CN106395908A - Preparation method of bamboo joint structure Mn2O3 - Google Patents
Preparation method of bamboo joint structure Mn2O3 Download PDFInfo
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- CN106395908A CN106395908A CN201610804036.4A CN201610804036A CN106395908A CN 106395908 A CN106395908 A CN 106395908A CN 201610804036 A CN201610804036 A CN 201610804036A CN 106395908 A CN106395908 A CN 106395908A
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- C—CHEMISTRY; METALLURGY
- 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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- 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
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
Abstract
The invention provides a preparation method of bamboo joint structure Mn2O3. According to the method, at first, rod-metal organic framework material Mn-MOF precursors are prepared by a guide agent assisting solvent volatilization method; then, in the air environment, the Mn-MOF precursors are calcined; the calcining temperature is controlled to be 400 to 650 DEG C; the time is 2 to 4h; finally, the materials are cooled to the room temperature along with the furnace temperature; the bamboo joint structure Mn2O3 nanometer structure materials can be obtained. The method provided by the invention has the advantages that the operation is simple; the process cost is low; the appearance is regular; the product stability is high, and the like. The industrial production is facilitated. The bamboo joint structure Mn2O3 nanometer structure material obtained by the method has the advantages of good conductivity and great specific surface area; the electrode resistance can be favorably reduced; the materials can be used for supercapacitor electrode materials.
Description
Technical field
The invention belongs to materialogy field, it is related to a kind of electrode material of ultracapacitor, specifically a kind of ring
Structure Mn2O3Preparation method.
Background technology
With social development further, environment and energy problem become increasingly to project.Therefore people are in the urgent need to one
Plant environmental friendliness and continuable energy storage form.Ultracapacitor, as new cleaning fuel element, has widely
Application and huge potential market, be also subject to the extensive concern of national governments and enterprise.According to energy storage principle not
Double layer capacitor and pseudocapacitors can be divided into, ultracapacitor, the electrode material of pseudocapacitors have metal-oxide and
Conducting polymer two class.As the Typical Representative of metal-oxide, the preparation method of manganese oxide nanometer material, construction featuress and anti-
Principle is answered to be people's key problem of interest.It is generally acknowledged that produce considerable influence to material property is the knot of substance crystals
Structure, therefore, the different crystal forms prepared using distinct methods, the manganese oxide nanometer material of different-shape will have different property
Energy.Prepare manganese oxide at present and mostly be the method such as hydro-thermal method, the sedimentation method, sol-gel, these method conditions are harsh, and obtain
Product is easily reunited, and causes maldistribution of precipitation etc., leads to product specific capacity relatively low, and be unfavorable for high power discharge and recharge
Therefore, patent of the present invention explores the preparation method of synthesis manganese oxide nanometer material, and its tool is of great significance.
Metal-organic framework coordination compound (metal-organic frameworks, MOFs), is also called porous polycomplexation
Compound (porous coordination polymers, PCPs), is often referred to metal ion or metal cluster and is passed through with organic ligand
Self assembling process is formed has the crystalline material of periodicity infinite network structure, and therefore it has had both organic polymer and inorganization
The feature of both compounds.As the new porous material of a class, specific surface area is big, structure diversity, duct chi because having for MOFs
Very little adjustable and the advantages of skeleton can be modified, it is widely used in catalyst, adsorbing separation, the storage of gas and photoelectromagnetic material etc. each
Individual field.
In recent years, MOFs material constantly extends as the research in ultracapacitor, due to their controlled micropore chi
Very little (0.6-2 nanometer) and huge surface area, MOFs material is used for preparing the new template of porous metal oxide.
Disclose a kind of preparation method of super-capacitor manganese oxide material in patent CN101950686A, prepared by this method
Manganese oxide there is nano bar-shape structure, high specific surface area and the distribution of uniform space, excellent chemical property, but adopt
Prepared with hydro-thermal method, morphology controllable is low, condition is harsh.Chinese patent CN101851008A potassium permanganate is dissolved in N, N- bis-
In methylformamide, alkali formula manganese oxide nanometer rods are obtained by solvent thermal reaction, but method is with substantial amounts of DMF
For solvent, big for environment pollution.A kind of method preparing inorganic oxide manganese nanometer rods is disclosed in patent CN104878469A,
This method has operation and preparation process is simple using electrostatic spinning technique preparation manganese oxide nanometer material, and experiment condition is gentle, shape
The advantages of looks controlled diameter, but electrostatic spinning is difficult to obtain nano material separated from one another;Second, current electrostatic spinning machine
Yield is very low;3rd, the intensity of electrostatic spinning nano fiber is relatively low.
Content of the invention
For above-mentioned technical problem of the prior art, the invention provides a kind of bamboo joint structure Mn2O3Preparation method,
Described this bamboo joint structure Mn2O3Preparation method to solve method of the prior art preparation manganese oxide specific capacity relatively low,
It is unfavorable for the technical problem of high power discharge and recharge.
The invention provides a kind of bamboo joint structure Mn2O3Preparation method, comprise the steps：
1）One step preparing bar-shaped metal-organic framework materials Mn-MOF presoma；
A) trimesic acid is dissolved in the ethanol solution that volume fraction is 50%, be configured to solution concentration be 0.02～
The trimesic acid solution of 0.08mol/L；
B) four water manganese acetates are dissolved in the ethanol solution that volume fraction is 50% so that solution concentration be 0.01～
0.04mol/L；
C) and then weigh directed agents, described directed agents are Polyvinylpyrrolidone, Macrogol 600 and emulsifying agent alkyl polyoxy
The combination of ethylene (10) ether (OP-10), the quality of described directed agents is the 2～8% of acetic acid manganese solution；Wherein, polyvinyl pyrrole
The mass ratio of alkanone, Macrogol 600 and emulsifying agent alkyl polyoxyethylene (10) ether (OP-10) three is（2～6）:（1～3）:
（1～3）；
D) step a) and solution b) with volume ratio are（1～3）:After 1 is mixed, add the solution of step c), finally will
Mixed solution proceeds in water heating kettle, reacts 24～72h, gained reactant liquor sucking filtration, the anhydrous second of gained filter cake at 80～90 DEG C
Alcohol centrifugation, washing, then be vacuum dried in 60～80 DEG C of baking ovens, that is, obtain Mn-MOF presoma；
2）Under air ambient, calcine 1）Gained Mn-MOF presoma, control programming rate is 2～4 DEG C/min, and calcining heat is
400～650 DEG C, the time is 2～4 h, finally drops to room temperature with stove, obtains bamboo joint structure Mn2O3Material.
Emulsifying agent alkyl polyoxyethylene (10) ether (OP-10) that the present invention adopts is a kind of commercially available industrial chemicals, is alkane
Base phenol and the condensation substance of oxirane, have excellent emulsifying, moistening, diffusion, antistatic behaviour.
The present invention prepares before bar-shaped metal-organic framework materials Mn-MOF initially with directed agents secondary solvent volatility process
Drive body；Then under air ambient, calcine Mn-MOF presoma, control calcining heat to be 400～650 DEG C, the time is 2～4h,
Finally drop to room temperature with stove, you can obtain bamboo joint structure Mn2O3Nano structural material.One aspect of the present invention, nanostructured has very
High specific surface area, is conducive to the specific capacity improving manganese sesquioxide managnic oxide, the effective rate of utilization improving material；On the other hand, one-dimensional
Bamboo joint structure is conducive to improving electric conductivity between the electric conductivity in one-dimensional square and increase granule for the material, finally improves electrode
The performance of material.
The present invention prepares MOF presoma using the solvent thermal process that directed agents assist, and the growth for MOF for the directed agents provides
Structure directing, Mn-MOF is along in macromolecule chain longitudinal direction determinate growth, it is easy to accomplish the club shaped structure control of Mn-MOF
System；The frame structure passing through MOF afterwards acts on to the confinement of central ion, can obtain central ion oxidation by simple roasting
Thing, effective control calcining heat, time can obtain bamboo joint structure Mn2O3.Instant invention overcomes directly prepared club shaped structure in the past
Harsh conditions in structural adjustment, preparation method is simple to operate, process costs are low, and easy to operate, morphology controllable, beneficial to industrialization
Produce, and the bamboo joint structure Mn being obtained by the inventive method2O3Nano structural material has good electric conductivity and larger ratio
Surface area, is conducive to reducing electrode resistance, can be used for electrode material for super capacitor.
Novelty of the present invention proposes first to prepare the Mn-MOF presoma with club shaped structure using directed agents, by framework
Structure confinement effect, was calcined by the later stage, obtained the Mn of one-dimensional bamboo joint structure structure2O3Nano material.This preparation method make use of
Metal-organic framework（MOF）The template action of material, part therein is sintered, and realizes central ion oxidation, and keeps
Former MOF structure.The Mn of preparation2O3There is high-specific surface area, being remarkably improved the diffusive migration speed of electronics and ion, thus carrying
High specific capacitance.
The present invention compares with prior art, and its technological progress is significant.The invention provides one kind is with the organic bone of metal
The method that frame material prepares bamboo joint structure metal manganese oxide nanometer material for template, the product of this method preparation will not be reunited, technique
Simply, flow process is short, product quality is stable, be easy to industrialized production, and scale is easy to control, and the Mn with bamboo joint structure synthesizing2O3
Nano material has good chemical property.
Brief description
Fig. 1 is the scanning electron microscope (SEM) photograph of the manganese sesquioxide managnic oxide material that embodiment 1 is obtained 1-dimention nano bamboo joint structure.
Fig. 2 is the XRD spectra of the manganese sesquioxide managnic oxide material of embodiment 1 gained 1-dimention nano chain.
Specific embodiment
Embodiment 1
The invention provides a kind of bamboo joint structure Mn2O3Preparation method, comprise the steps：
1) step that directed agents secondary solvent volatility process prepares bar-shaped metal-organic framework materials Mn-MOF presoma；Including as follows
Step：
A) trimesic acid is dissolved in the ethanol solution that volume fraction is 50%, being configured to solution concentration is 0.04mol/L
Trimesic acid solution；
B) four water manganese acetates are dissolved in the ethanol solution that volume fraction is 50% so that solution concentration is 0.02mol/L；
C) and then weigh directed agents, described directed agents are Polyvinylpyrrolidone, Macrogol 600, emulsifying agent alkyl polyoxy
Ethylene (10) ether (OP-10), its quality is the 3% of acetic acid manganese solution；Wherein, Polyvinylpyrrolidone, Macrogol 600 and breast
The mass ratio of agent alkyl polyoxyethylene (10) ether (OP-10) three is 2:1:1；
D) by a) and b) solution with volume ratio for 2:After 1 is mixed, add c) solution, proceed in water heating kettle；In 80 DEG C of baking ovens
Middle reaction 24h, the white precipitate dehydrated alcohol centrifuge washing of gained, filtration, it is vacuum dried in 80 DEG C of baking ovens, obtained final product
To Mn-MOF presoma.
）Under air ambient, calcine 1）Gained Mn-MOF presoma, control programming rate is 3 DEG C/min, and calcining heat is
400 DEG C, the time is 2h, finally drops to room temperature with stove, obtains chain Mn2O3Nano structural material.
The preparation of manganese oxide electrode：By manganese oxide, carbon black and ptfe emulsion in mass ratio 7:2:1 ratio mixing
Uniformly, it is tuned into pulpous state, and even application, in nickel foam, is pressed into piece with powder compressing machine 15MPa pressure, then by electrode slice
Put into 60 DEG C of vacuum drying ovens and be vacuum dried 24 h.With saturated calomel electrode as reference electrode, it is to electrode with platinum plate electrode.
Chemical property using CHI660E model electrochemical workstation test sample.With constant current charge charging method in 0.5Ag-1
Under electric current density, recording than electric capacity is 245Fg-1.
Embodiment 2
The invention provides a kind of bamboo joint structure Mn2O3Preparation method, comprise the steps：
1) step that directed agents secondary solvent volatility process prepares bar-shaped metal-organic framework materials Mn-MOF presoma；Including as follows
Step：
A) trimesic acid is dissolved in the ethanol solution that volume fraction is 50%, being configured to solution concentration is 0.04mol/L
Trimesic acid solution；
B) four water manganese acetates are dissolved in the ethanol solution that volume fraction is 50% so that solution concentration is 0.02mol/L；
C) and then weigh directed agents, described directed agents are Polyvinylpyrrolidone, Macrogol 600, emulsifying agent alkyl polyoxy
Ethylene (10) ether (OP-10), its quality is the 3% of acetic acid manganese solution；Wherein, Polyvinylpyrrolidone, Macrogol 600 and breast
The mass ratio of agent alkyl polyoxyethylene (10) ether (OP-10) three is 2:1:1；
D) by a) and b) solution with volume ratio for 2:After 1 is mixed, add c) solution, proceed in water heating kettle；In 80 DEG C of baking ovens
Middle reaction 24h, the white precipitate dehydrated alcohol centrifuge washing of gained, filtration, it is vacuum dried in 80 DEG C of baking ovens, that is,
Obtain Mn-MOF presoma.
2）Under air ambient, calcine 1）Gained Mn-MOF presoma, control programming rate is 3 DEG C/min, calcining heat
For 500 DEG C, the time is 2 h, finally drops to room temperature with stove, obtains chain Mn2O3Nano structural material.
The preparation of manganese oxide electrode：By manganese oxide, carbon black and ptfe emulsion in mass ratio 7:2:1 ratio mixing
Uniformly, it is tuned into pulpous state, and even application, in nickel foam, is pressed into piece with powder compressing machine 15MPa pressure, then by electrode slice
Put into 60 DEG C of vacuum drying ovens and be vacuum dried 24 h.With saturated calomel electrode as reference electrode, it is to electrode with platinum plate electrode.
Chemical property using CHI660E model electrochemical workstation test sample.With constant current charge charging method in 0.5Ag-1
Under electric current density, recording than electric capacity is 310Fg-1.
Embodiment 3
The invention provides a kind of bamboo joint structure Mn2O3Preparation method, comprise the steps：
1) step that directed agents secondary solvent volatility process prepares bar-shaped metal-organic framework materials Mn-MOF presoma；Including as follows
Step：
A) trimesic acid is dissolved in the ethanol solution that volume fraction is 50%, being configured to solution concentration is 0.04mol/L
Trimesic acid solution；
B) four water manganese acetates are dissolved in the ethanol solution that volume fraction is 50% so that solution concentration is 0.02mol/L；
C) and then weigh directed agents, described directed agents are Polyvinylpyrrolidone, Macrogol 600, emulsifying agent alkyl polyoxy
Ethylene (10) ether (OP-10), its quality is the 3% of acetic acid manganese solution；Wherein, Polyvinylpyrrolidone, Macrogol 600 and breast
The mass ratio of agent alkyl polyoxyethylene (10) ether (OP-10) three is 2:1:1；
D) by a) and b) solution with volume ratio for 2:After 1 is mixed, add c) solution, proceed in water heating kettle；In 80 DEG C of baking ovens
Middle reaction 24h, the white precipitate dehydrated alcohol centrifuge washing of gained, filtration, it is vacuum dried in 80 DEG C of baking ovens, that is,
Obtain Mn-MOF presoma.
2）Under air ambient, calcine 1）Gained Mn-MOF presoma, control programming rate is 3 DEG C/min, calcining heat
For 570 DEG C, the time is 2h, finally drops to room temperature with stove, obtains chain Mn2O3Nano structural material.
The preparation of manganese oxide electrode：By manganese oxide, carbon black and ptfe emulsion in mass ratio 7:2:1 ratio mixing
Uniformly, it is tuned into pulpous state, and even application, in nickel foam, is pressed into piece with powder compressing machine 15MPa pressure, then by electrode slice
Put into 60 DEG C of vacuum drying ovens and be vacuum dried 24 h.With saturated calomel electrode as reference electrode, it is to electrode with platinum plate electrode.
Chemical property using CHI660E model electrochemical workstation test sample.With constant current charge charging method in 0.5Ag-1
Under electric current density, recording than electric capacity is 350Fg-1.
Claims (1)
1. a kind of bamboo joint structure Mn2O3Preparation method it is characterised in that comprising the steps：
1）One step preparing bar-shaped metal-organic framework materials Mn-MOF presoma；
A) trimesic acid is dissolved in the ethanol solution that volume fraction is 50%, be configured to solution concentration be 0.02～
The trimesic acid solution of 0.08mol/L；
B) four water manganese acetates are dissolved in the ethanol solution that volume fraction is 50% so that solution concentration be 0.01～
0.04mol/L；
C) and then weigh directed agents, described directed agents are Polyvinylpyrrolidone, Macrogol 600 and alkyl polyoxyethylene
(10) combination of ether, the quality of described directed agents is the 2～8% of four water manganese acetate solution qualities；Wherein, polyvinylpyrrolidine
The mass ratio of ketone, Macrogol 600 and alkyl polyoxyethylene (10) ether three is（2～6）:（1～3）:（1～3）；
D) by step a) and solution b) with volume ratio for 1～3:After 1 is mixed, add the solution of step c), finally will mix
Close solution to proceed in water heating kettle, react 24～72h, gained reactant liquor sucking filtration, gained filter cake dehydrated alcohol at 80～90 DEG C
Centrifugation, washing, then be vacuum dried in 60～80 DEG C of baking ovens, that is, obtain Mn-MOF presoma；
2）Under air ambient, calcine 1）Gained Mn-MOF presoma, control programming rate is 2～4 DEG C/min, and calcining heat is
400～650 DEG C, the time is 2～4 h, finally drops to room temperature with stove, obtains bamboo joint structure Mn2O3Material.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106865618A (en) * | 2017-02-23 | 2017-06-20 | 广西大学 | One kind " peanut shape " Mn2O3The preparation method of/C particles |
| CN108133834A (en) * | 2017-12-27 | 2018-06-08 | 信阳师范学院 | A kind of nickel foam is the MOFs-Mn of substrate2O3The preparation method of electrode material for super capacitor |
| CN110836921A (en) * | 2019-12-02 | 2020-02-25 | 青岛大学 | Preparation method of nano electrochemical aptamer sensor for detecting stress-induced phosphoprotein |
| CN113184962A (en) * | 2021-03-26 | 2021-07-30 | 宿州学院 | Mn (manganese)2O3Preparation method of/PANI composite electrode material and application of PANI composite electrode material in hybrid capacitor deionization technology |
| CN115155566A (en) * | 2022-06-16 | 2022-10-11 | 桂林理工大学 | Metal oxide material and preparation method and application thereof |
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| CN102557143A (en) * | 2010-12-07 | 2012-07-11 | 海洋王照明科技股份有限公司 | Preparation method of Mn2O3 and catalyst |
| CN105347402A (en) * | 2015-11-12 | 2016-02-24 | 安徽师范大学 | Mn2O3, preparing method thereof and applications of the Mn2O3 in ORR |
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| CN102557143A (en) * | 2010-12-07 | 2012-07-11 | 海洋王照明科技股份有限公司 | Preparation method of Mn2O3 and catalyst |
| CN105347402A (en) * | 2015-11-12 | 2016-02-24 | 安徽师范大学 | Mn2O3, preparing method thereof and applications of the Mn2O3 in ORR |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106865618A (en) * | 2017-02-23 | 2017-06-20 | 广西大学 | One kind " peanut shape " Mn2O3The preparation method of/C particles |
| CN106865618B (en) * | 2017-02-23 | 2018-05-04 | 广西大学 | One kind " peanut shape " Mn2O3The preparation method of/C particles |
| CN108133834A (en) * | 2017-12-27 | 2018-06-08 | 信阳师范学院 | A kind of nickel foam is the MOFs-Mn of substrate2O3The preparation method of electrode material for super capacitor |
| CN110836921A (en) * | 2019-12-02 | 2020-02-25 | 青岛大学 | Preparation method of nano electrochemical aptamer sensor for detecting stress-induced phosphoprotein |
| CN110836921B (en) * | 2019-12-02 | 2020-05-08 | 青岛大学 | Preparation method of nano electrochemical aptamer sensor for detecting stress-induced phosphoprotein |
| CN113184962A (en) * | 2021-03-26 | 2021-07-30 | 宿州学院 | Mn (manganese)2O3Preparation method of/PANI composite electrode material and application of PANI composite electrode material in hybrid capacitor deionization technology |
| CN115155566A (en) * | 2022-06-16 | 2022-10-11 | 桂林理工大学 | Metal oxide material and preparation method and application thereof |
| CN115155566B (en) * | 2022-06-16 | 2023-11-28 | 桂林理工大学 | Metal oxide material and preparation method and application thereof |
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