CN106395908B - A kind of bamboo joint structure Mn2O3Preparation method - Google Patents
A kind of bamboo joint structure Mn2O3Preparation method Download PDFInfo
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- CN106395908B CN106395908B CN201610804036.4A CN201610804036A CN106395908B CN 106395908 B CN106395908 B CN 106395908B CN 201610804036 A CN201610804036 A CN 201610804036A CN 106395908 B CN106395908 B CN 106395908B
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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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- 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 kind of bamboo joint structure Mn2O3Preparation method, bar-shaped metal-organic framework materials Mn MOF presomas are prepared using directed agents secondary solvent volatility process first；Then under air ambient, Mn MOF presomas are calcined, it is 400~650 DEG C to control calcining heat, and the time is 2~4h, finally drops to room temperature with stove, you can obtain bamboo joint structure Mn2O3Nano structural material.The method of the present invention has the advantages that simple to operate, process costs are low, pattern is regular, product stability good, beneficial to industrialized production.The bamboo joint structure Mn obtained by the method for the present invention2O3Nano structural material has good electric conductivity and larger specific surface area, is conducive to reducing electrode resistance, available for electrode material for super capacitor.
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 the further development of society, environment and energy problem become more and more prominent.Therefore people are in the urgent need to one
Plant environment-friendly and sustainable energy storage form.Ultracapacitor is as new cleaning fuel element, with widely
Application field and huge potential market, also by the extensive concern of national governments and enterprise.According to energy storage principle not
Together, ultracapacitor can be divided into double layer capacitor and pseudocapacitors, the electrode materials of pseudocapacitors have metal oxide and
The class of conducting polymer two.As the Typical Representative of metal oxide, the preparation method of manganese oxide nanometer material, design feature and anti-
It is people's key problem of interest to answer principle.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 are by with different property
Energy.It is generally the methods such as hydro-thermal method, the precipitation method, sol-gel to prepare manganese oxide at present, and these method conditions are harsh, and obtain
Product is easily reunited, and is caused the distribution of precipitation uneven etc., is caused 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 complex (metal-organic frameworks, MOFs), also known as porous polycomplexation
Compound (porous coordination polymers, PCPs), is often referred to metal ion or metal cluster and passes through with organic ligand
Crystalline material of the self assembling process formation with periodicity infinite network structure, therefore it has had both organic polymer and inorganization
The characteristics of both compounds.As the new porous material of a class, MOFs is because with specific surface area is big, structure diversity, duct chi
The advantages of very little adjustable and skeleton can be modified, is widely used in catalyst, adsorbing separation, the storage of gas and photoelectromagnetic material etc. each
Individual field.
In recent years, MOFs materials have constantly extended as the research in ultracapacitor, due to their controllable micropore chi
Very little (0.6-2 nanometers) and huge surface area, MOFs materials are used for the new template for preparing porous metal oxide.
A kind of preparation method of super-capacitor manganese oxide material is disclosed 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 is dissolved in N, N- bis- with potassium permanganate
Alkali formula manganese oxide nanometer rods are obtained by solvent thermal reaction in NMF, but method is with substantial amounts of DMF
It is big for environment pollution for solvent.A kind of method for preparing inorganic oxide manganese nanometer rods is disclosed in patent CN104878469A,
This method prepares manganese oxide nanometer material using electrostatic spinning technique has operation simple with preparation technology, and experiment condition is gentle, shape
The advantages of looks controlled diameter, but electrostatic spinning is difficult to the nano material separated each other;Second, current electrostatic spinning machine
Yield is very low;3rd, the intensity of electrostatic spinning nano fiber is relatively low.
The 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 manganese oxide specific capacity prepared by method of the prior art 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 following steps：
1）One the step of prepare bar-shaped metal-organic framework materials Mn-MOF presomas；
A) trimesic acid is dissolved in the ethanol solution that volume fraction is 50%, be configured to solution concentration for 0.02~
0.08mol/L trimesic acid solution；
B) by four water manganese acetates be dissolved in volume fraction be 50% ethanol solution in so that solution concentration be 0.01~
0.04mol/L；
C) directed agents are weighed and then, described directed agents are polyvinylpyrrolidone, Macrogol 600 and emulsifying agent alkyl
The combination of polyoxyethylene (10) ether (OP-10), the quality of described directed agents is the 2~8% of acetic acid manganese solution；Wherein, polyethylene
The mass ratio of pyrrolidones, Macrogol 600 and emulsifying agent alkyl polyoxyethylene (10) ether (OP-10) three is（2~6）:（1
~3）:（1~3）；
D) solution by step a) and b) using volume ratio as（1~3）:After 1 is mixed, step c) solution is added, most
Mixed solution is transferred in water heating kettle afterwards, 24~72h, gained reaction solution suction filtration, gained filter cake nothing are reacted at 80~90 DEG C
Water-ethanol centrifugation, washing, then be dried in vacuo in 60~80 DEG C of baking ovens, that is, obtain Mn-MOF presomas；
2）Under air ambient, calcining 1）Gained Mn-MOF presomas, it is 2~4 DEG C/min, calcining temperature to control programming rate
Spend for 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 is used is a kind of commercially available industrial chemicals, is alkane
The condensation product of base phenol and oxirane, with excellent emulsification, wetting, diffusion, antistatic behaviour.
The present invention is prepared before bar-shaped metal-organic framework materials Mn-MOF using directed agents secondary solvent volatility process first
Drive body；Then under air ambient, Mn-MOF presomas are calcined, it is 400~650 DEG C to control calcining heat, the time is 2~4h,
Finally room temperature is dropped to 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 improving the specific capacity of manganese sesquioxide managnic oxide, improves the effective rate of utilization of material；On the other hand, it is one-dimensional
Bamboo joint structure is conducive to improving the electric conductivity between electric conductivity and increase particle of the material in one-dimensional square, finally improves electrode
The performance of material is played.
The solvent thermal process that the present invention is aided in using directed agents prepares MOF presomas, and directed agents provide for MOF growth
Structure directing, Mn-MOF is along in macromolecule chain longitudinal direction determinate growth, it is easy to accomplish Mn-MOF club shaped structure control
System；The confinement by MOF frame structure to central ion is acted on afterwards, and central ion oxidation can be obtained by being simply calcined
Thing, effectively controls calcining heat, time to obtain bamboo joint structure Mn2O3.Instant invention overcomes directly prepare club shaped structure in the past
Harsh conditions in structural adjustment, preparation method is simple to operate, process costs are low, easy to operate, morphology controllable, beneficial to industrialization
Production, and the bamboo joint structure Mn obtained by the inventive method2O3Nano structural material has good electric conductivity and larger ratio
Surface area, is conducive to reducing electrode resistance, available for electrode material for super capacitor.
Innovative proposition of the invention first prepares the Mn-MOF presomas with club shaped structure using directed agents, passes through framework
Structure confinement effect, is calcined by the later stage, obtains 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 that central ion is aoxidized, and keep
Former MOF structures.The Mn of preparation2O3With high-specific surface area, the diffusive migration speed of electronics and ion is remarkably improved, so as to carry
High specific capacitance.
The present invention is compared with prior art, and its technological progress is significant.The invention provides one kind with the organic bone of metal
Frame material is the method that template prepares bamboo joint structure metal manganese oxide nanometer material, and product prepared by the method will not reunite, technique
Simply, flow is short, product quality is stable, be easy to industrialized production, and scale is easy to control, and the Mn with bamboo joint structure of synthesis2O3
Nano material has good chemical property.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph for the manganese sesquioxide managnic oxide material that 1-dimention nano bamboo joint structure is made in embodiment 1.
Fig. 2 is the XRD spectra of the manganese sesquioxide managnic oxide material of the gained 1-dimention nano chain of embodiment 1.
Embodiment
Embodiment 1
The invention provides a kind of bamboo joint structure Mn2O3Preparation method, comprise the following steps：
1) the step of directed agents secondary solvent volatility process prepares bar-shaped metal-organic framework materials Mn-MOF presomas；Including
Following steps：
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) directed agents are weighed and then, described directed agents are polyvinylpyrrolidone, Macrogol 600, emulsifying agent alkyl
Polyoxyethylene (10) ether (OP-10), its quality is the 3% of acetic acid manganese solution；Wherein, polyvinylpyrrolidone, Macrogol 600
Mass ratio with emulsifying agent alkyl polyoxyethylene (10) ether (OP-10) three is 2:1:1；
D) by a) and b) solution using volume ratio as 2:After 1 is mixed, c) solution is added, is transferred in water heating kettle；At 80 DEG C
24h is reacted in baking oven, the white precipitate absolute ethyl alcohol centrifuge washing of gained, filtering are dried in vacuo in 80 DEG C of baking ovens,
Obtain Mn-MOF presomas.
）Under air ambient, calcining 1）Gained Mn-MOF presomas, it is 3 DEG C/min to control programming rate, 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, pulpous state is tuned into, and even application is in nickel foam, is pressed into piece with 15MPa pressure with powder compressing machine, then by electrode slice
It is put into 60 DEG C of vacuum drying chambers and is dried in vacuo 24 h.Using saturated calomel electrode as reference electrode, using platinum plate electrode as to electrode.
Utilize the chemical property of CHI660E model electrochemical workstation test samples.With constant current charge charging method in 0.5Ag-1
Under current density, specific capacitance is measured for 245Fg-1。
Embodiment 2
The invention provides a kind of bamboo joint structure Mn2O3Preparation method, comprise the following steps：
1) the step of directed agents secondary solvent volatility process prepares bar-shaped metal-organic framework materials Mn-MOF presomas；Including
Following steps：
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) directed agents are weighed and then, described directed agents are polyvinylpyrrolidone, Macrogol 600, emulsifying agent alkyl
Polyoxyethylene (10) ether (OP-10), its quality is the 3% of acetic acid manganese solution；Wherein, polyvinylpyrrolidone, Macrogol 600
Mass ratio with emulsifying agent alkyl polyoxyethylene (10) ether (OP-10) three is 2:1:1；
D) by a) and b) solution using volume ratio as 2:After 1 is mixed, c) solution is added, is transferred in water heating kettle；At 80 DEG C
24h is reacted in baking oven, the white precipitate absolute ethyl alcohol centrifuge washing of gained, filtering carry out vacuum dry in 80 DEG C of baking ovens
It is dry, that is, obtain Mn-MOF presomas.
2）Under air ambient, calcining 1）Gained Mn-MOF presomas, it is 3 DEG C/min, calcining heat to control programming rate
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, pulpous state is tuned into, and even application is in nickel foam, is pressed into piece with 15MPa pressure with powder compressing machine, then by electrode slice
It is put into 60 DEG C of vacuum drying chambers and is dried in vacuo 24 h.Using saturated calomel electrode as reference electrode, using platinum plate electrode as to electrode.
Utilize the chemical property of CHI660E model electrochemical workstation test samples.With constant current charge charging method in 0.5Ag-1
Under current density, specific capacitance is measured for 310Fg-1。
Embodiment 3
The invention provides a kind of bamboo joint structure Mn2O3Preparation method, comprise the following steps：
1) the step of directed agents secondary solvent volatility process prepares bar-shaped metal-organic framework materials Mn-MOF presomas；Including
Following steps：
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) directed agents are weighed and then, described directed agents are polyvinylpyrrolidone, Macrogol 600, emulsifying agent alkyl
Polyoxyethylene (10) ether (OP-10), its quality is the 3% of acetic acid manganese solution；Wherein, polyvinylpyrrolidone, Macrogol 600
Mass ratio with emulsifying agent alkyl polyoxyethylene (10) ether (OP-10) three is 2:1:1；
D) by a) and b) solution using volume ratio as 2:After 1 is mixed, c) solution is added, is transferred in water heating kettle；At 80 DEG C
24h is reacted in baking oven, the white precipitate absolute ethyl alcohol centrifuge washing of gained, filtering carry out vacuum dry in 80 DEG C of baking ovens
It is dry, that is, obtain Mn-MOF presomas.
2）Under air ambient, calcining 1）Gained Mn-MOF presomas, it is 3 DEG C/min, calcining heat to control programming rate
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, pulpous state is tuned into, and even application is in nickel foam, is pressed into piece with 15MPa pressure with powder compressing machine, then by electrode slice
It is put into 60 DEG C of vacuum drying chambers and is dried in vacuo 24 h.Using saturated calomel electrode as reference electrode, using platinum plate electrode as to electrode.
Utilize the chemical property of CHI660E model electrochemical workstation test samples.With constant current charge charging method in 0.5Ag-1
Under current density, specific capacitance is measured for 350Fg-1。
Claims (1)
1. a kind of bamboo joint structure Mn2O3Preparation method, it is characterised in that comprise the following steps：
1）One the step of prepare bar-shaped metal-organic framework materials Mn-MOF presomas；
A) trimesic acid is dissolved in the ethanol solution that volume fraction is 50%, be configured to solution concentration for 0.02~
0.08mol/L trimesic acid solution；
B) by four water manganese acetates be dissolved in volume fraction be 50% ethanol solution in so that solution concentration be 0.01~
0.04mol/L；
C) directed agents are weighed and then, described directed agents are polyvinylpyrrolidone, Macrogol 600 and emulsifier op-10
Combination, the quality of described directed agents is the 2~8% of four water manganese acetate solution qualities；Wherein, polyvinylpyrrolidone, poly- second two
Alcohol 600 and the mass ratio of emulsifier op-10 three are（2~6）:（1~3）:（1~3）；
D) solution by step a) and b) is using volume ratio as 1~3:After 1 is mixed, step c) solution is added, finally will be mixed
Close solution to be transferred in water heating kettle, 24~72h, gained reaction solution suction filtration, gained filter cake absolute ethyl alcohol are reacted at 80~90 DEG C
Centrifugation, washing, then be dried in vacuo in 60~80 DEG C of baking ovens, that is, obtain Mn-MOF presomas；
2) under air ambient, calcining 1）Gained Mn-MOF presomas, it is 2~4 DEG C/min, calcining heat to control programming rate
For 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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| 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 |
| 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 |
| 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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| CN102557143B (en) * | 2010-12-07 | 2015-03-18 | 海洋王照明科技股份有限公司 | Preparation method of Mn2O3 and catalyst |
| CN105347402B (en) * | 2015-11-12 | 2017-01-18 | 安徽师范大学 | Mn2O3, preparing method thereof and applications of the Mn2O3 in ORR |
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