CN102107909B - Method for preparing mesoporous nano manganese dioxide - Google Patents
Method for preparing mesoporous nano manganese dioxide Download PDFInfo
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- CN102107909B CN102107909B CN2011100044824A CN201110004482A CN102107909B CN 102107909 B CN102107909 B CN 102107909B CN 2011100044824 A CN2011100044824 A CN 2011100044824A CN 201110004482 A CN201110004482 A CN 201110004482A CN 102107909 B CN102107909 B CN 102107909B
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Abstract
The invention discloses a method for preparing mesoporous nano manganese dioxide under non-template action. The method comprises the following steps of: slowly adding aqueous solution of potassium permanganate with certain molar ratio concentration into aqueous solution of glucose at room temperature; stirring until the reaction is finished; filtering; and washing and drying filter cakes to obtain the mesoporous nano manganese dioxide. The preparation method has the advantages of readily available raw materials, low cost, low pollution, mild reaction condition, short reaction time, simple and practicable process, high controllability, easiness in large-scale production and the like. By the preparation method, pure alpha type amorphous mesoporous nano manganese dioxide with the aperture of 3 to 15 nm and the specific surface area of 135 to 220 m<2>/g can be obtained, has the specific capacity of a single electrode of 170 to 300 F/g, the coulomb efficiency of up to 67 percent and excellent electrochemical capacitance performance, and can serve as an electrode material of a super capacitor.
Description
Technical field
The present invention relates to the preparation method of meso-porous nano Manganse Dioxide, specifically, relate to a kind of preparation method who can be used as the adjustable meso-porous nano Manganse Dioxide of electrode material for super capacitor, aperture and specific surface area, belong to the nano material preparation technical field.
Background technology
Ultracapacitor is as a kind of green novel energy; Have the capacity height, discharge and recharge fast and have extended cycle life (several ten thousand times), the wide characteristics such as (25～85 ℃) of operating temperature range; In fields such as electric car power supply, portable instrument equipment, data accumulating storage system and power pulsers wide application prospect is arranged, thereby caused countries in the world scientists' extensive concern.
At present, ultracapacitor electrode used therein material mainly is divided three classes: carbon material, MOX and conductive polymers.Wherein, metal oxide electrode material because of it can overcome the capacity limit of carbon-based electrode material, can obtain more jumbo ultracapacitor, becomes the focus of research.That research is the most successful at present is ruthenium dioxide (RuO
2) and H
2SO
4Water solution system (being worth up to 760F/g) than electric capacity SC.But because RuO
2Material price is expensive and to the pollution of environment, has limited its industrialization.Manganse Dioxide (MnO
2) compare with it, resource is extensive, and cheap and environmental friendliness has multiple oxidation valence state.And along with finding MnO in 1999 first
2After the fake capacitance behavior in neutral and alkaline aqueous solution, MnO
2Become the focus of electrode material for super capacitor research, and be considered to the most promising electrode material for super capacitor.
At present, to MnO
2Electrode materials preparing method's research is more, like liquid phase co-electrodeposition method, sol-gel method, solid reaction process, hydrothermal method etc.For example; Chinese patent CN1513767A has announced a kind of preparation method of ultra-fine Manganse Dioxide; Form microemulsion through in soluble manganese salt, adding tensio-active agent, add alkali again and generate manganous hydroxide, make the Manganse Dioxide powder of particle diameter at 50nm through oxidation, dehydration, calcining; Chinese patent CN101597086A has announced a kind of method for preparing the different crystal forms nano-manganese dioxide; Adopting potassium permanganate and acid solution is raw material; Under the low temperature (below 200 ℃), prepared the δ type nano-manganese dioxide or the α type nano-manganese dioxide of single crystal form.Different preparing methods can obtain the manganese oxide of different-shape structure, and the chemical property that the manganese oxide of different structure has in ultracapacitor is widely different, return its reason to be that the utilization ratio of poor electric conductivity and active substance of Manganse Dioxide self is low.According to cationic absorption, embed and deviate from mechanism, on the one hand because the electrochemical capacitor behavior mainly betides the upper layer of manganese bioxide electrode material, therefore increase the utilization ratio that specific surface area can effectively improve active substance, thereby obtain bigger specific storage.To the nanometer research of manganese bioxide electrode material, improved the ratio electric capacity of material greatly.On the other hand, because there is cationic embedding in the electrochemistry storage process and deviates from, therefore improve the contact area that porosity can increase active substance and electrolytic solution, thereby improve rate of diffusion and IX speed.Existing result of study shows that mesopore orbit helps the ionic embedding and deviates from, thereby improves IX speed.Though Chinese patent CN101343080A has announced a kind of method for preparing meso-porous titanium dioxide manganese; The method that utilization is peeled off/recombinated; Through cationic assembling, oxidation, sinter process step, prepare have unordered pore passage structure, the homogeneous aperture, than the layered mesoporous Manganse Dioxide of bigger serface and pore volume, but this preparing method's complicated operation; Need specific installation " to have the teflon-lined Pressure solution bullet "; And preparation time is long, and one-period reaches more than 20 days, is not suitable for large-scale production.
Summary of the invention
The present invention is directed to above-mentioned existing in prior technology defective and problem, the technical problem that solve provides a kind of preparation method that technology is simple, raw material is easy to get, cost is low, pollution is little and be easy to handle, be easy to the eco-friendly meso-porous nano Manganse Dioxide of advantages such as industrialization that has.
For solving the problems of the technologies described above, the technical scheme that the present invention adopts is following:
A kind of preparation method of meso-porous nano Manganse Dioxide comprises following concrete steps:
A) prepare D/W and potassium permanganate solution respectively;
B) at room temperature the potassium permanganate solution of preparing is slowly added in the D/W of preparation;
C) continue under the room temperature to stir, become colorless by purple, finish reaction up to reaction soln;
D) filter, cakes with deionized water washing back oven dry promptly gets meso-porous nano Manganse Dioxide.
The glucose in the step a) and the mol ratio of potassium permanganate are recommended as (0.2～0.7): 1.
The concentration of the D/W in the step a) is recommended as 0.005～0.1mol/L.
The concentration of the potassium permanganate solution in the step a) is recommended as 0.1～0.3mol/L.
Alr mode in the step c) can be magnetic agitation, mechanical stirring or ultrasonic dispersing, preferentially recommends ultrasonic dispersing.
Reaction times in the step c) is 1～3 hour.
The method that the present invention adopts is different from traditional template or surfactant method, and it is that the soluble salt with manganese is a raw material, is reductive agent and linking agent with glucose, and deionized water is solvent and pore-forming material.The soluble salt of manganese is bonded the connection of agent glucose and is dispersed in the deionized water, and the soluble salt of manganese and glucose response generate Manganse Dioxide then.Adopt method provided by the present invention; Need not add tensio-active agent; The mol ratio of the volume through changing water and the soluble salt of glucose and manganese can realize the accuracy controlling of aperture and specific surface area, thereby prepares the meso-porous nano Manganse Dioxide aperture homogeneous, high-specific surface area.
Compared with prior art, the present invention has following beneficial effect:
1) not only raw material is easy to get, cost is low, does not produce harmful, toxic chemical substance in the preparation process, pollutes little and is easy to purifying treatment; And reaction conditions is gentle, and the reaction times is short, and only need 1～3 hour a reaction time; Advantages such as it is simple, practical to have technology, can be handling strong are accomplished scale production easily.
2) by preparation method of the present invention can obtain the aperture in 3～15nm, specific surface area at 135～220m
2/ g, impurity cationic (K
+) content (atom number) is less than 0.12 pure a type non-crystalline state meso-porous nano Manganse Dioxide, and unipolar specific storage is at 170～300F/g, enclosed pasture efficient can reach 67%, has demonstrated superior electrochemical capacitor performance, can be used as the electrode materials of ultracapacitor.
Description of drawings
Fig. 1 is the transmission electron microscope picture of embodiment 1 prepared meso-porous nano Manganse Dioxide sample.
Fig. 2 is embodiment 1 prepared meso-porous nano Manganse Dioxide sample (a) and this sample XRD figure at nitrogen atmosphere gained sample (b) behind 400 ℃ of constant temperature 3h.
Fig. 3 is the nitrogen adsorption and the desorption isothermal curve figure of embodiment 1～3 prepared meso-porous nano Manganse Dioxide sample, and wherein: a represents embodiment 1, and b represents embodiment 2, and c represents embodiment 3.
Fig. 4 is the graph of pore diameter distribution of embodiment 1～3 prepared meso-porous nano Manganse Dioxide sample, and wherein: a represents embodiment 1, and b represents embodiment 2, and c represents embodiment 3.
Fig. 5 is the nitrogen adsorption and the desorption isothermal curve figure of embodiment 4～6 prepared meso-porous nano Manganse Dioxide samples, and wherein: a represents embodiment 4, and b represents embodiment 5, and c represents embodiment 6.
Fig. 6 is the nitrogen adsorption and the desorption isothermal curve figure of embodiment 10 prepared meso-porous nano Manganse Dioxide samples.
Fig. 7 is that embodiment 10 prepared meso-porous nano Manganse Dioxide samples are as the cyclic voltammetry curve figure of ultracapacitor in the sodium sulfate electrolyte solution.
The practical implementation method
Below in conjunction with embodiment the present invention is done further in detail, intactly explains, but do not limit content of the present invention.
Under the room temperature, 1.8g (0.01mol) glucose adding 200ml deionized water for stirring is even, be mixed with the D/W that concentration is 0.05mol/L;
Under the room temperature, slowly add the potassium permanganate solution that 100ml concentration is 0.2mol/L while stirring;
Continue under the room temperature to stir 2h, solution is become colorless by purple, finishes reaction;
Filter, cakes with deionized water washing 2～3 times obtains the brown filter cake, and oven dry promptly gets the black manganese dioxide powder.
Fig. 1 is the transmission electron microscope picture of the prepared Manganse Dioxide sample of present embodiment, and visible by Fig. 1: prepared Manganse Dioxide sample is the nano particle of size distribution homogeneous.
Fig. 2 be the prepared Manganse Dioxide sample of present embodiment (a) and this sample nitrogen atmosphere, behind 400 ℃ of constant temperature 3h the XRD figure of gained sample (b); Can show the undefined structure that the prepared Manganse Dioxide sample of present embodiment is a partial crystallization by a among Fig. 2, can show that by the b among Fig. 2 the prepared Manganse Dioxide sample of present embodiment is a type Manganse Dioxide (a-MnO
2).
A curve among Fig. 3 is the nitrogen adsorption and the desorption isothermal curve figure of the prepared meso-porous nano Manganse Dioxide of present embodiment sample; A curve among Fig. 4 is the graph of pore diameter distribution of the prepared meso-porous nano Manganse Dioxide of present embodiment sample.
Learn through calculating: the specific surface area of the prepared Manganse Dioxide sample of present embodiment is 135m
2/ g, the aperture is 3.85nm.
Learn through the atomic absorption spectrum icp analysis: the impurity cationic (K in the prepared Manganse Dioxide sample of present embodiment
+) content (atom number) is less than 0.12.
Embodiment 2
The difference of present embodiment and embodiment 1 only is:
Under the room temperature, 1.8g (0.01mol) glucose adding 500ml deionized water for stirring is even, be mixed with the D/W that concentration is 0.02mol/L.
All the other contents are all with identical described in the embodiment 1.
B curve among Fig. 3 is the nitrogen adsorption and the desorption isothermal curve figure of the prepared meso-porous nano Manganse Dioxide of present embodiment sample; B curve among Fig. 4 is the graph of pore diameter distribution of the prepared meso-porous nano Manganse Dioxide of present embodiment sample.
Learn through calculating: the specific surface area of the prepared Manganse Dioxide sample of present embodiment is 160m
2/ g, the aperture is 4.01nm.
Learn through the atomic absorption spectrum icp analysis: the impurity cationic (K in the prepared Manganse Dioxide sample of present embodiment
+) content (atom number) is less than 0.12.
Embodiment 3
The difference of present embodiment and embodiment 1 only is:
Under the room temperature, 1.8g (0.01mol) glucose adding 700ml deionized water for stirring is even, be mixed with the D/W that concentration is 0.0143mol/L.
All the other contents are all with identical described in the embodiment 1.
C curve among Fig. 3 is the nitrogen adsorption and the desorption isothermal curve figure of the prepared meso-porous nano Manganse Dioxide of present embodiment sample; C curve among Fig. 4 is the graph of pore diameter distribution of the prepared meso-porous nano Manganse Dioxide of present embodiment sample.
Learn through calculating: the specific surface area of the prepared Manganse Dioxide sample of present embodiment is 191m
2/ g, the aperture is 4.25nm.
Learn through the atomic absorption spectrum icp analysis: the impurity cationic (K in the prepared Manganse Dioxide sample of present embodiment
+) content (atom number) is less than 0.12.
Embodiment 4
Under the room temperature, 0.72g (0.004mol) glucose adding 200ml deionized water for stirring is even, be mixed with the D/W that concentration is 0.02mol/L;
Under the room temperature, slowly add the potassium permanganate solution that 100ml concentration is 0.2mol/L while stirring;
Continue under the room temperature to stir 2h, solution is become colorless by purple, finishes reaction;
Filter, cakes with deionized water washing 2～3 times obtains the brown filter cake, and oven dry promptly gets the black manganese dioxide powder.
A curve among Fig. 5 is the nitrogen adsorption and the desorption isothermal curve figure of the prepared meso-porous nano Manganse Dioxide of present embodiment sample.
Learn through calculating: the specific surface area of the prepared Manganse Dioxide sample of present embodiment is 165m
2/ g, the aperture is 6.95nm.
Learn through the atomic absorption spectrum icp analysis: the impurity cationic (K in the prepared Manganse Dioxide sample of present embodiment
+) content (atom number) is less than 0.12.
Embodiment 5
The difference of present embodiment and embodiment 4 only is:
Under the room temperature, 0.72g (0.004mol) glucose adding 500ml deionized water for stirring is even, be mixed with the D/W that concentration is 0.008mol/L.
All the other contents are all with identical described in the embodiment 4.
B curve among Fig. 5 is the nitrogen adsorption and the desorption isothermal curve figure of the prepared meso-porous nano Manganse Dioxide of present embodiment sample.
Learn through calculating: the specific surface area of the prepared Manganse Dioxide sample of present embodiment is 195m
2/ g, the aperture is 7.16nm.
Learn through the atomic absorption spectrum icp analysis: the impurity cationic (K in the prepared Manganse Dioxide sample of present embodiment
+) content (atom number) is less than 0.12.
Embodiment 6
The difference of present embodiment and embodiment 4 only is:
Under the room temperature, 0.72g (0.004mol) glucose adding 700ml deionized water for stirring is even, be mixed with the D/W that concentration is 0.0057mol/L.
All the other contents are all with identical described in the embodiment 4.
C curve among Fig. 5 is the nitrogen adsorption and the desorption isothermal curve figure of the prepared meso-porous nano Manganse Dioxide of present embodiment sample.
Learn through calculating: the specific surface area of the prepared Manganse Dioxide sample of present embodiment is 210m
2/ g, the aperture is 7.36nm.
Learn through the atomic absorption spectrum icp analysis: the impurity cationic (K in the prepared Manganse Dioxide sample of present embodiment
+) content (atom number) is less than 0.12.
Embodiment 7
Under the room temperature, 2.52g (0.014mol) glucose adding 200ml deionized water for stirring is even, be mixed with the D/W that concentration is 0.07mol/L;
Under the room temperature, slowly add the potassium permanganate solution that 100ml concentration is 0.2mol/L while stirring;
Continue under the room temperature to stir 2h, solution is become colorless by purple, finishes reaction;
Filter, cakes with deionized water washing 2～3 times obtains the brown filter cake, and oven dry promptly gets the black manganese dioxide powder.
Learn through calculating: the specific surface area of the prepared Manganse Dioxide sample of present embodiment is 148m
2/ g, the aperture is 3.38nm.
Learn through the atomic absorption spectrum icp analysis: the impurity cationic (K in the prepared Manganse Dioxide sample of present embodiment
+) content (atom number) is less than 0.12.
Embodiment 8
The difference of present embodiment and embodiment 7 only is:
Under the room temperature, 1.44g (0.008mol) glucose adding 200ml deionized water for stirring is even, be mixed with the D/W that concentration is 0.04mol/L.
All the other contents are all with identical described in the embodiment 7.
Learn through calculating: the specific surface area of the prepared Manganse Dioxide sample of present embodiment is 152m
2/ g, the aperture is 6.21nm.
Learn through the atomic absorption spectrum icp analysis: the impurity cationic (K in the prepared Manganse Dioxide sample of present embodiment
+) content (atom number) is less than 0.12.
Embodiment 9
The difference of present embodiment and embodiment 7 only is:
Under the room temperature, 1.08g (0.006mol) glucose adding 200ml deionized water for stirring is even, be mixed with the D/W that concentration is 0.03mol/L.
All the other contents are all with identical described in the embodiment 7.
Learn through calculating: the specific surface area of the prepared Manganse Dioxide sample of present embodiment is 154m
2/ g, the aperture is 7.62nm.
Learn through the atomic absorption spectrum icp analysis: the impurity cationic (K in the prepared Manganse Dioxide sample of present embodiment
+) content (atom number) is less than 0.12.
The difference of present embodiment and embodiment 3 only is:
Alr mode in the preparation process is a ultrasonic dispersing.
All the other contents are all with identical described in the embodiment 3.
Fig. 6 is the nitrogen adsorption and the desorption isothermal curve figure of the prepared meso-porous nano Manganse Dioxide of present embodiment sample.
Learn through calculating: the specific surface area of the prepared Manganse Dioxide sample of present embodiment is 215m
2/ g, the aperture is 5.35nm.
Learn through the atomic absorption spectrum icp analysis: the impurity cationic (K in the prepared Manganse Dioxide sample of present embodiment
+) content (atom number) is less than 0.12.
With the prepared Manganse Dioxide sample of present embodiment is that active substance, acetylene black AB are that static eliminator, polytetrafluoroethylene PTFE are sticker, MnO
2: AB: PTFE (mass ratio)=7: 2: 1, the electrode of making ultracapacitor.Concrete steps are: at first active substance is mixed with acetylene black, fully grinds; Then with ground powder be dissolved in the PTFE thorough mixing among the N-N-methyl-2-2-pyrrolidone N-NMP; After mixing well into pasty state; Evenly coat on the collector nickel foil,, promptly get electrode slice at the dry 12h of 80 ℃ of vacuum drying ovens.With the 1mol/L metabisulfite solution is electrolytic solution, and Ag/AgCl is a reference electrode, and the Pt silk is a counter electrode, forms three-electrode system with electrode slice, in-0.1～0.8V voltage range, carries out the cyclic voltammetric test.Single electrode electric capacity takes formula to calculate:
In the formula: C is a specific capacitance of single electrode, and unit is F/g; Q is an electric weight, and unit is a coulomb; M is the electrode active material quality, and unit is g; Δ E is the current potential width of scanning, and unit is V.
The cyclic voltammetry curve of this ultracapacitor in the sodium sulfate electrolyte solution is as shown in Figure 7, demonstrates superior electrochemical capacitor performance.
Learn through calculating: the specific capacitance of single electrode of this ultracapacitor is 285F/g, and conservation rate is 67.8% (194F/g) under the 50mV/s charge-discharge velocity, and visible this ultracapacitor has higher specific storage and good enclosed pasture efficient.
Claims (3)
1. the preparation method of a meso-porous nano Manganse Dioxide is characterized in that, comprises following concrete steps:
A) prepare D/W and potassium permanganate solution respectively; Wherein: the mol ratio of glucose and potassium permanganate is (0.2～0.7): 1, and the concentration of D/W is 0.005～0.1mol/L, the concentration of potassium permanganate solution is 0.1～0.3mol/L;
B) at room temperature the potassium permanganate solution of preparing is slowly added in the D/W of preparation;
C) continue under the room temperature to stir, become colorless by purple, finish reaction up to reaction soln;
D) filter, cakes with deionized water washing back oven dry promptly gets meso-porous nano Manganse Dioxide.
2. the preparation method of meso-porous nano Manganse Dioxide according to claim 1 is characterized in that: the alr mode in the step c) is magnetic agitation or mechanical stirring.
3. the preparation method of meso-porous nano Manganse Dioxide according to claim 1 is characterized in that: the alr mode in the step c) is a ultrasonic dispersing.
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| CN102867655B (en) * | 2012-10-16 | 2015-08-05 | 桂林电子科技大学 | Ultracapacitor of tubulose meso-porous titanium dioxide manganese and preparation method thereof |
| CN104310486B (en) * | 2014-10-14 | 2015-09-30 | 吉林大学 | A kind of method of one-step synthesis monolayer manganese dioxide nano-plates |
| CN105481018B (en) * | 2016-01-14 | 2018-04-06 | 上海大学 | Adjustable 3D network structures meso-porous titanium dioxide manganese of structure and preparation method thereof |
| CN107500361B (en) * | 2017-09-12 | 2019-12-03 | 黄山学院 | A kind of environment-friendly preparation method thereof of manganese dioxide |
| CN110002501A (en) * | 2019-04-11 | 2019-07-12 | 华东师范大学 | A kind of manganese dioxide electrode material for super capacitor and preparation method and application |
| CN110482610B (en) * | 2019-08-05 | 2022-03-15 | 广东美的白色家电技术创新中心有限公司 | High-purity alpha-MnO with large surface area2Hydrothermal synthesis method |
| CN110302776A (en) * | 2019-08-06 | 2019-10-08 | 河北科技大学 | A kind of confinement growth manganese-based catalyst and preparation method thereof for VOCs catalysis burning |
| CN111533172A (en) * | 2020-05-09 | 2020-08-14 | 上海大学 | Mesoporous manganese dioxide prepared based on biological material and preparation method thereof |
| CN112456560B (en) * | 2020-12-09 | 2023-03-21 | 安徽科技学院 | Preparation method of two-dimensional manganese oxide material formed by self-assembly of nanoparticles |
| CN113797925A (en) * | 2021-09-30 | 2021-12-17 | 佛山市顺德区阿波罗环保器材有限公司 | Formaldehyde removal catalyst and preparation method and application thereof |
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| CN1013434B (en) * | 1988-01-11 | 1991-08-07 | 福建师范大学 | Method for producing chemical manganese dioxide for battery |
| CN1023694C (en) * | 1990-11-21 | 1994-02-09 | 重庆干电池总厂 | Prepn. of manganese dioxide |
| US6465129B1 (en) * | 1998-05-01 | 2002-10-15 | Regents Of The University Of Minnesota | Lithium batteries with new manganese oxide materials as lithium intercalation hosts |
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