CN103440996A - Method for preparing nanometer manganous-manganic oxide/carbon composite energy storage material - Google Patents
Method for preparing nanometer manganous-manganic oxide/carbon composite energy storage material Download PDFInfo
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- CN103440996A CN103440996A CN2013103949574A CN201310394957A CN103440996A CN 103440996 A CN103440996 A CN 103440996A CN 2013103949574 A CN2013103949574 A CN 2013103949574A CN 201310394957 A CN201310394957 A CN 201310394957A CN 103440996 A CN103440996 A CN 103440996A
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Abstract
The invention discloses a method for preparing a nanometer manganous-manganic oxide/carbon composite energy storage material. The method comprises the steps that potassium permanganate is reacted with oleic acid in the ratio of 100:1 (g/L) in an aqueous solution, obtained solid substances are dispersed in alcohol solvent, single substance iodine is added into the aqueous solution according to the mass ratio of 0-2:1, and the solid substances are dissolved. The solution reaction time is 12 hours-48 hours in a reaction kettle at the temperature of 120 DEG C to 200 DEG C. After centrifugal separation, washing and drying are conducted, the manganous-manganic oxide/carbon composite energy storage material is obtained. The method can be conducted on the low temperature and non-alkaline conditions and is simple in technology and low in energy consumption. Meanwhile, the super capacitive property of the manganous-manganic oxide/carbon composite energy storage material obtained according to the method is remarkably improved.
Description
Technical field
The present invention relates to the inorganic non-metal composite material technical field, particularly relate to the preparation method of a kind of nano manganic manganous oxide/carbon composite energy-storage material.
Background technology
With material with carbon element, compare, the mangano-manganic oxide energy storage material has the advantages such as specific capacity is large, energy density is high, corrosion-resistant, simultaneously because of characteristics such as aboundresources, cheap, low toxicities, at new energy field, has obtained increasing attention.But the conductivity of mangano-manganic oxide is low, the electronics transfer impedance while in electrolyte, redox reaction occurring is large, causes its actual specific capacity far below theoretical specific capacity.Usually mangano-manganic oxide and material with carbon element are carried out to the compound conductivity that improves material, thus increase substantially specific capacity and cycle performance (Journal of Power Sources, 2002,104:52-61).(the ACS Applied Materials& such as Yin Longwei; Interfaces, 2012,4:1636-1642) reported that making presoma, ethylene glycol with a water manganese acetate is that nucleator, polyvinylpyrrolidone are made the synthetic mangano-manganic oxide/carbon composite of carbon source two steps: at first 180 ℃ of lower hydro-thermal reactions 48 hours, sintering 4 hours in 700 ℃ of lower blanket of nitrogen again, its shortcoming is complex process, need high temperature, energy consumption is large.Chinese patent CN101901916A has reported a kind of preparation method of carbon-carried manganese tetraoxide: at first in water, with carbon black, adsorb manganese nitrate, dry rear 400 ℃ of constant temperature 3 hours, obtain the carbon-carried manganese tetraoxide composite material after grinding, its shortcoming is to generate nitrogen oxide gas after manganese nitrate decomposes to be easy to environment, and needs greater energy consumption.(the Chemistry-A European Journal such as Wang Zhilin, 2013,19,7084-7089) reported with manganese sesquioxide managnic oxide to be that presoma, glucose are 180 ℃ of lower hydro-thermal reactions of carbon source 12 hours, 30 minutes synthetic mangano-manganic oxide/carbon composites of 400 ℃ of constant temperature in argon atmospher again, its shortcoming is also high temperature, and synthetic by the method mangano-manganic oxide/specific capacity of carbon hybrid supercapacitor material when 1A/g is only 174F/g.
Summary of the invention
In order to overcome above-mentioned the deficiencies in the prior art, the invention provides the method for a kind of synthesis of nano mangano-manganic oxide/carbon composite energy-storage material.The technical solution adopted in the present invention is:
The mangano-manganic oxide presoma adopted is potassium permanganate;
The solvent heat medium and the carbon source that adopt are one or more in methyl alcohol, ethanol, propyl alcohol;
Adopt iodine to control carbon content and mangano-manganic oxide degree of crystallinity;
The mass ratio of iodine and manganese dioxide is 0-2: 1.
Potassium permanganate is reacted according to the ratio of 100: 1 (g/L) with oleic acid in the aqueous solution, the solid product obtained is scattered in alcoholic solvent, according to 0～2: 1 mass ratio adds iodine and dissolves.By mixed material in reactor 120～200 ℃ carry out solvent thermal reaction 12～48 hours.Centrifugation, obtain nano manganic manganous oxide/carbon composite after lease making washing, drying.
Compared with prior art, solvent heat synthesizes target nano manganic manganous oxide/carbon composite energy-storage material at a lower temperature in the present invention, and without process high temperature sintering and carbon activation step, energy consumption is low; The mangano-manganic oxide size of microcrystal is less than 100nm.The iodine of the method reaction needed can be recycled, without noxious gas emission.Simultaneously, the synthetic composite material of the method has excellent super capacitor performance.
The accompanying drawing explanation
X-ray diffraction (XRD) collection of illustrative plates that Fig. 1 is nano manganic manganous oxide/carbon (20%) composite material;
ESEM (SEM) figure that Fig. 2 is nano manganic manganous oxide/carbon (20%) composite material;
X-ray diffraction (XRD) collection of illustrative plates that Fig. 3 is nano manganic manganous oxide/carbon (7%) composite material;
ESEM (SEM) figure that Fig. 4 is nano manganic manganous oxide/carbon (7%) composite material;
First charge-discharge curve during 0.2A/g that Fig. 5 is nano manganic manganous oxide/carbon composite
Fig. 6 is mangano-manganic oxide and mangano-manganic oxide/carbon composite high rate performance comparison curves.
Embodiment
Embodiment 1: the preparation of nano manganic manganous oxide/carbon (20%) composite material
50 milliliters of oleic acid are under agitation slowly joined in the liquor potassic permanganate of 1.5 liters of 0.04mol/L.After room temperature reaction 24 hours, by solid filtering, washing, the drying obtained.Take the above-mentioned product of 0.3 gram, add 100 milliliters of absolute ethyl alcohols, ultrasonic dispersion.Then solution is transferred in reactor, under 160 ℃, reaction is 24 hours.Centrifugation obtains product after washing, drying.Product X ray powder diffraction spectrogram (Fig. 1) conforms to hausmannite type mangano-manganic oxide standard spectrogram (JCPDS No.24-0734), but occurs the wide diffraction maximum of agraphitic carbon near 20 °; Diffraction maximum is wider, shows that crystal grain is less, calculates average grain diameter through the Scherrer formula and is about 11.4nm.Be irregular particle by the visible mangano-manganic oxide/material with carbon element of scanning electron microscope (SEM) photograph (Fig. 2), agglomeration is arranged, elementary analysis shows in material to contain 20% carbon.
Embodiment 2: the preparation of nano manganic manganous oxide/carbon (7%) composite material
Take the solid intermediate product that 0.3 gram embodiment 1 obtains, add 100 milliliters of absolute ethyl alcohols, ultrasonic dispersion.The mass ratio that is 1: 1 according to iodine/manganese dioxide adds 0.3 gram iodine and dissolves.Then solution is transferred in reactor, under 160 ℃, reaction is 24 hours.Centrifugation obtains nano manganic manganous oxide/carbon composite after washing, drying.X-ray powder diffraction spectrogram (Fig. 3) is consistent with hausmannite type mangano-manganic oxide standard spectrogram (JCPDS No.24-0734); With the product of embodiment 1, compare, it is sharp-pointed that diffraction maximum becomes, and shows that degree of crystallinity improves, and calculating average grain diameter through the Scherrer formula is 27nm.This is because the carbon generated in reaction reduces, and has reduced the inhibitory action to the mangano-manganic oxide grain growth, causes size of microcrystal to become large, but, also because the carbon that grain surface coats reduces, makes on the contrary the composite material granular particle diameter become less, sees Fig. 4.Results of elemental analyses shows that the material phosphorus content is 7%, and the product obtained with embodiment 1 has relatively reduced 13%, and this conforms to the XRD test result.
Embodiment 3: mangano-manganic oxide and mangano-manganic oxide/carbon composite electrochemical property test
At room temperature test the electrochemical properties of pure mangano-manganic oxide and mangano-manganic oxide/carbon composite with three-electrode system, wherein reference electrode is saturated calomel electrode, and auxiliary electrode is platinum electrode.The metabisulfite solution that electrolyte is 1mol/L.Adopt blue electric CT2001A type battery test system to carry out the constant current charge-discharge test, voltage range is 0-1.0V.Result is as follows:
(1) as seen from Figure 5, by the current density of 0.2A/g, discharge and recharge, the specific capacity of mangano-manganic oxide/carbon that phosphorus content is 7% and 20% is respectively as 218.2F/g and 207.8F/g.Voltage curve over time has mirror symmetry well, and illustrative material has electrochemical reversibility and excellent cycle performance well.
(2) as shown in Figure 6,, under different current densities, the specific capacity of mangano-manganic oxide/carbon composite is all higher than the specific capacity of pure mangano-manganic oxide.Along with the increase of current density, pure mangano-manganic oxide specific discharge capacity decay is very fast; Mangano-manganic oxide/carbon composite presents good heavy-current discharge characteristic, and specific capacity is still up to 180F/g when 5A/g for the specific capacity of the composite material that especially carbon content is 7%, and the specific capacity during than 0.2A/g only decays 17%.
(3) under less current density, during as 0.2A/g, electrolyte can fully permeate carbon coating layer and infiltrate and react to material internal and mangano-manganic oxide, and the composite material specific capacity of different phosphorus content is very approaching.But along with the increase of current density, electrolyte can not permeate to granule interior well, thereby causes the decline of specific capacity, and the composite material that wherein phosphorus content is 20% shows more obviously because carbon coating layer is thicker.Therefore carry out phosphorus content and the carbon-coating thickness in controlled material by adding iodine, can reach the purpose of the super capacitor energy-storage performance of optimizing material.
Claims (5)
1. the preparation method of nano manganic manganous oxide/carbon composite energy-storage material, its concrete steps are:
Potassium permanganate is reacted according to the ratio of 100: 1 (g/L) with oleic acid in the aqueous solution, the solid product obtained is scattered in alcoholic solvent, according to 0～2: 1 mass ratio adds iodine and dissolves.Then above-mentioned solution is reacted 12～48 hours under (compactedness 60～80%) 120～200 ℃ in reactor.Centrifugation obtains mangano-manganic oxide/carbon composite after washing, drying.
2. the preparation method of a kind of nano manganic manganous oxide according to claim 1/carbon composite energy storage material year siccative, is characterized in that described alcoholic solvent is one or more in methyl alcohol, ethanol, propyl alcohol.
3. the preparation method of a kind of nano manganic manganous oxide according to claim 1/carbon composite energy-storage material, is characterized in that coming phosphorus content in controlled material and the degree of crystallinity of mangano-manganic oxide by adding iodine, thereby optimize the energy-storage property of material.
4. the preparation method of a kind of nano manganic manganous oxide according to claim 1/carbon composite energy-storage material, is characterized in that the average crystal grain particle diameter of mangano-manganic oxide in composite material is less than 100nm.
5. the preparation method of a kind of nano manganic manganous oxide according to claim 1/carbon composite energy-storage material, described energy storage material is by the described method preparation of power 1.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106098403A (en) * | 2016-08-17 | 2016-11-09 | 华中科技大学 | A kind of ultracapacitor, negative pole and preparation method thereof |
| CN110518230A (en) * | 2019-09-24 | 2019-11-29 | 吉林大学 | The preparation method of lithium ion battery negative material |
| CN111495385A (en) * | 2020-04-24 | 2020-08-07 | 山东师范大学 | Flower cluster-shaped Fe3O4@MnO2And preparation method and application thereof |
| CN112387271A (en) * | 2020-11-16 | 2021-02-23 | 湖南大学 | Carbon-coated manganous-manganic oxide composite material and preparation method and application thereof |
| CN114229904A (en) * | 2021-12-06 | 2022-03-25 | 桂林理工大学 | Mn for water-based zinc ion battery2O3/Mn3O4Preparation method of composite electrode material |
| CN114345322A (en) * | 2022-01-13 | 2022-04-15 | 贵州民族大学 | Carbon-supported manganese oxide catalyst and preparation method thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106098403A (en) * | 2016-08-17 | 2016-11-09 | 华中科技大学 | A kind of ultracapacitor, negative pole and preparation method thereof |
| CN106098403B (en) * | 2016-08-17 | 2018-07-24 | 华中科技大学 | A kind of ultracapacitor, cathode and preparation method thereof |
| CN110518230A (en) * | 2019-09-24 | 2019-11-29 | 吉林大学 | The preparation method of lithium ion battery negative material |
| CN111495385A (en) * | 2020-04-24 | 2020-08-07 | 山东师范大学 | Flower cluster-shaped Fe3O4@MnO2And preparation method and application thereof |
| CN111495385B (en) * | 2020-04-24 | 2023-02-24 | 山东师范大学 | Flower cluster-shaped Fe 3 O 4 @MnO 2 And preparation method and application thereof |
| CN112387271A (en) * | 2020-11-16 | 2021-02-23 | 湖南大学 | Carbon-coated manganous-manganic oxide composite material and preparation method and application thereof |
| CN112387271B (en) * | 2020-11-16 | 2022-08-12 | 湖南大学 | Carbon-coated manganous-manganic oxide composite material and preparation method and application thereof |
| CN114229904A (en) * | 2021-12-06 | 2022-03-25 | 桂林理工大学 | Mn for water-based zinc ion battery2O3/Mn3O4Preparation method of composite electrode material |
| CN114229904B (en) * | 2021-12-06 | 2023-06-23 | 桂林理工大学 | Mn for water-based zinc ion battery 2 O 3 /Mn 3 O 4 Preparation method of composite electrode material |
| CN114345322A (en) * | 2022-01-13 | 2022-04-15 | 贵州民族大学 | Carbon-supported manganese oxide catalyst and preparation method thereof |
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Application publication date: 20131211 |