CN104045114B - The preparation method of the mesoporous self-assembled structures manganese oxide of bigger serface - Google Patents
The preparation method of the mesoporous self-assembled structures manganese oxide of bigger serface Download PDFInfo
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- CN104045114B CN104045114B CN201410275473.2A CN201410275473A CN104045114B CN 104045114 B CN104045114 B CN 104045114B CN 201410275473 A CN201410275473 A CN 201410275473A CN 104045114 B CN104045114 B CN 104045114B
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- manganese oxide
- assembled structures
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Abstract
The invention discloses the preparation method of the mesoporous self-assembled structures manganese oxide of a kind of bigger serface, by water content be 50% ~ 60% stratiform manganese oxide nanometer layer peel off mud and monoammonium sulfate and grind evenly, gained mixture is calcined in air atmosphere, is prepared into the mesoporous self-assembled structures manganese oxide of bigger serface.Reaction conditions of the present invention is gentle, production cost is low, do not add template and tensio-active agent, and products therefrom is mesoporous self-assembled structures δ type manganese oxide nano granule, and its specific surface area is 184 ~ 456m
2g
-1, be expected to as a kind of electrode materials assembling high-energy-density and high power density ultracapacitor.
Description
Technical field
The invention belongs to field of material technology, be specifically related to the preparation method of bigger serface mesoporous self-assembled structures manganese oxide material.
Background technology
Manganese oxide is as a kind of important transition metal oxide, and the physicochemical property due to its uniqueness make this type of material show wide application prospect 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 microstructure with its pattern, and with its specific surface area and pore size distribution in close relations.The mesoporous manganese oxide nano-electrode material with bigger serface can provide more redox reaction avtive spot, shortens the ion diffuse 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 prepares product, scale can not be expanded, 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 template is removed thoroughly or introduce other impurity in last handling process.At present, a lot, specific surface area is generally 50 ~ 100m to the technology of preparing report of bigger serface mesoporous manganese oxide material
2g
-1, prepare that the specific surface area of material is maximum is no more than 340m according to the literature
2g
-1, this brings significant limitation to the application preparing material.Therefore, develop crystalline phase and morphology controllable, specific surface area manganese oxide nano-electrode material new preparation technology that is large and mesoporous pore size is significant.
Summary of the invention
Technical problem to be solved by this invention is the preparation method providing 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: by water content be 50% ~ 60% stratiform manganese oxide nanometer layer peel off mud and monoammonium sulfate be in mass ratio 1: 0.25 ~ 2 fully grind even, calcine 1 ~ 5 hour for 120 ~ 175 DEG C in air atmosphere, naturally cool to room temperature, be neutral with deionized water wash to filtrate, drying, is prepared into the mesoporous self-assembled structures manganese oxide of bigger serface.
Preferred water content of the present invention is the stratiform manganese oxide nanometer layer stripping mud of 50% ~ 60% and the mass ratio of monoammonium sulfate is 1: 1.0 ~ 1.5, and the best is 1: 1.5.
The present invention preferably in air atmosphere 175 DEG C calcining 5 hours.
Above-mentioned water content be 50% ~ 60% stratiform manganese oxide nanometer layer peel off the preparation method of mud and be: be the H of 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 temperature condition
24H
2in the O aqueous solution, wherein H
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 temperature 24 hours, centrifugation, discard the unstripped mud of lower floor, by turbid for upper strata liquid centrifuge washing to neutral, discard supernatant liquid, dry lower floor mud, obtains the stratiform manganese oxide nanometer layer stripping mud that water content is 50% ~ 60%.
The present invention adopt water content be 50% ~ 60% stratiform manganese oxide nanometer layer peel off mud and monoammonium sulfate calcination reaction and prepare mesoporous self-assembled structures manganese oxide.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 prepared by embodiment 1.
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 prepared by embodiment 1.
Fig. 5 is the transmission electron microscope photo of the mesoporous self-assembled structures manganese oxide of bigger serface prepared by embodiment 1.
Fig. 6 is the N of the mesoporous self-assembled structures manganese oxide of bigger serface prepared by embodiment 1
2adsorption-desorption isothermal figure.
Fig. 7 is the cyclic voltammetry curve figure of the mesoporous self-assembled structures manganese oxide of bigger serface prepared by embodiment 1.
Fig. 8 is the transmission electron microscope photo of the mesoporous self-assembled structures manganese oxide of bigger serface prepared by embodiment 2.
Fig. 9 is the transmission electron microscope photo of the mesoporous self-assembled structures manganese oxide of bigger serface prepared by embodiment 3.
Figure 10 is the transmission electron microscope photo of the mesoporous self-assembled structures manganese oxide of bigger serface prepared by embodiment 4.
Figure 11 is the transmission electron microscope photo of the mesoporous self-assembled structures manganese oxide of bigger serface prepared by embodiment 5.
Figure 12 is the transmission electron microscope photo of the mesoporous self-assembled structures manganese oxide of bigger serface prepared by embodiment 6.
Figure 13 is the transmission electron microscope photo of the mesoporous self-assembled structures manganese oxide of bigger serface prepared by embodiment 7.
Figure 14 is the transmission electron microscope photo of the mesoporous self-assembled structures manganese oxide of bigger serface prepared by embodiment 8.
Figure 15 is the transmission electron microscope photo of the mesoporous self-assembled structures manganese oxide of bigger serface prepared by embodiment 9.
Figure 16 is the transmission electron microscope photo of the mesoporous self-assembled structures manganese oxide of bigger serface prepared by embodiment 10.
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 embodiments.
Embodiment 1
Be the H of 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 temperature condition
24H
2in the O aqueous solution, stirring at room temperature 24 hours, centrifugal 15 minutes of gained suspension liquid 8000 revs/min, 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 DEG C of dryings 2 hours, obtain the stratiform manganese oxide nanometer layer stripping mud that water content is 55%.By 2.0g water content be 55% stratiform manganese oxide nanometer layer peel off mud and 3.0g monoammonium sulfate and add in mortar, abundant 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, calcine 5 hours for 175 DEG C in air atmosphere, naturally cool to room temperature, be neutral with deionized water filtering and washing to filtrate, pressed powder is placed in baking oven 50 DEG C of dryings 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 carry out characterizing and testing, 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 of the nano-particles self assemble of preparation 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 its capacitive properties had is described, is sweeping speed for 10mVs
-1time, its specific discharge capacity is 316Fg
-1, can as the electrode materials of ultracapacitor.
Embodiment 2
By 2.0g water content be 55% stratiform manganese oxide nanometer layer peel off mud and 0.5g monoammonium sulfate and add in mortar, abundant 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 (see Fig. 8) of bigger serface, 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
By 2.0g water content be 55% stratiform manganese oxide nanometer layer peel off mud and 1.0g monoammonium sulfate and add in mortar, abundant 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 (see Fig. 9) of bigger serface, 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
By 2.0g water content be 55% stratiform manganese oxide nanometer layer peel off mud and 2.0g monoammonium sulfate and add in mortar, abundant 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 (see Figure 10) of bigger serface, 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
By 2.0g water content be 55% stratiform manganese oxide nanometer layer peel off mud and 4.0g monoammonium sulfate and add in mortar, abundant 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 (see Figure 11) of bigger serface, 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 in air atmosphere 120 DEG C calcining 5 hours, other steps are identical with embodiment 1, and be prepared into the mesoporous self-assembled structures manganese oxide (see Figure 12) of bigger serface, 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 in air atmosphere 150 DEG C calcining 5 hours, other steps are identical with embodiment 1, and be prepared into the mesoporous self-assembled structures manganese oxide (see Figure 13) of bigger serface, 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 in air atmosphere 200 DEG C calcining 1 hour, other steps are identical with embodiment 1, and be prepared into the mesoporous self-assembled structures manganese oxide (see Figure 14) of bigger serface, 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 in air atmosphere 175 DEG C calcining 1 hour, other steps are identical with embodiment 1, and be prepared into the mesoporous self-assembled structures manganese oxide (see Figure 15) of bigger serface, 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 in air atmosphere 175 DEG C calcining 3 hours, other steps are identical with embodiment 1, and be prepared into the mesoporous self-assembled structures manganese oxide (see Figure 16) of bigger serface, 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 (4)
1. the preparation method of the mesoporous self-assembled structures manganese oxide of bigger serface, it is characterized in that: by water content be 50% ~ 60% stratiform manganese oxide nanometer layer peel off mud and monoammonium sulfate be in mass ratio 1: 0.25 ~ 2 fully grind even, calcine 1 ~ 5 hour for 120 ~ 175 DEG C in air atmosphere, naturally cool to room temperature, be neutral with deionized water wash to filtrate, drying, is prepared into the mesoporous self-assembled structures manganese oxide of bigger serface;
Above-mentioned water content be 50% ~ 60% stratiform manganese oxide nanometer layer peel off the preparation method of mud and be: be the H of 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 temperature condition
24H
2in the O aqueous solution, wherein H
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 temperature 24 hours, centrifugation, discard the unstripped mud of lower floor, by turbid for upper strata liquid centrifuge washing to neutral, discard supernatant liquid, dry lower floor mud, obtains the stratiform manganese oxide nanometer layer stripping mud that water content is 50% ~ 60%.
2. the preparation method of the mesoporous self-assembled structures manganese oxide of bigger serface according to claim 1, is characterized in that: described water content is the stratiform manganese oxide nanometer layer stripping mud of 50% ~ 60% and the mass ratio of 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: described water content is the stratiform manganese oxide nanometer layer stripping mud of 50% ~ 60% and the mass ratio of monoammonium sulfate is 1: 1.5.
4. the preparation method of the mesoporous self-assembled structures manganese oxide of the bigger serface according to claims 1 to 3 any one, is characterized in that: calcine 5 hours for 175 DEG C in air atmosphere.
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