparation method of the mesoporous self-assembled structures manganese oxide of bigger serface according to claim 1, is characterized in that: the mass ratio that the stratiform manganese oxide nanometer layer that described water content is 50%～60% is peeled off mud and monoammonium sulfate is 1: 1.0～1.5.
3. the preparation method of the mesoporous self-assembled structures manganese oxide of bigger serface according to claim 1, is characterized in that: the mass ratio that the stratiform manganese oxide nanometer layer that described water content is 50%～60% is peeled off mud and monoammonium sulfate is 1: 1.5.
4. according to the preparation method of the mesoporous self-assembled structures manganese oxide of bigger serface described in claim 1～3 any one, it is characterized in that: in air atmosphere, calcine 5 hours for 175 ℃.
5. the preparation method of the mesoporous self-assembled structures manganese oxide of bigger serface according to claim 1, is characterized in that stratiform manganese oxide nanometer layer that described water content is 50%～60% peels off the preparation method of mud and be: the H that is 3% by massfraction
2o
2the aqueous solution mixes with the tetramethylammonium hydroxide aqueous solution of 0.6mol/L, and gained mixed solution adds the MnCl of 0.3mol/L under stirring at room condition
24H
2in the O aqueous solution, H wherein
2o
2the aqueous solution and tetramethylammonium hydroxide aqueous solution, MnCl
24H
2the volume ratio of the O aqueous solution is 1: 3: 2, stirring at room 24 hours, centrifugation, discard the unstripped mud of lower floor, the turbid liquid centrifuge washing in upper strata, to neutral, is discarded to supernatant liquid, dry lower floor mud, obtains water content and is 50%～60% stratiform manganese oxide nanometer layer and peel off mud.
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| CN113735089A (en) * | 2021-09-18 | 2021-12-03 | 西安理工大学 | Preparation method of nanoparticle self-assembly hydrated manganese phosphate nanospheres |
| CN114180632A (en) * | 2022-01-18 | 2022-03-15 | 西安理工大学 | Method for rapidly preparing porous trimanganese tetroxide nano material with large specific surface area in one step |
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