CN106745282B - A kind of preparation method with yolk eggshell structure manganese sesquioxide managnic oxide - Google Patents
A kind of preparation method with yolk eggshell structure manganese sesquioxide managnic oxide Download PDFInfo
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- CN106745282B CN106745282B CN201610995500.2A CN201610995500A CN106745282B CN 106745282 B CN106745282 B CN 106745282B CN 201610995500 A CN201610995500 A CN 201610995500A CN 106745282 B CN106745282 B CN 106745282B
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/02—Oxides; Hydroxides
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- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
Abstract
The present invention relates to a kind of preparation method with yolk eggshell structure manganese sesquioxide managnic oxide.Mainly include the following steps that：Manganese salt solution and alkaline agent solution are prepared respectively, according to manganese ion and alkaline reagent mol ratio are 1 after abundant dissolving:(1~8) is added in reaction vessel jointly, stirring, the condensing reflux under microwave-excitation heating condition, manganese carbonate presoma is centrifugally separating to obtain after naturally cooling to room temperature, put it into high temperature furnace and be heat-treated 1~10 hour at a temperature of 200~700 DEG C, cool to room temperature with the furnace and obtain yolk eggshell structure manganese sesquioxide managnic oxide.Preparation method technique of the present invention is simple, and easy to operate, cost is low, has the advantages that controllable preparation, largely synthesizes, beneficial to industrial volume production.
Description
Technical field
The invention belongs to the preparing technical field of metal oxide materials, and in particular to one kind has yolk-eggshell structure
The preparation method of manganese sesquioxide managnic oxide.
Background technology
Manganese sesquioxide managnic oxide is widely used, its high catalytic activity can be used for field of Environment Protection decompose toxic gas, chlorobenzaldehyde,
In the synthesis technique of the organic matters such as p-bromobenzaldehyde, used as high performance oxidant.In addition, manganese sesquioxide managnic oxide can be additionally used in
The electrode material of lithium ion battery negative material and ultracapacitor.
The pattern of material its physical and chemical performance with structures shape.In the last few years, yolk-eggshell structure (yolk-
Shell structure) material due to special nucleus void/shell profile, imparting the excellent performance of material, may move
Nuclear energy reach weight fraction by increasing active material, improve the volume energy density of material.In addition, between core and shell
Space can effectively buffer caused bulk strain in lithium ion insertion/withdrawal process, yolk-eggshell structure has attracted
The very big concern of scientific research personnel.Liquid-phase synthesis process is heated based on advanced microwave, be used to synthesize various nanometer materials in recent years
Material.Method (the China Patent Publication No. that cutting edge of a knife or a sword etc. discloses a kind of synthesizing fluorescent nano particles of rare earth chlorides by microwave aqueous phase is learned in analogy
CNIO1864314A), obtained product grain is uniform in size.Compared with traditional liquid-phase synthesis process, microwave liquid phase synthesis
Method is a kind of simple and environmentally-friendly material synthesis method, can greatly shorten the reaction time, and selectivity heating has different microwave absorptions
The compound of characteristic, homogeneous heating, combined coefficient is high, is adapted to extensive prepare.Simultaneously as far as the applicant is aware, having no up to now
Reported and utilize method of the microwave liquid phase auxiliary synthesis with yolk-eggshell structure manganese sesquioxide managnic oxide.
The content of the invention
The purpose of the present invention is with overcoming above-mentioned prior art to exist the defects of, there is provided convenient, simple, the cheap energy-conservation of one kind
Preparation with yolk-eggshell structure manganese sesquioxide managnic oxide preparation method.For the present invention by a kind of quick, simple microwave method can
Substantial amounts of manganese carbonate presoma is synthesized, by controllable heat treatment in 200~700 DEG C of temperature ranges, due to Ke Kendaer effects occur
Should can directly obtain general 1 micron of diameter has yolk-eggshell structure manganese sesquioxide managnic oxide.
The technical scheme of the preparation method with yolk-eggshell structure manganese sesquioxide managnic oxide of the present invention is as follows：
(1) manganese salt and alkaline reagent are dissolved in hydrophilic solvent respectively, after dissolving in solution manganese ion molar concentration
For 0.05~1.50mol/L, the molar concentration of alkaline reagent is 0.20~6.00mol/L, fully standby after dissolving；
(2) two kinds of solution obtained by step (1) are mixed, mixed proportion is that the mol ratio of manganese ion and alkaline reagent is 1:
(1~8)；The condensing reflux under microwave-excitation heating condition, manganese carbonate presoma is centrifugally separating to obtain after naturally cooling to room temperature；
(3) the manganese carbonate presoma that upper step obtains is put into high temperature furnace at a temperature of 200~700 DEG C and is heat-treated 1~10
Hour, cool to room temperature with the furnace and obtain yolk-eggshell structure manganese sesquioxide managnic oxide.
Above-described manganese salt is：Mixing more than one or both of manganese chloride, manganese nitrate, manganese acetate, manganese sulfate
Salt；The alkaline reagent is：Mixed base more than one or both of urea, sodium hydroxide, ammoniacal liquor, ammonium hydrogen carbonate；It is described
Hydrophilic agent is：One or both of deionized water, ethanol, ethylene glycol, isopropanol, normal propyl alcohol, n-butanol, isobutanol with
On mixed solvent.
Obtained yolk-eggshell structure manganese sesquioxide managnic oxide material morphology produced according to the present invention is homogeneous, good dispersion, can use
In lithium ion battery material, ultracapacitor active material and catalyst.In addition, the microwave liquid phase synthesis that the present invention uses
Method, reaction time is short, and reaction yield is high, and cost is low, and process route is simple, and energy consumption is low, is adapted to industrial volume production.
Brief description of the drawings
Fig. 1 is the X-ray diffractogram (XRD) of manganese sesquioxide managnic oxide in the embodiment of the present invention 1.
Fig. 2 is the scanning electron microscope diagram (SEM) of manganese sesquioxide managnic oxide in the embodiment of the present invention 1.
Fig. 3 is the high resolution transmission electron microscopy (TEM) of manganese sesquioxide managnic oxide in the embodiment of the present invention 1.
Embodiment
From following examples it will be further appreciated that the present invention, but the claimed scope of the invention is not limited to following reality
Apply the express ranges of example.
Embodiment 1
(1) manganese nitrate and urea are dissolved in deionized water respectively, the molar concentration of manganese ion is in solution after dissolving
1mol/L, the molar concentration of urea is 1mol/L, fully standby after dissolving；
(2) two kinds of solution obtained by step (1) are mixed, mixed proportion is that the mol ratio of manganese ion and urea is 1:3；
Condensing reflux 60 minutes, carbonic acid is centrifugally separating to obtain after naturally cooling to room temperature under the microwave-excitation heating condition that power is 700W
Manganese presoma；
(3) the manganese carbonate presoma that upper step obtains is put into high temperature furnace and be heat-treated 5 hours at a temperature of 400 DEG C, with stove
It is cooled to room temperature and obtains yolk-eggshell structure manganese sesquioxide managnic oxide.
Fig. 1 is the X ray diffracting spectrum with yolk-eggshell structure manganese sesquioxide managnic oxide obtained by the present embodiment, is analyzed
The crystal structure of material.Fig. 2 is the scanning electron microscope diagram piece for having yolk-eggshell structure manganese sesquioxide managnic oxide, can from figure
See, obtained material morphology and size ratio are more uniform, good dispersion.Fig. 3 is that the present embodiment preparation has yolk-eggshell structure
The transmission electron micrograph of manganese sesquioxide managnic oxide, obtained material show yolk-eggshell structure.
Embodiment 2
(1) manganese acetate and sodium hydroxide are dissolved in deionized water and ethylene glycol respectively, manganese ion in solution after dissolving
Molar concentration is 0.1mol/L, and the molar concentration of sodium hydroxide is 0.5mol/L, fully standby after dissolving；
(2) two kinds of solution obtained by step (1) are mixed, mixed proportion is that the mol ratio of manganese ion and sodium hydroxide is 1:
1；In the case where power is 700W microwave-excitation heating condition, condensing reflux 60 minutes, is centrifugally separating to obtain after naturally cooling to room temperature
Manganese carbonate presoma；
(3) the manganese carbonate presoma that upper step obtains is put into high temperature furnace and be heat-treated 6 hours at a temperature of 450 DEG C, with stove
It is cooled to room temperature and obtains yolk-eggshell structure manganese sesquioxide managnic oxide.
Embodiment 3
(1) manganese sulfate and sodium hydroxide are dissolved in deionized water and isopropanol respectively, manganese ion in solution after dissolving
Molar concentration is 0.2mol/L, and the molar concentration of sodium hydroxide is 0.5mol/L, fully standby after dissolving；
(2) two kinds of solution obtained by step (1) are mixed, mixed proportion is that the mol ratio of manganese ion and sodium hydroxide is 1:
2；In the case where power is 700W microwave-excitation heating condition, condensing reflux 60 minutes, is centrifugally separating to obtain after naturally cooling to room temperature
Manganese carbonate presoma；
(3) the manganese carbonate presoma that upper step obtains is put into high temperature furnace and be heat-treated 3 hours at a temperature of 500 DEG C, with stove
It is cooled to room temperature and obtains yolk-eggshell structure manganese sesquioxide managnic oxide.
Embodiment 4
(1) manganese chloride and ammonium hydrogen carbonate are dissolved in deionized water and normal propyl alcohol respectively, manganese ion in solution after dissolving
Molar concentration is 1mol/L, and the molar concentration of ammonium hydrogen carbonate is 2mol/L, fully standby after dissolving；
(2) two kinds of solution obtained by step (1) are mixed, mixed proportion is that the mol ratio of manganese ion and ammonium hydrogen carbonate is 1:
3；In the case where power is 700W microwave-excitation heating condition, condensing reflux 60 minutes, is centrifugally separating to obtain after naturally cooling to room temperature
Manganese carbonate presoma；
(3) the manganese carbonate presoma that upper step obtains is put into high temperature furnace and be heat-treated 6 hours at a temperature of 300 DEG C, with stove
It is cooled to room temperature and obtains yolk-eggshell structure manganese sesquioxide managnic oxide.
Embodiment 5
(1) manganese acetate and urea are dissolved in deionized water and ethylene glycol respectively, after dissolving in solution manganese ion mole
Concentration is 1.2mol/L, and the molar concentration of urea is 3mol/L, fully standby after dissolving；
(2) two kinds of solution obtained by step (1) are mixed, mixed proportion is that the mol ratio of manganese ion and urea is 1:4；
Condensing reflux 60 minutes, carbonic acid is centrifugally separating to obtain after naturally cooling to room temperature under the microwave-excitation heating condition that power is 700W
Manganese presoma；
(3) the manganese carbonate presoma that upper step obtains is put into high temperature furnace and be heat-treated 1 hour at a temperature of 600 DEG C, with stove
It is cooled to room temperature and obtains yolk-eggshell structure manganese sesquioxide managnic oxide.
Embodiment 6
(1) manganese sulfate and sodium hydroxide are dissolved in deionized water and n-butanol respectively, manganese ion in solution after dissolving
Molar concentration is 0.2mol/L, and the molar concentration of sodium hydroxide is 1mol/L, fully standby after dissolving；
(2) two kinds of solution obtained by step (1) are mixed, mixed proportion is that the mol ratio of manganese ion and sodium hydroxide is 1:
5；In the case where power is 700W microwave-excitation heating condition, condensing reflux 60 minutes, is centrifugally separating to obtain after naturally cooling to room temperature
Manganese carbonate presoma；
(3) the manganese carbonate presoma that upper step obtains is put into high temperature furnace and be heat-treated 2 hours at a temperature of 700 DEG C, with stove
It is cooled to room temperature and obtains yolk-eggshell structure manganese sesquioxide managnic oxide.
Embodiment 7
(1) manganese nitrate and ammonium hydrogen carbonate are dissolved in ethylene glycol and isobutanol respectively, manganese ion rubs in solution after dissolving
Your concentration is 0.2mol/L, and the molar concentration of sodium hydroxide is 1mol/L, fully standby after dissolving；
(2) two kinds of solution obtained by step (1) are mixed, mixed proportion is that the mol ratio of manganese ion and ammonium hydrogen carbonate is 1:
4；In the case where power is 700W microwave-excitation heating condition, condensing reflux 60 minutes, is centrifugally separating to obtain after naturally cooling to room temperature
Manganese carbonate presoma；
(3) the manganese carbonate presoma that upper step obtains is put into high temperature furnace and be heat-treated 5 hours at a temperature of 400 DEG C, with stove
It is cooled to room temperature and obtains yolk-eggshell structure manganese sesquioxide managnic oxide.
Embodiment 8
(1) manganese sulfate and sodium hydroxide are dissolved in ethylene glycol and n-butanol respectively, manganese ion rubs in solution after dissolving
Your concentration is 0.5mol/L, and the molar concentration of sodium hydroxide is 2mol/L, fully standby after dissolving；
(2) two kinds of solution obtained by step (1) are mixed, mixed proportion is that the mol ratio of manganese ion and sodium hydroxide is 1:
5；In the case where power is 700W microwave-excitation heating condition, condensing reflux 60 minutes, is centrifugally separating to obtain after naturally cooling to room temperature
Manganese carbonate presoma；
(3) the manganese carbonate presoma that upper step obtains is put into high temperature furnace and be heat-treated 8 hours at a temperature of 300 DEG C, with stove
It is cooled to room temperature and obtains yolk-eggshell structure manganese sesquioxide managnic oxide.
Claims (4)
1. a kind of preparation method with yolk-eggshell structure manganese sesquioxide managnic oxide, comprises the following steps：
(1) by manganese salt and the alkaline reagent of carbanion be provided be dissolved in respectively in hydrophilic solvent, after dissolving in solution manganese from
The molar concentration of son be 0.05~1.50mol/L, there is provided the molar concentration of the alkaline reagent of carbanion for 0.20~
It is standby after 6.00mol/L, fully dissolving；
(2) two kinds of solution obtained by step (1) are mixed, mixed proportion is alkaline reagent of the manganese ion with providing carbanion
Mol ratio be 1:(1~8)；The condensing reflux under microwave-excitation heating condition, it is centrifugally separating to obtain after naturally cooling to room temperature
Manganese carbonate presoma；
(3) the manganese carbonate presoma that upper step obtains is put into high temperature furnace and is heat-treated 1~10 hour at a temperature of 200~700 DEG C,
Cool to room temperature with the furnace and obtain yolk-eggshell structure manganese sesquioxide managnic oxide.
2. preparation method as claimed in claim 1, it is characterised in that：The soluble manganese salt is manganese chloride, manganese nitrate, acetic acid
Salt-mixture more than one or both of manganese, manganese sulfate.
3. preparation method as claimed in claim 1, it is characterised in that：The alkaline reagent for providing carbanion is urine
Mixed base more than one or both of element, sodium acid carbonate, ammonium hydrogen carbonate.
4. preparation method as claimed in claim 1, it is characterised in that：The hydrophilic agent is deionized water, ethanol, second two
Mixed solvent more than one or both of alcohol, isopropanol, normal propyl alcohol, n-butanol, isobutanol.
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| CN109019694B (en) * | 2018-10-25 | 2020-10-23 | 中国科学院青海盐湖研究所 | Micro-nano structure spherical MnCO3Preparation method of (1) |
| CN109279656B (en) * | 2018-10-25 | 2020-11-10 | 中国科学院青海盐湖研究所 | Micro-nano mesoporous spherical Mn2O3Preparation method of (1) |
| CN109482175B (en) * | 2018-11-23 | 2020-12-22 | 华南理工大学 | Manganese-potassium ore type manganese dioxide catalyst with yolk-shell structure and preparation method and application thereof |
| CN110078111B (en) * | 2019-04-19 | 2020-03-17 | 西安交通大学 | Metal oxide nano-particles with adjustable components and yolk-eggshell structure and preparation method thereof |
| CN115872451A (en) * | 2022-11-19 | 2023-03-31 | 杭州电子科技大学 | Preparation method of sulfur-free spherical manganese carbonate powder |
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| CN103521205A (en) * | 2013-10-10 | 2014-01-22 | 上海大学 | Method of preparing core-shell structure TiO2 material with high photocatalytic activity |
| CN103816897B (en) * | 2014-03-11 | 2015-11-18 | 中国科学院合肥物质科学研究院 | Titanium dioxide-Yin complex nucleus shell structure ball and its production and use |
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