CN113658809B - Preparation method of amorphous manganese oxide electrode material - Google Patents
Preparation method of amorphous manganese oxide electrode material Download PDFInfo
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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 146
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- 229910003176 Mn-O Inorganic materials 0.000 description 1
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- 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 description 1
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Images
Classifications
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- 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
- 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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- 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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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
A preparation method of an amorphous manganese oxide electrode material comprises the following steps: preparing a potassium permanganate solution, a PVA (polyvinyl alcohol) aqueous solution, a conductive agent and a sticky patch; mixing the potassium permanganate solution and the PVA aqueous solution to obtain a precursor solution; heating the precursor solution to obtain amorphous manganese oxide; cooling the amorphous manganese oxide to room temperature; washing the amorphous manganese oxide; drying the amorphous manganese oxide; mixing the conductive agent, the adhesive agent and the amorphous manganese oxide to obtain electrode slurry; uniformly coating the electrode slurry on a current collector to obtain a semi-finished product; and drying the semi-finished product and directly pressing into an electrode. The high-performance amorphous manganese oxide electrode material is prepared by adopting a redox method, the preparation process is simple, the requirement on the precision of equipment is low, and the pollution of subsequent treatment of a sample is small; the manufacturing process and the cost of the low-cost super capacitor energy storage device are greatly benefited, and the use cost of the super capacitor by a new energy automobile is reduced.
Description
Technical Field
The application relates to the field of electrodes, in particular to a preparation method of an amorphous manganese oxide electrode material.
Background
The super capacitor has the advantages of larger capacity than the traditional capacitor and higher power than the storage battery, can be charged and discharged quickly, has long service life, and is one of the most promising energy storage devices. In recent years, an electric double layer capacitor composed of a carbon material that stores energy by electrostatically adsorbing ions at an electrode/electrolyte interface has low energy density and limited market applications, and a faraday capacitor mainly composed of a transition metal oxide has attracted attention worldwide, has good power density, and is expected to be a new high-performance energy storage material. Transition metal oxide (RuO 2, niO, co3O4, mnO2 and the like) materials can store energy through fast and reversible Faraday reaction by surface drawing, have higher specific capacitance, and can form a Faraday pseudo capacitor with high energy density with a carbon material, so that the material has important significance for development and research of the material.
At present, compared with other transition metal oxides, manganese oxide has the advantages of low cost, environmental friendliness, large reserves and the like, and is an ideal pseudocapacitance material. However, manganese oxide materials have disadvantages such as poor conductivity (10-5 S.multidot.cm-1 to 10-6 S.multidot.cm-1), small ion diffusion constant, and volume expansion/contraction due to ion intercalation/deintercalation of manganese oxide crystals, and their theoretical specific capacitance (1100 F.multidot.g-1 to 1300 F.multidot.g-1) is difficult to realize. In order to solve the problems, the reasonable regulation and control of the structure of the manganese oxide material is a common effective method, and for example, the nano structures such as MnO2 nano flowers, mnOOH nano rods, mnO2 hollow spheres, mnO2 arrays and the like can increase the ion adsorption area, accelerate the electron transfer rate, shorten the ion transfer path and improve the electrochemical performance of the manganese oxide material. However, the preparation period of the manganese oxide material with a special structure is long, the process control is complex, and even a template is needed, so that the preparation of the manganese oxide material in large quantity is not facilitated.
Patent CN102616860a discloses a method for preparing nanometer amorphous manganese dioxide from sacrificial template, which comprises the following steps: dropwise adding the deionized water solution of potassium permanganate into the deionized water solution of octyl phenol polyoxyethylene ether under stirring, reacting at normal temperature, performing centrifugal separation, pouring out supernatant, washing the solid sample with deionized water and absolute ethyl alcohol for 3-6 times respectively, and drying at constant temperature to obtain the nanoscale amorphous manganese dioxide. However, the preparation period and engineering control of the materials in the method are fine, and large-scale preparation is not facilitated.
Patent CN100558644C uses cheap potassium permanganate and oleic acid as reactants, and does not need acid or alkali treatment, and oxidation-reduction reaction occurs in neutral aqueous solution, and by controlling the molar ratio of potassium permanganate/oleic acid, monodisperse layered mesoporous birnessite type MnO2 cellular nanospheres and hollow nanospheres can be obtained respectively. However, in the method, the control of the material preparation process is fine, and the sample is not applied chemically.
Disclosure of Invention
The application provides a preparation method of an amorphous manganese oxide electrode material, which aims to solve the technical problem of defects in electrode preparation.
The application provides a preparation method of an amorphous manganese oxide electrode material, which comprises the following steps:
preparing a potassium permanganate solution, a PVA (polyvinyl alcohol) aqueous solution, a conductive agent and a sticky patch;
mixing the potassium permanganate solution and the PVA aqueous solution to obtain a precursor solution;
heating the precursor solution to obtain amorphous manganese oxide;
cooling the amorphous manganese oxide to room temperature;
washing the amorphous manganese oxide;
drying the amorphous manganese oxide;
mixing the conductive agent, the adhesive agent and the amorphous manganese oxide to obtain electrode slurry;
uniformly coating the electrode slurry on a current collector to obtain a semi-finished product;
and drying the semi-finished product and directly pressing into an electrode.
Optionally, the concentration of the potassium permanganate solution is 13-13.4g/L.
Optionally, the concentration of the PVA aqueous solution is 6.4-6.8g/L.
Optionally, the mass concentration ratio of the potassium permanganate solution to the PVA aqueous solution is 1: 3.
Optionally, the step of heating the precursor solution to obtain amorphous manganese oxide includes:
heating the precursor solution at 230-270 deg.C for 25-35min.
Optionally, the washing the amorphous manganese oxide includes:
preparing deionized water and ethanol;
washing the amorphous manganese oxide with the deionized water and the ethanol until it is neutral.
Optionally, the drying the amorphous manganese oxide includes:
drying the amorphous manganese oxide at the temperature of 50-70 ℃ for 10-14h.
Optionally, the mass ratio of the conductive agent to the adhesive to the amorphous manganese oxide is 1: 8.
Compared with the prior art, the technical scheme provided by the embodiment of the application has the following advantages:
according to the preparation method of the amorphous manganese oxide electrode material, the high-performance amorphous manganese oxide electrode material is prepared by adopting the redox method, the preparation process is simple, the requirement on the precision of equipment is low, and the pollution of subsequent treatment of a sample is small; the manufacturing process and the cost of the low-cost super capacitor energy storage device are greatly benefited, and the use cost of the super capacitor by a new energy automobile is reduced.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the invention and together with the description, serve to explain the principles of the invention.
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without inventive exercise.
FIG. 1 is an SEM image of a sample obtained by a method for preparing an amorphous manganese oxide electrode material provided by an embodiment of the application;
fig. 2 is an XRD pattern of a sample obtained by a method for preparing an amorphous manganese oxide electrode material provided in an embodiment of the present application;
FIG. 3 is a XPS curve of a sample II obtained by a method for preparing an amorphous manganese oxide electrode material according to an embodiment of the present application;
FIG. 4 is a schematic view of a CV/GCD curve of a sample obtained by a method for preparing an amorphous manganese oxide electrode material according to an embodiment of the present application;
FIG. 5 is a schematic diagram of a cycle/EIS curve of a sample II obtained by a method for preparing an amorphous manganese oxide electrode material according to an embodiment of the present application;
fig. 6 is a schematic diagram of a cycle curve of an asymmetric capacitor obtained by a method for preparing an amorphous manganese oxide electrode material according to an embodiment of the present application.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
Abbreviations and key term definitions in this application:
CV (cyclic voltammetry): a method for researching electrochemical behavior of test electrode in electrolyte includes controlling electrode potential by triangular wave signal with different scanning speed, carrying out one or multiple repeated scanning on electrode along with time, when preset end potential is reached, scanning reversely to preset initial potential and recording current curve along with potential variation.
GCD (galvanostatic charge/discharge, constant current charge and discharge method): under a certain constant current density, the change of voltage along with time is tested, and the size of the specific capacitance of the electrode can be quickly calculated and the stability of the electrode material can be judged.
EIS (electrochemical impedance spectroscopy, ac impedance test): the conventional method for measuring the internal resistance of a material and the equivalent resistance in an electrochemical reaction.
PVA (polyvinyl alcohol): a chemical raw material.
SEM (standard electronic modules, scanning Electron microscope): an apparatus for observing the surface characteristics of a material.
XRD (X-ray diffraction): a method of testing the crystal structure of a material.
XPS (X-ray photoelectron spectroscopy ): method for testing the chemical state of a material.
In an embodiment of the present application, the present application provides a method for preparing an amorphous manganese oxide electrode material, the method comprising the steps of:
preparing a potassium permanganate solution, a PVA (polyvinyl alcohol) aqueous solution, a conductive agent and a sticky patch;
mixing the potassium permanganate solution and the PVA aqueous solution to obtain a precursor solution;
heating the precursor solution to obtain amorphous manganese oxide;
cooling the amorphous manganese oxide to room temperature;
washing the amorphous manganese oxide;
drying the amorphous manganese oxide;
mixing the conductive agent, the adhesive agent and the amorphous manganese oxide to obtain electrode slurry;
uniformly coating the electrode slurry on a current collector to obtain a semi-finished product;
and drying the semi-finished product and directly pressing into an electrode.
In the embodiment of the application, the concentration of the potassium permanganate solution is 13-13.4g/L.
In the examples of the present application, the concentration of the aqueous PVA solution is 6.4 to 6.8g/L.
In the embodiment of the application, the mass concentration ratio of the potassium permanganate solution to the PVA aqueous solution is 1: 3.
In an embodiment of the present application, the heating the precursor solution to obtain the amorphous manganese oxide includes:
heating the precursor solution at 230-270 deg.C for 25-35min.
In an embodiment of the present application, the washing the amorphous manganese oxide includes:
preparing deionized water and ethanol;
washing the amorphous manganese oxide with the deionized water and the ethanol until it is neutral.
In an embodiment of the present application, the drying the amorphous manganese oxide includes:
drying the amorphous manganese oxide at the temperature of 50-70 ℃ for 10-14h.
In the examples of the present application, the mass ratio of the conductive agent, the adhesive agent, and the amorphous manganese oxide is 1: 8.
In the examples of the present application, the conductive agent was acetylene black, and the adhesive agent was 20 g.L-1 of polymethylpyrrolidone.
In the embodiment of the application, the current collector is foamed nickel.
The present application is described in detail below with specific examples.
Samples prepared from KMnO4 solutions of 6.6 g.L-1, 13.2 g.L-1 and 19.8 g.L-1 and aqueous PVA solutions were designated I, II and III, with other experimental parameters unchanged.
FIG. 1 is an SEM photograph of a sample prepared by reducing KMnO4 with PVA, and the sample morphology is 5 μm to 50 μm irregular aggregates as seen by low magnification SEM (FIGS. 1a, 1c, 1 e). As can be further understood from fig. 1b, 1d and 1f, the microstructure of sample II is slightly different from that of samples I and III, and lamellar manganese oxide is generated. Research shows that the manganese oxide with the two-dimensional sheet structure is beneficial to electrolyte ions entering the material, so that the utilization rate of the material is improved, and the electrochemical reaction process is accelerated.
FIG. 2 is an XRD pattern of all samples I-III, which shows that the manganese oxide synthesized using PVA and KMnO4 is amorphous.
As can be seen in fig. 3a, sample II is composed primarily of manganese, oxygen and potassium elements. The impurity K + may serve to shorten the diffusion distance of electrolyte ions in the electrode material, thereby increasing the specific capacitance of the electrode material. While the difference between the two spin-orbit binding energies of 2p3/2 and 2p1/2 of Mn atom is 11.7eV (FIG. 3 b) and the difference between the multiple splitting energies of 3s electron orbitals of Mn atom is 4.9eV (FIG. 3 c), indicating that the main valence of Mn element is +4. Oxygen in the sample originated from the bond with Mn, and Mn-O (530.2 eV), mn-O-Mn (531.9 eV) could be detected as shown in FIG. 3 d. These data indicate that sample II is amorphous Mn02 containing K +.
TABLE 1 specific surface area and pore size of the samples
As can be seen from Table 1, the specific surface areas and the pore volumes of the samples I to III were respectively 19.6m2. G-1, 30.9m2. G-1, 23.8m2. G-1 and 0.085cm3. G-1, 0.124cm3. G-1, 0.070cm3. G-1, which are advantageous in that the electrolyte ions and the active substance were sufficiently brought into contact, and the specific surface area for effective utilization was increased. Sample II has a high specific surface area, pore volume and mesopore volume and a layered microstructure is present (fig. 1 d), which is advantageous for accelerating the kinetics of the electrochemical reaction.
The electrochemical performance of the samples I-III is tested by CV and GCD, and the sample V can be clearly found to have the highest specific capacitance from the closed area of the CV curve in FIG. 4a, which indicates that the high specific surface area and the mesoporous channel are beneficial to the full contact between the electrode material and the electrolyte and the acceleration of the electrochemical reaction rate. FIG. 4b shows that all the GCD curves of the samples are non-linear due to the redox reactions occurring, and the specific capacitances at 1 A.g-1 current densities of samples I-III can be calculated as 323 F.g-1, 451 F.g-1 and 200 F.g-1, respectively. FIG. 4c is a CV curve of sample II at 10mV · s-1 to 100mV · s-1, with no significant distortion of the CV curve as the scan rate increases, all being approximately rectangular, demonstrating good pseudocapacitive behavior of sample V. FIG. 4d shows that sample II has specific capacitance values of 451F g-1, 301F g-1, 200F g-1, 150F g-1 and 118F g-1 respectively at current densities of 1A g-1, 2.5A g-1, 5A g-1, 7.5A g-1 and 10A g-1, and has good multiplying power performance.
FIG. 5A is a graph of the cycle of sample II from a continuous GCD test at a current density of 5 A.g-1, showing that 62.5% of the initial specific capacitance is retained after 2000 cycles. As can be seen in the EIS of fig. 5b, the resistance of the sample material deteriorates after cycling, and the slope of the line in the low frequency region increases significantly, indicating that the ion diffusion rate of the electrolyte in the material decreases, which is most likely due to the decrease in the active species caused by the volume expansion/contraction of the electrode cycling during the process.
In order to verify the application prospect of the amorphous manganese oxide material prepared by the patent, an asymmetric super capacitor is formed by taking a sample II as an anode, commercial carbon as a cathode and 2 mol.L < -1 > KOH solution as electrolyte (the loading of an active substance of the anode is 1.6 mg.cm < -2 >, and the loading of an active substance of the cathode is 1.5 mg.cm < -2 >). The charge-discharge cycling tests were conducted over a voltage range of 0-1.6V and a current density of 1A · g-1, and fig. 6 shows that the capacity still retained 63.9% of the initial specific capacitance after 2000 cycles.
According to the preparation method of the amorphous manganese oxide electrode material, the high-performance amorphous manganese oxide electrode material is prepared by adopting the redox method, the preparation process is simple, the requirement on the precision of equipment is low, and the pollution of subsequent treatment of a sample is small; the manufacturing process and the cost of the low-cost super capacitor energy storage device are greatly benefited, and the use cost of the super capacitor by a new energy automobile is reduced.
It is noted that, in this document, relational terms such as "first" and "second," and the like, are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising a … …" does not exclude the presence of another identical element in a process, method, article, or apparatus that comprises the element.
The foregoing are merely exemplary embodiments of the present invention, which enable those skilled in the art to understand or practice the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (4)
1. A preparation method of an amorphous manganese oxide electrode material is characterized by comprising the following steps:
preparing a potassium permanganate solution, a PVA (polyvinyl alcohol) aqueous solution, a conductive agent and a sticky patch;
mixing the potassium permanganate solution and the PVA aqueous solution to obtain a precursor solution;
heating the precursor solution to obtain amorphous manganese oxide;
cooling the amorphous manganese oxide to room temperature;
washing the amorphous manganese oxide;
drying the amorphous manganese oxide;
mixing the conductive agent, the adhesive agent and the amorphous manganese oxide to obtain electrode slurry;
uniformly coating the electrode slurry on a current collector to obtain a semi-finished product;
drying the semi-finished product and directly pressing into an electrode;
the concentration of the potassium permanganate solution is 13-13.4g/L;
the concentration of the PVA aqueous solution is 6.4-6.8g/L;
the mass concentration ratio of the potassium permanganate solution to the PVA aqueous solution is 1: 3;
the step of heating the precursor solution to obtain amorphous manganese oxide comprises the following steps:
heating the precursor solution at 230-270 ℃ for 25-35min;
the amorphous manganese oxide includes a lamellar manganese oxide.
2. The method for preparing an amorphous manganese oxide electrode material according to claim 1, wherein said washing said amorphous manganese oxide comprises the steps of:
preparing deionized water and ethanol;
washing the amorphous manganese oxide to neutral using the deionized water and the ethanol.
3. The method for preparing the amorphous manganese oxide electrode material according to claim 1, wherein the step of drying the amorphous manganese oxide comprises the steps of:
drying the amorphous manganese oxide at the temperature of 50-70 ℃ for 10-14h.
4. The method for preparing an amorphous manganese oxide electrode material according to claim 1, wherein the mass ratio of the conductive agent, the adhesive agent and the amorphous manganese oxide is 1: 8.
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