CN116605911A - Fibrous alpha-type or stone bell-type delta-type manganese dioxide and low-temperature preparation method and application thereof - Google Patents
Fibrous alpha-type or stone bell-type delta-type manganese dioxide and low-temperature preparation method and application thereof Download PDFInfo
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 157
- 239000004575 stone Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 229940099596 manganese sulfate Drugs 0.000 claims abstract description 30
- 235000007079 manganese sulphate Nutrition 0.000 claims abstract description 30
- 239000011702 manganese sulphate Substances 0.000 claims abstract description 30
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims abstract description 30
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 238000001035 drying Methods 0.000 claims abstract description 25
- 239000000839 emulsion Substances 0.000 claims abstract description 22
- 239000007790 solid phase Substances 0.000 claims abstract description 21
- 238000005406 washing Methods 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 15
- 239000011148 porous material Substances 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 8
- 239000003990 capacitor Substances 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 56
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 238000001027 hydrothermal synthesis Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- 239000006230 acetylene black Substances 0.000 description 4
- 239000006258 conductive agent Substances 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000000643 oven drying Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 229910000474 mercury oxide Inorganic materials 0.000 description 2
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000004587 polysulfide sealant Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
- C01P2006/12—Surface area
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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
- C01P2006/14—Pore volume
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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
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
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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
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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
- C01P2006/80—Compositional purity
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- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Power Engineering (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a fibrous alpha-type or stone bell emulsion delta-type manganese dioxide, a low-temperature preparation method and application thereof, wherein the preparation method comprises the following steps: preparing a manganese sulfate solution, stirring, heating in a water bath at 70-90 ℃, dropwise adding a potassium permanganate solution into the manganese sulfate solution, and reacting for 60-90 min at 60-90 ℃ after the dropwise adding is finished to obtain a reaction solution; carrying out solid-liquid separation on the reaction solution, washing the obtained solid phase, drying the solid phase at 50-70 ℃ for 6-12 h to obtain delta manganese dioxide, and drying the solid phase at 50-70 ℃ for 84-120 h to obtain alpha manganese dioxide; the fibrous alpha-manganese dioxide is 1Ag ‑1 Is 343Fg at current density of (3) ‑1 Is a specific capacitance of (2); the stone bell emulsion delta-shaped manganese dioxide is 1Ag ‑1 586Fg is obtained at current density of (2) ‑1 Is a specific capacitance of (2); the obtained product can be used as super capacitor, catalyst, etc.
Description
Technical Field
The invention relates to the field of inorganic material synthesis, in particular to fibrous alpha-type or stone bell emulsion delta-type manganese dioxide, a low-temperature preparation method and application thereof.
Background
Manganese dioxide is used as an important industrial raw material, has good oxidation-reduction catalytic activity, low toxicity, environmental protection and good economic benefit, and has irreplaceable effects in the fields of catalysis, metal smelting, super capacitor and the like. Manganese dioxide has various crystal forms and respectively shows different morphologies, such as alpha-MnO 2 、β-MnO 2 、γ-MnO 2 、δ-MnO 2 All of these crystal structures are composed of [ MnO ] 6 ]Is composed of the common edges, angles or planes of the octahedron, oxygen atoms are at the four corners, and Mn atoms are at the center. In addition, [ MnO ] 6 ]Basic unit connection makes MnO 2 Forming various tunnel structures, alpha-MnO 2 (2×2 tunnel structure), γ -MnO 2 (mixed tunnel structure of 2×1 and 1×1), delta-MnO 2 (layered structure). Different types of manganese dioxide can play an important role in different fields of application, such as gamma-MnO 2 Can be used as negative electrode material of zinc ion battery and lithium ion battery, alpha-MnO 2 、β-MnO 2 Is an excellent super capacitor electrode material, delta-MnO 2 Is a good polysulfide sealant precursor. There are many methods for synthesizing manganese dioxide in a laboratory, including hydrothermal method, low-temperature solid-phase method, sol-gel method, electric potential deposition method, etc., and there are many methods for obtaining manganese dioxide with different crystal forms, such as adjusting the proportion of raw materials, the temperature and time of hydrothermal reaction, etc., and the manganese dioxide with different crystal forms can be converted, and common methods have high temperature, ionic liquid assistance, metal ion synergistic effect, etc., but these methods all increase cost and energy consumption, and simple and effective manganese dioxide crystal form conversion methods have been the focus of research.
The current method for preparing the manganese dioxide three-dimensional structure is generally a hydrothermal method, a catalytic method, a template method and the like. The template method needs to carry out post-treatment on the template after the reaction is finished, and needs to carry out high-temperature calcination or acid-base etching, so that a large amount of energy is consumed, the obtained product is easy to agglomerate, the size distribution is uneven, and the morphology of the product is possibly damaged or other impurities are possibly introduced. The hydrothermal method is to generate high pressure at high temperature by using a closed container, so that the reaction is rapidly performed, but the large-scale production is generally difficult due to the limitation of the volume of the container and the reaction temperature. The catalytic reaction time is long and noble metals are required as catalysts.
Chinese patent document 202011489595.3 discloses a preparation method of alpha-MnO 2 without channel ions: dissolving manganese salt in water, then adding sodium hypochlorite solution, standing, suction filtering, washing and drying to obtain amorphous manganese dioxide; adding amorphous manganese oxide into water, adding concentrated sulfuric acid, uniformly dispersing, and standing for reaction to obtain alpha-MnO 2 without channel ions; concentrated sulfuric acid is needed in the preparation method, so that more waste liquid is generated, and the preparation method is not friendly to the environment.
Chinese patent document 201610672452.3 discloses a coral-shaped porous delta-MnO 2 Is prepared by KMnO 4 Solution and MnSO 4 Uniformly mixing the solutions; adjusting the pH value of the mixed solution by using dilute hydrochloric acid; transferring the mixed solution with the pH value adjusted into a high-pressure reaction kettle; after the high-pressure reaction kettle reacts, cooling, washing the obtained product to be neutral by distilled water, washing the product by absolute ethyl alcohol, and drying the product by a baking oven to obtain coralline porous delta-MnO 2 Powder; the reaction temperature and the reaction pressure required by the reaction are large, and the cost is high.
It is currently difficult to prepare alpha-MnO 2 or delta-MnO under mild conditions without any template, surfactant or catalyst 2 。
Disclosure of Invention
In order to solve the defects in the prior art, the invention aims to provide fibrous alpha-type or stone bell-type delta-type manganese dioxide, a low-temperature preparation method and application thereof, and the method is simple in preparation method, and reduces the cost and energy consumption for producing different crystal forms of manganese dioxide by controlling the drying rate of a sample in the post-treatment process of sample synthesis.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a low-temperature preparation method of fibrous alpha-type or stone bell emulsion delta-type manganese dioxide, which is characterized by comprising the following steps: preparing a manganese sulfate solution, dropwise adding a potassium permanganate solution into the manganese sulfate solution under the conditions of stirring and water bath heating, and reacting to obtain a reaction solution after the dropwise adding is finished; carrying out solid-liquid separation on the reaction solution, washing and drying the obtained solid phase to obtain fibrous alpha-shaped manganese dioxide or stone bell emulsion delta-shaped manganese dioxide;
wherein, the drying conditions of the fibrous alpha-manganese dioxide are as follows: drying at 50-70 ℃ for 84-120 h;
the drying conditions of the stone bell emulsion delta manganese dioxide are as follows: and drying at 50-70 deg.c for 6-12 hr.
Preferably, the water bath temperature of the manganese sulfate solution is 60-90 ℃.
Preferably, the reaction condition is 60-90 ℃ for 60-90 min.
Preferably, the mass ratio of the solute solvent of the potassium permanganate solution is 7-10: 100.
preferably, the mass ratio of the solute solvent of the manganese sulfate solution is 6-9: 100.
preferably, the solute solvent mass ratio of the potassium permanganate solution is 8:100.
preferably, the mass ratio of solute solvent of the manganese sulfate solution is 8:100.
preferably, the potassium permanganate solution is added dropwise for no more than 5min.
The invention also claims a fibrous alpha-type manganese dioxide or a kefir-like delta-type manganese dioxide prepared by the method, wherein the specific surface area of the fibrous alpha-type manganese dioxide is 30-55 m 2 Per gram, pore volume of 0.1-0.4 cm 3 And/g, wherein the surface aperture is 2-8 nm; the specific surface area of the stone bell emulsion delta-shaped manganese dioxide is 110-130 m 2 Per gram, pore volume of 0.3-0.6 cm 3 And/g, wherein the surface pore diameter is 4-12 nm.
The invention also claims the use of said fibrous alpha-type manganese dioxide or lime-bell-type delta-type manganese dioxide in supercapacitors.
Compared with the prior art, the invention has the following beneficial effects:
1) The invention provides a low-temperature preparation method of fibrous alpha-type or shizu delta-type manganese dioxide, which adopts a simple hydrothermal method, is quick and effective, has low temperature, short reaction time, low cost, low energy consumption, stability, reliability and good safety.
2) The invention provides a low-temperature preparation method of fibrous alpha-type or shizu delta-type manganese dioxide, which has the advantages of low raw material price, wide sources, easy storage and large-scale production.
3) The invention provides a low-temperature preparation method of fibrous alpha-shaped or stone bell-shaped delta-shaped manganese dioxide, which can prepare fibrous alpha-shaped or stone bell-shaped delta-shaped manganese dioxide with high purity and good crystallization degree, wherein the specific surface area of the fibrous alpha-shaped manganese dioxide is 30-55 m 2 Per gram, pore volume of 0.1-0.4 cm 3 Per g, surface pore diameter of 2-8 nm, 1Ag -1 Is 343Fg at current density of (3) -1 Is a specific capacitance of (2); the specific surface area of the stone bell emulsion delta-shaped manganese dioxide is 110-130 m 2 Per gram, pore volume of 0.3-0.6 cm 3 Per g, surface pore diameter of 4-12 nm, 1Ag -1 586Fg is obtained at current density of (2) -1 Is a specific capacitance of (2); the obtained product can be directly applied to various required fields, such as super capacitors, catalysts and the like.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is XRD of alpha-manganese dioxide prepared in example 1;
FIG. 2 is XRD of delta-type manganese dioxide prepared in example 1;
FIG. 3 is an SEM of the alpha manganese dioxide prepared in example 1;
FIG. 4 is a SEM of delta manganese dioxide prepared in example 1;
FIG. 5 is a cyclic voltammogram of delta manganese dioxide prepared in example 1 at different scan rates;
FIG. 6 is a graph showing constant current charge and discharge of delta-type manganese dioxide prepared in example 1 at different current densities;
FIG. 7 is a cyclic voltammogram of delta manganese dioxide prepared in example 1 at different scan rates for a two-electrode system with positive and negative electrode assemblies, respectively;
FIG. 8 is a graph showing constant current charge and discharge of the delta-type manganese dioxide prepared in example 1 under different current densities for a two-electrode system with assembled positive and negative electrodes, respectively;
FIG. 9 is a cyclic voltammogram of the α manganese dioxide prepared in example 1 at various scan rates;
FIG. 10 is a constant current charge-discharge curve of the α -type manganese dioxide prepared in example 1 at different current densities;
FIG. 11 is a cyclic voltammogram of the two-electrode system with anode and cathode assembly for the α -type manganese dioxide prepared in example 1 at different scan rates;
FIG. 12 is a constant current charge-discharge curve diagram of a two-electrode system with positive and negative electrodes assembled respectively for the α -type manganese dioxide prepared in example 1 under different current densities;
fig. 13 is a graph showing nitrogen adsorption and desorption of delta-type manganese dioxide and alpha-type manganese dioxide obtained in example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the following examples. Of course, the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Unless otherwise specified, both chemical reagents and materials in the present invention are purchased through a market route or synthesized from raw materials purchased through a market route.
Example 1
A low-temperature preparation method of fibrous alpha-type or stone bell emulsion delta-type manganese dioxide comprises the following steps:
6g of manganese sulfate is dissolved in 100g of deionized water to prepare manganese sulfate solution, and the solution is stirred and heated in water bath at 80 ℃; dissolving 7g of potassium permanganate in 100g of deionized water to prepare a potassium permanganate solution, dropwise adding the potassium permanganate solution into a manganese sulfate solution, after 2 minutes of dropwise adding, reacting at 60 ℃ for 90 minutes to obtain a reaction solution, then carrying out solid-liquid separation, and washing the obtained solid phase;
drying a part of the solid phase product at 60 ℃ for 6 hours to obtain the stone bell emulsion delta manganese dioxide;
and (3) drying the rest solid phase product at 60 ℃ for 84 hours to obtain fibrous alpha-manganese dioxide.
Example 2
A low-temperature preparation method of fibrous alpha-type or stone bell emulsion delta-type manganese dioxide comprises the following steps:
7g of manganese sulfate is dissolved in 100g of deionized water to prepare manganese sulfate solution, and the solution is stirred and heated in 80 water bath; dissolving 8g of potassium permanganate in 100g of deionized water to prepare a potassium permanganate solution, dropwise adding the potassium permanganate solution into a manganese sulfate solution, after 3 minutes of dropwise adding, reacting at 70 ℃ for 80 minutes to obtain a reaction solution, then carrying out solid-liquid separation, and washing the obtained solid phase;
drying a part of the solid phase product at 60 ℃ for 7 hours to obtain the stone bell emulsion delta manganese dioxide;
and drying the rest solid phase product at 60 ℃ for 96 hours to obtain fibrous alpha-manganese dioxide.
Example 3
A low-temperature preparation method of fibrous alpha-type or stone bell emulsion delta-type manganese dioxide comprises the following steps:
dissolving 8g of manganese sulfate solution in 100g of deionized water to prepare manganese sulfate solution, stirring, and heating in water bath at 80 ℃; 9g of potassium permanganate is dissolved in deionized water to prepare a potassium permanganate solution, the potassium permanganate solution is dropwise added into a manganese sulfate solution, the dropwise addition is finished for 4min, then the reaction is carried out for 70min at 80 ℃ to obtain a reaction solution, then solid-liquid separation is carried out, and the obtained solid phase is washed;
drying a part of the solid phase product at 60 ℃ for 10 hours to obtain the stone bell emulsion delta manganese dioxide;
and (3) drying the rest solid-phase product at 60 ℃ for 108 hours to obtain fibrous alpha-manganese dioxide.
Example 4
A low-temperature preparation method of fibrous alpha-type or stone bell emulsion delta-type manganese dioxide comprises the following steps:
9g of manganese sulfate is dissolved in 100g of deionized water to prepare manganese sulfate solution, and the solution is stirred and heated in 80 water bath; dissolving 10g of potassium permanganate in 100g of deionized water to prepare a potassium permanganate solution, dropwise adding the potassium permanganate solution into a manganese sulfate solution, after 5 minutes of dropwise adding, reacting at 90 ℃ for 60 minutes to obtain a reaction solution, then carrying out solid-liquid separation, and washing the obtained solid phase;
drying a part of the solid phase product at 60 ℃ for 12 hours to obtain the stone bell emulsion delta manganese dioxide;
and (3) drying the rest solid phase product at 60 ℃ for 120 hours to obtain fibrous alpha-manganese dioxide.
Example 5
Delta manganese dioxide, polyvinylidene fluoride and acetylene black serving as a conductive agent prepared in example 1 are prepared according to the mass ratio of 8:1:1, dropwise adding 400 mu L N-methyl pyrrolidone solution, uniformly mixing to obtain paste, coating on 1cm multiplied by 1cm foam nickel, drying at 60 ℃ to obtain an electrode sheet as a working electrode, using a mercury oxide electrode as a reference electrode, using a platinum sheet as a counter electrode, using 1mol/L KOH as an electrolyte to assemble a three-electrode working system, and using 1Ag in a voltage interval range of-0.2-0.6V -1 586Fg is obtained at current density of (2) -1 Is a specific capacitance of (a).
Example 6
Delta manganese dioxide, polyvinylidene fluoride and acetylene black serving as a conductive agent prepared in example 1 are prepared according to the mass ratio of 8:1:1, dripping 400 mu L N-methyl pyrrolidone solution, mixing uniformly to obtain pasteCoating on 1cm×1cm foam nickel, loading 4mg, oven drying at 60deg.C to obtain electrode plates as positive electrode and negative electrode, respectively, and assembling two-electrode working system with 1mol/L KOH as electrolyte, wherein the maximum energy density and working density of the assembled system are 17.8Whkg respectively -1 And 0.2. 0.2Wkg -1 。
Example 7
The alpha-manganese dioxide, polyvinylidene fluoride and conductive agent acetylene black prepared in the example 1 are mixed according to the mass ratio of 8:1:1, dropwise adding 400 mu L N-methyl pyrrolidone solution, uniformly mixing to obtain paste, coating on 1cm×1cm foam nickel with load of 4mg, and oven drying at 60deg.C to obtain electrode sheet as working electrode, mercury oxide electrode as reference electrode, platinum sheet as counter electrode, and 1mol L -1 KOH is used as electrolyte to assemble a three-electrode working system, and 1Ag is used in a voltage interval range of-0.2 to 0.6V -1 Is 343Fg at current density of (3) -1 Is a specific capacitance of (a).
Example 8
The alpha-manganese dioxide, polyvinylidene fluoride and conductive agent acetylene black prepared in the example 1 are mixed according to the mass ratio of 8:1:1, dropwise adding 400 mu L N-methyl pyrrolidone solution, mixing to obtain paste, coating on 1cm×1cm foam nickel with load of 4mg, and oven drying at 60deg.C to obtain electrode sheets as positive and negative electrodes, respectively, 1mol L -1 KOH is used as electrolyte to assemble a two-electrode working system, and the maximum energy density and the working density of the assembled system are respectively 17.8Whkg -1 And 0.2. 0.2Wkg -1 。
Comparative example 1
A low-temperature preparation method of manganese dioxide comprises the following steps:
6g of manganese sulfate is dissolved in 100g of deionized water to prepare manganese sulfate solution, and the solution is stirred and heated in water bath at 80 ℃; dissolving 7g of potassium permanganate in 100g of deionized water to prepare a potassium permanganate solution, dropwise adding the potassium permanganate solution into a manganese sulfate solution, after 2 minutes of dropwise adding, reacting at 60 ℃ for 90 minutes to obtain a reaction solution, then carrying out solid-liquid separation, and washing the obtained solid phase;
the solid phase product was dried at 60 ℃ for 24 hours to obtain manganese dioxide with poor crystallization, and stone bell emulsion delta type manganese dioxide could not be obtained.
Comparative example 2
A low-temperature preparation method of manganese dioxide comprises the following steps:
6g of manganese sulfate is dissolved in 100g of deionized water to prepare manganese sulfate solution, and the solution is stirred and heated in water bath at 80 ℃; dissolving 7g of potassium permanganate in 100g of deionized water to prepare a potassium permanganate solution, dropwise adding the potassium permanganate solution into a manganese sulfate solution, after 2 minutes of dropwise adding, reacting at 60 ℃ for 90 minutes to obtain a reaction solution, then carrying out solid-liquid separation, and washing the obtained solid phase;
and drying the solid phase product at 60 ℃ for 48 hours to obtain manganese dioxide with poor crystallization, and obtaining fibrous alpha manganese dioxide.
The manganese dioxide of two different crystal forms prepared in example 1 was tested by BET specific surface area meter, and specific data are shown in Table 1.
TABLE 1 results of surface Properties detection of manganese dioxide of two different crystalline forms
| Sample of | Specific surface area (m) 2 /g) | Pore volume (cm) 3 /g) | Aperture (nm) |
| δ-MnO 2 | 121.140 | 0.331 | 6.148 |
| α-MnO 2 | 46.433 | 0.117 | 4.128 |
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (10)
1. A low-temperature preparation method of fibrous alpha-type or stone bell emulsion delta-type manganese dioxide, which is characterized by comprising the following steps: preparing a manganese sulfate solution, dropwise adding a potassium permanganate solution into the manganese sulfate solution under the conditions of stirring and water bath heating, and reacting to obtain a reaction solution after the dropwise adding is finished; carrying out solid-liquid separation on the reaction solution, washing and drying the obtained solid phase to obtain fibrous alpha-shaped manganese dioxide or stone bell emulsion delta-shaped manganese dioxide;
wherein, the drying conditions of the fibrous alpha-manganese dioxide are as follows: drying at 50-70 ℃ for 84-120 h;
the drying conditions of the stone bell emulsion delta manganese dioxide are as follows: and drying at 50-70 deg.c for 6-12 hr.
2. The method according to claim 1, wherein the water bath temperature of the manganese sulfate solution is 70-90 ℃.
3. The preparation method according to claim 1, wherein the reaction condition is 60 to 90 ℃ for 60 to 90min.
4. The preparation method according to claim 1, wherein the solute-solvent mass ratio of the potassium permanganate solution is 7-10: 100.
5. the preparation method according to claim 1, wherein the mass ratio of the solute solvent of the manganese sulfate solution is 6-9: 100.
6. the preparation method according to claim 1, wherein the solute-solvent mass ratio of the potassium permanganate solution is 8:100.
7. the preparation method according to claim 1, wherein the mass ratio of solute solvents of the manganese sulfate solution is 8:100.
8. the method according to claim 1, wherein the potassium permanganate solution is added dropwise for a period of not more than 5 minutes.
9. A fibrous alpha-manganese dioxide or a stone bell-shaped delta-manganese dioxide prepared by the method of any one of claims 1 to 8, characterized in that the fibrous alpha-manganese dioxide has a specific surface area of 30 to 55m 2 Per gram, pore volume of 0.1-0.4 cm 3 And/g, wherein the surface aperture is 2-8 nm; the specific surface area of the stone bell emulsion delta-shaped manganese dioxide is 110-130 m 2 Per gram, pore volume of 0.3-0.6 cm 3 And/g, wherein the surface pore diameter is 4-12 nm.
10. Use of the fibrous alpha manganese dioxide or the stone bell emulsion delta manganese dioxide according to claim 9 in supercapacitors.
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| CN117383617B (en) * | 2023-10-20 | 2024-03-19 | 广州南科高新材料科技有限公司 | Efficient active manganese preparation method |
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