CN109659145A - A method of preparing porous spherical manganese oxide/carbon complex - Google Patents
A method of preparing porous spherical manganese oxide/carbon complex Download PDFInfo
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- CN109659145A CN109659145A CN201811545328.6A CN201811545328A CN109659145A CN 109659145 A CN109659145 A CN 109659145A CN 201811545328 A CN201811545328 A CN 201811545328A CN 109659145 A CN109659145 A CN 109659145A
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- manganese oxide
- fluosite
- aminophenyl
- ball
- oxide precursor
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- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 title claims abstract description 145
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 42
- -1 m-aminophenyl Chemical group 0.000 claims abstract description 39
- 150000001875 compounds Chemical class 0.000 claims abstract description 29
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 15
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 239000006185 dispersion Substances 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 238000013021 overheating Methods 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 22
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 21
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 claims description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- 229940018563 3-aminophenol Drugs 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 6
- 239000011572 manganese Substances 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 238000003763 carbonization Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical group [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 4
- 238000005255 carburizing Methods 0.000 claims description 3
- 230000014759 maintenance of location Effects 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 abstract 1
- 239000002131 composite material Substances 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 10
- 229920001568 phenolic resin Polymers 0.000 description 6
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 5
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 4
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 239000000908 ammonium hydroxide Substances 0.000 description 4
- 239000011565 manganese chloride Substances 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- JXNCBISRWFPKJU-UHFFFAOYSA-N acetic acid;manganese Chemical compound [Mn].CC(O)=O JXNCBISRWFPKJU-UHFFFAOYSA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000006193 liquid solution Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 229940099607 manganese chloride Drugs 0.000 description 2
- 235000002867 manganese chloride Nutrition 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- RMGKEMOPXZNHJG-UHFFFAOYSA-N 2-aminophenol;formaldehyde Chemical compound O=C.NC1=CC=CC=C1O RMGKEMOPXZNHJG-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 230000005264 electron capture Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
Porous spherical manganese oxide/carbon complex method is prepared the present invention relates to a kind of, the following steps are included: 1) certain density manganese oxide precursor is added in the dispersion liquid of m-aminophenyl fluosite ball, a few hours are stirred, m-aminophenyl fluosite ball/manganese oxide precursor compound is obtained after centrifuge separation；2) it by the resulting m-aminophenyl fluosite ball of step 1)/manganese oxide precursor compound, is put into standing in baking oven and is heat-treated for a period of time；3) by m-aminophenyl fluosite ball/manganese oxide precursor compound through Overheating Treatment in a nitrogen atmosphere high temperature cabonization to get porous spherical manganese oxide/carbon complex；Compared with the existing technology, this method is simply mild by the present invention, can adjust the size of the content of manganese oxide and compound mesopore volume in compound by the concentration of the precursor of change manganese, and apparatus and process is simple, low in cost, the period is shorter, and yield is higher.
Description
[technical field]
The invention belongs to technical field of material, specifically a kind of to prepare porous spherical manganese oxide/carbon complex
Method.
[background technique]
Supercapacitor also known as electrochemical capacitor rely primarily on electric double layer and redox fake capacitance (the counterfeit electricity of faraday
Hold) charge storage electric energy.Supercapacitor is the energy storage device between conventional capacitor and secondary cell, while having electricity concurrently
The advantage that container power density is big and secondary cell energy density is high, with power density is high, charge/discharge speed is fast, environment is friendly
Get well, have extended cycle life, good reversibility, wide, highly-safe and at low cost use temperature range the features such as.
Manganese dioxide specific capacitance with higher is a kind of important Electrode Materials in Electrochemical Supercapacitors, still
As metal oxide, the electric conductivity of itself is poor.And porous spherical manganese oxide/carbon complex is special because of its unique structure
Property, it is highly beneficial to the specific surface area and energy density and electric conductivity that improve supercapacitor, thus widely paid close attention to.
C/MnO2Composite material can improve the electric conductivity of electrode material, thus in the electrode material of preparation supercapacitor
In, manganese oxide is usually prepared into carbon/manganese oxide compound.C/MnO2There are many composite material and preparation method thereofs, such as growth in situ
Method, coprecipitation, hydro-thermal method, electrodeposition process etc..
C/MnO2There are many kinds of composite material patterns, and different-shape influences the different physical and chemical properties of sample.Wherein,
Spherical porous oxidation manganese/carbon composite has lower density, high-specific surface area and good electron capture ability etc., causes
More concerns of people.Currently, patent and manganese oxide reported in the literature/carbon composite material preparation method are mainly infusion process,
Porous carbon is first synthesized, is then impregnated the solution such as the precursor of manganese such as potassium permanganate, then high-temperature roasting, carbon/oxidation is obtained
Manganese composite materials.But it is reported in terms of the preparation of porous spherical manganese oxide/carbon complex less.
[summary of the invention]
Present invention aim to solve above-mentioned deficiency and provide a kind of to prepare porous spherical manganese oxide/carbon complex
Method, this method is simply mild, can adjust containing for manganese oxide in compound by changing the concentration of manganese oxide precursor
The size of amount and compound mesopore volume, and it is low in cost, the period is shorter, and yield is higher.
It designs to achieve the above object and a kind of prepares porous spherical manganese oxide/carbon complex method, comprising the following steps:
1) certain density manganese oxide precursor is added in the dispersion liquid of m-aminophenyl fluosite ball, stirs a few hours, from
M-aminophenyl fluosite ball/manganese oxide precursor compound is obtained after heart separation；2) by the resulting m-aminophenyl of step 1)
Fluosite ball/manganese oxide precursor compound is put into standing in baking oven and is heat-treated for a period of time；3) at will be through overheat
M-aminophenyl fluosite ball/manganese oxide precursor compound of reason in a nitrogen atmosphere high temperature cabonization to get porous spherical
Manganese oxide/carbon complex.
Further, in step 1), the manganese oxide precursor is one or two kinds of mixtures of manganese acetate, manganese chloride.
Further, in step 1), the concentration of the manganese oxide precursor is 0.2~2.0mol.L-1。
Further, in step 1), volume and the m-aminophenyl fluosite ball of the manganese oxide precursor solution
Mass ratio is 10~30:1.
Further, in step 2), the temperature of the heat treatment is 40-200 degree, and the processing time is 2-24 hours.
Further, in step 3), the carburizing temperature under nitrogen atmosphere is 600-800 degree, and retention time is 2-4 hours.
Further, above-mentioned preparation method comprises the following specific steps that:
1) it first by m-aminophenol and formaldehyde according to equimolar ratio, is added in the ammonia spirit that pH is 9~11, stirring 24
After hour, filtering obtains m-aminophenyl fluosite ball, is then distributed to a certain amount of m-aminophenyl fluosite ball
In deionized water, manganese oxide precursor is added, volume is pressed between manganese oxide precursor solution and m-aminophenyl fluosite ball
Mass ratio is 10~30:1, after stirring 10~24 hours, centrifuge separation, before obtaining m-aminophenyl fluosite ball/manganese oxide
Body compound；
2) then m-aminophenyl fluosite ball/manganese oxide precursor compound is put into the baking oven of 40-200 degree,
Heating is taken out after 2~24 hours；
3) again compound is continued to be put into Muffle furnace, is first warming up in a nitrogen atmosphere under 600-800 degree and keeps 2~4
Hour carbonization, to get porous spherical manganese oxide/carbon complex after cooling.
The present invention compared with the existing technology, by the way that the precursor of manganese is added to freshly prepd amino-phenol formaldehyde resin ball
Aqueous dispersions in, filtered after stirring a few hours, be then put into baking oven and stand a period of time, then place it under nitrogen atmosphere
High temperature cabonization obtains porous spherical manganese oxide/carbon complex, and this method is simply mild, can pass through the precursor of change manganese
Concentration adjust the size of the content of manganese oxide and compound mesopore volume in compound, and apparatus and process is simple, cost
Cheap, the period is shorter, and yield is higher, is worthy of popularization.
[Detailed description of the invention]
Fig. 1 is the scanning electron microscope (SEM) photograph of obtained porous spherical manganese oxide/carbon composite material in embodiment 1；
Fig. 2 is the scanning electron microscope (SEM) photograph of obtained porous spherical manganese oxide/carbon composite material in embodiment 2.
[specific embodiment]
Porous spherical manganese oxide/carbon complex method is prepared the present invention provides a kind of, including the following steps: will be certain
The manganese oxide precursor of concentration is added in m-aminophenyl fluosite ball dispersion liquid, stirring a period of time, then centrifugation point
M-aminophenyl fluosite ball/manganese oxide precursor compound is obtained from after；By m-aminophenyl fluosite ball/manganese oxide
Precursor compound is put into placement in the baking oven of certain temperature and is heat-treated for a period of time；It will be through amino between Overheating Treatment
Phenol formaldehyde resin ball/manganese oxide precursor compound high temperature cabonization in a nitrogen atmosphere, it is multiple to obtain porous spherical manganese oxide/carbon
Close object.Wherein, the type of manganese oxide precursor be manganese acetate, manganese chloride one or two kinds of mixtures, concentration be 0.2~
2.0mol.L-1；The mass ratio of the volume (0.5~2.0) of manganese oxide precursor solution and m-aminophenyl fluosite is 10~
30:1；For the temperature of heat treatment in 40-200 degree, handling the time is 2-24 hours；Carburizing temperature under nitrogen atmosphere is 600-800
Degree, retention time are 2-4 hours.
The above-mentioned more specific step of preparation method are as follows: m-aminophenol and formaldehyde are first added to pH according to equimolar ratio
It, then will be a certain amount of in 9~11 ammonia spirit, after stirring 24 hours, filtering obtains spherical m-aminophenyl fluosite
Resin balls be distributed in deionized water, be added manganese oxide precursor such as concentration be 0.2~2.0mol.L-1Acetic acid manganese solution
Deng, between the manganese oxide precursor solution being added and m-aminophenyl fluosite ball, according to volume mass ratio be 10~30:
After 1, stirring 10~24 hours, centrifuge separation obtains macromolecule resin ball/manganese oxide precursor composition compound.Then will
The compound of macromolecule resin ball/manganese oxide precursor composition is put into heated 2~24 hours in the baking oven of 40-200 degree after take out.
Again resulting compound is continued to be put into Muffle furnace, is first warming up under 600-800 degree and is kept for 2~4 hours in a nitrogen atmosphere
Carbonization, finally obtains porous spherical manganese oxide/carbon complex.
The present invention is made combined with specific embodiments below further explained below:
Embodiment 1
(1) preparation of m-aminophenyl fluosite ball: toward 30 containing 24 grams of deionized waters and 10 milliliters of dehydrated alcohols
It spends in solution and 2.0 gram 25% of ammonium hydroxide is added, be added 0.71 gram of m-aminophenol, after stirring and dissolving, 35% formaldehyde is then added
1.0 grams of solution, continue stirring 24 hours, centrifuge separation；Sample is 12 hours dry in 50 degree of baking oven；By ammonia between 0.5 gram
Base phenol formaldehyde resin ball is distributed in 20 milliliters of water, and 15 milliliters of 0.5mol.L are added-1Manganese acetate；In this way, body before manganese oxide
The volume of liquid solution and the mass ratio of m-aminophenyl fluosite are 30:1, and stirring is taken out after 24 hours.
(2) it is put into 40 degree of baking oven, after standing 24 hours, takes out.
(3) 600 degree of carbonizations under nitrogen atmosphere are put into tube furnace, it is compound to get porous spherical manganese oxide/carbon is arrived after cooling
Object material.
It as shown in Fig. 1, is porous spherical manganese oxide/carbon composite material scanning electron microscope (SEM) photograph, sample particle probably exists
550nm or so.
Embodiment 2
(1) preparation of m-aminophenyl fluosite ball: toward 30 containing 24 grams of deionized waters and 10 milliliters of dehydrated alcohols
It spends in solution and 2.0 gram 25% of ammonium hydroxide is added, be added 0.71 gram of m-aminophenol, after stirring and dissolving, 35% formaldehyde is then added
1.0 grams of solution, continue stirring 24 hours, centrifuge separation；Sample is 12 hours dry in 50 degree of baking oven；By ammonia between 1.0 grams
Base phenol formaldehyde resin ball is distributed in 20 milliliters of water, and 10 milliliters of 1.0mol.L are added-1Manganese chloride solution；In this way, manganese oxide
The volume of precursor solution and the mass ratio of m-aminophenyl fluosite are 10:1, and stirring is taken out after 24 hours.
(2) it is put into 100 degree of baking oven, after standing 12 hours, takes out.
(3) it is put into tube furnace under nitrogen atmosphere and is carbonized to get porous spherical manganese oxide/carbon composite material is arrived for 800 degree.
It as shown in Fig. 2, is porous spherical manganese oxide/carbon composite material scanning electron microscope (SEM) photograph.Sample particle probably exists
500nm or so.
Embodiment 3
(1) preparation of m-aminophenyl fluosite ball: toward 30 containing 24 grams of deionized waters and 10 milliliters of dehydrated alcohols
It spends in solution and 2.0 gram 25% of ammonium hydroxide is added, be added 0.71 gram of m-aminophenol, after stirring and dissolving, 35% formaldehyde is then added
1.0 grams of solution, continue stirring 24 hours, centrifuge separation；Sample is 12 hours dry in 50 degree of baking oven；By ammonia between 1.5 grams
Base phenol formaldehyde resin ball is distributed in 20 milliliters of water, and 30 milliliters of 1.5mol.L are added-1Acetic acid manganese solution；In this way, manganese oxide
The volume of precursor solution and the mass ratio of m-aminophenyl fluosite are 20:1, and stirring is taken out after 24 hours.
(2) it is put into the baking oven of 40-200 degree, after standing 2 hours, takes out.
(3) it is put into tube furnace under nitrogen atmosphere and is carbonized to get porous spherical manganese oxide/carbon composite material is arrived for 750 degree.
Embodiment 4.
(1) preparation of m-aminophenyl fluosite ball: toward 30 containing 24 grams of deionized waters and 10 milliliters of dehydrated alcohols
It spends in solution and 2.0 gram 25% of ammonium hydroxide is added, be added 0.71 gram of m-aminophenol, after stirring and dissolving, 35% formaldehyde is then added
1.0 grams of solution, continue stirring 24 hours, centrifuge separation；Sample is 12 hours dry in 50 degree of baking oven；By ammonia between 1.0 grams
Base phenol formaldehyde resin ball is distributed in 10 milliliters of water, and 15 milliliters of 2.0mol.L are added-1Manganese chloride；In this way, body before manganese oxide
The volume of liquid solution and the mass ratio of m-aminophenyl fluosite are 15:1, and stirring is taken out after 24 hours.
(2) it is put into 150 degree of baking oven, after standing 10 hours, takes out.
(3) 800 degree of carbonizations under nitrogen atmosphere are put into tube furnace, it is compound to get porous spherical manganese oxide/carbon is arrived after cooling
Object material.
The present invention is simultaneously not limited to the embodiments described above, other any without departing from spiritual essence and principle of the invention
Changes, modifications, substitutions, combinations, simplifications made by lower, should be equivalent substitute mode, are included in protection model of the invention
Within enclosing.
Claims (7)
1. a kind of prepare porous spherical manganese oxide/carbon complex method, which comprises the following steps:
1) certain density manganese oxide precursor is added in the dispersion liquid of m-aminophenyl fluosite ball, stirring number is small
When, m-aminophenyl fluosite ball/manganese oxide precursor compound is obtained after centrifuge separation；
2) it by the resulting m-aminophenyl fluosite ball of step 1)/manganese oxide precursor compound, is put into baking oven and stands one
The section time is heat-treated；
3) by the pyrocarbon in a nitrogen atmosphere of m-aminophenyl fluosite ball/manganese oxide precursor compound through Overheating Treatment
Change to get porous spherical manganese oxide/carbon complex.
2. the method as described in claim 1, it is characterised in that: in step 1), the manganese oxide precursor is manganese acetate, chlorination
One or two kinds of mixtures of manganese.
3. the method as described in claim 1, it is characterised in that: in step 1), the concentration of the manganese oxide precursor is 0.2~
2.0mol.L-1。
4. the method as described in claim 1, it is characterised in that: in step 1), the volume of the manganese oxide precursor solution with
The mass ratio of m-aminophenyl fluosite ball is 10~30:1.
5. the method as described in claim 1, it is characterised in that: in step 2), the temperature of the heat treatment is 40-200 degree, place
Managing the time is 2-24 hours.
6. the method as described in claim 1, it is characterised in that: in step 3), the carburizing temperature under nitrogen atmosphere is 600-800
Degree, retention time are 2-4 hours.
7. the method as described in claim 1, which is characterized in that comprise the following specific steps that:
1) it first by m-aminophenol and formaldehyde according to equimolar ratio, is added in the ammonia spirit that pH is 9~11, stirs 24 hours
Afterwards, filter, obtain m-aminophenyl fluosite ball, then by a certain amount of m-aminophenyl fluosite ball be distributed to from
In sub- water, manganese oxide precursor is added, volume mass is pressed between manganese oxide precursor solution and m-aminophenyl fluosite ball
Than being centrifugated after stirring 10~24 hours for 10~30:1, obtaining m-aminophenyl fluosite ball/manganese oxide precursor
Compound；
2) then m-aminophenyl fluosite ball/manganese oxide precursor compound is put into the baking oven of 40-200 degree, heating 2
It is taken out after~24 hours；
3) again compound is continued to be put into Muffle furnace, is first warming up under 600-800 degree and is kept for 2~4 hours in a nitrogen atmosphere
Carbonization, to get porous spherical manganese oxide/carbon complex after cooling.
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| CN110386625A (en) * | 2019-08-16 | 2019-10-29 | 陕西科技大学 | A kind of manganese oxide carbon composite and preparation method thereof that molybdenum adulterates in situ |
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