CN113936925B - Bimetal ion doped manganese dioxide electrode and preparation method and application thereof - Google Patents

Bimetal ion doped manganese dioxide electrode and preparation method and application thereof Download PDF

Info

Publication number
CN113936925B
CN113936925B CN202111075403.9A CN202111075403A CN113936925B CN 113936925 B CN113936925 B CN 113936925B CN 202111075403 A CN202111075403 A CN 202111075403A CN 113936925 B CN113936925 B CN 113936925B
Authority
CN
China
Prior art keywords
manganese
electrode
metal ions
ion
ions
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202111075403.9A
Other languages
Chinese (zh)
Other versions
CN113936925A (en
Inventor
刘翠茵
温元峰
李景灵
龙航宇
翁沫炜
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Foshan University
Original Assignee
Foshan University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Foshan University filed Critical Foshan University
Priority to CN202111075403.9A priority Critical patent/CN113936925B/en
Publication of CN113936925A publication Critical patent/CN113936925A/en
Application granted granted Critical
Publication of CN113936925B publication Critical patent/CN113936925B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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

Abstract

The invention discloses a bimetal ion doped manganese dioxide electrode, a preparation method and application thereof, wherein the electrode comprises a base material and a load on the base materialThe manganese-based oxide nano-sheet comprises manganese oxide and bi-metal ions doped in the manganese oxide, wherein the bi-metal ions comprise alkali metal ions or alkaline earth metal ions, and transition metal ions do not comprise manganese ions. The electrode of the invention is doped in the manganese oxide layered structure by alkali metal ions or alkaline earth metal ions, which is beneficial to reducing the resistance of electrolyte ions in the electrolyte ions, promoting the kinetic process of energy storage, and simultaneously passing transition metal ions and Mn 2+ The metal oxyacid salt is formed, can effectively inhibit the dissolution behavior of manganese, has excellent multiplying power performance and cycle stability, has the specific capacity retention rate of 65-70F/g under the condition of 20A/g, and has the capacity retention rate of 94-98% after 1000 times of cycle charge and discharge.

Description

Bimetal ion doped manganese dioxide electrode and preparation method and application thereof
Technical Field
The invention belongs to the technical field of energy storage, and particularly relates to a bimetal ion doped manganese dioxide electrode, and a preparation method and application thereof.
Background
As an emerging electrochemical energy storage device, the super capacitor has the advantages of short charge and discharge time, long cycle service life, safety, cleanness and the like, and can supplement the technical blank of a secondary chemical battery. Currently, the main stream of electrode materials of supercapacitors includes carbon materials, conductive polymers and transition metal oxides. The manganese oxide has rich resource content, environmental friendliness, high electrochemical activity and high theoretical capacitance (1370F/g), and is a supercapacitor electrode material with great application prospect. The capacitance of manganese oxide is contributed by three processes of physical electrostatic adsorption of electrolyte ions on the surface, faradaic oxidation-reduction reaction of the surface and near surface and intercalation and deintercalation in the crystal lattice. However, manganese oxide has problems of low conductivity and poor ion diffusion, electrons and ions are difficult to transport freely inside the material, so that the utilization rate of active sites is not high, and the actual capacitance of the electrode is far lower than a theoretical value. Currently, the capacitance of manganese dioxide electrodes prepared by the tabletting method is about 200F/g. In addition, manganese oxides often have insufficient cycling stability during energy storage due to the ginger-taylor effect and manganese dissolution problems. In order to improve the energy storage performance of the manganese oxide, the most widely used solution is to use a carbon material with better conductivity and stability for coating treatment. Although the method can improve the conductivity and the stability of the manganese oxide, the method is unfavorable for the diffusion of electrolyte ions in a manganese oxide solid phase and reduces the energy storage kinetics process.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the prior art described above. Therefore, the invention provides a bimetal ion doped manganese dioxide electrode, and a preparation method and application thereof; the bimetal ion doped manganese dioxide electrode provided by the invention has excellent multiplying power performance and cycle stability.
A first aspect of the present invention provides a bimetal ion doped manganese dioxide electrode comprising a substrate and manganese-based oxide nanoplatelets supported on the surface of the substrate, the manganese-based oxide nanoplatelets comprising a manganese oxide and a bimetal ion doped in the manganese oxide, the bimetal ion comprising an alkali metal ion or an alkaline earth metal ion, and a transition metal ion, the transition metal ion not comprising a manganese ion.
The applicant of the invention discovers in the research that the manganese oxide electrode is modified by doping alkali metal ions or alkaline earth metal ions and transition metal ions, and compared with the traditional carbon material coating technology, the doping of the metal ions not only can effectively improve the conductivity of the manganese oxide, but also can reduce the diffusion resistance of electrolyte ions in the manganese oxide layered structure, and promote the kinetic process of energy storage; at the same time, transition metal ions pass through Mn 2+ The metal oxyacid salt is formed, and the dissolution behavior of manganese can be effectively inhibited, so that the rate capability and the cycle stability are improved.
Preferably, the width of the manganese-based oxide nano-sheet is 20-500nm, and the thickness is 1-20nm.
Preferably, the alkali metal ion or alkaline earth metal ion comprises a Li ion, a Na ion, a K ion, a Ca ion, or a Mg ion; the transition metal ion includes Cr ion, mo ion, W ion, V ion, or Nb ion.
Preferably, the manganese oxide comprises manganese monoxide, manganese dioxide, manganese sesquioxide or manganese tetraoxide.
Preferably, in the manganese-based oxide nano-sheet, the atomic percentage content of the alkali metal ion or alkaline earth metal ion is 0.01-20%; the atom percentage content of the transition metal ions is 0.01-5%.
Preferably, the substrate comprises nickel foam, carbon paper, carbon cloth or titanium foil.
The second aspect of the invention provides a preparation method of the bimetal ion doped manganese dioxide electrode, which comprises the following steps:
preparing a mixed solution containing the alkali metal ions or alkaline earth metal ions and the transition metal ions;
reacting the substrate with manganese salt to obtain a manganese oxide precursor electrode;
and immersing the manganese oxide precursor electrode in the mixed solution, and performing in-situ electrochemical driving oxidation doping treatment in a three-electrode device by using an electrochemical workstation mode to obtain the bimetal ion doped manganese dioxide electrode.
Preferably, the manganese oxide precursor electrode comprises a trimanganese tetroxide precursor electrode or a manganese monoxide precursor electrode; in the mixed solution, the concentration of the alkali metal ions or alkaline earth metal ions is 0.1-10mol/L, and the concentration of the transition metal ions is 0.01-5mmol/L; more preferably, the concentration of the alkali metal ion or alkaline earth metal ion is 0.1 to 1mol/L, and the concentration of the transition metal ion is 0.01 to 0.2mmol/L; most preferably, the concentration of the alkali metal ion or alkaline earth metal ion is 0.1 to 0.5mol/L, and the concentration of the transition metal ion is 0.04 to 0.06mmol/L.
Preferably, the preparation method of the manganous oxide precursor electrode comprises the following steps:
and (3) placing the base material in a reaction kettle filled with manganese salt aging liquid, and heating and reacting for a certain time to obtain the manganese salt aging liquid. Further, the manganese salt aging liquid is obtained by dissolving manganese acetate in a mixed liquid of deionized water, absolute ethyl alcohol and ethylene glycol and aging for 3 days; the heating reaction temperature is 150-250 ℃, the reaction time is 2-10h, and the manganous manganic oxide precursor electrode is obtained.
Preferably, the preparation method of the manganese monoxide precursor electrode comprises the following steps:
and (3) placing the manganous manganic oxide precursor electrode in a tube furnace, introducing argon, and carrying out high-temperature annealing treatment for a certain time to obtain the manganous manganic oxide precursor electrode. Further, the high temperature condition is 800-1200 ℃, the treatment time is 1-5h, and the manganese monoxide precursor electrode is obtained.
Preferably, the electrochemical workstation mode comprises cyclic voltammetry or constant current charge-discharge.
Preferably, the cyclic voltammetry sets the lower limit of a voltage window to be-0.5-0V, the upper limit of the voltage window to be 0.8-1.5V, the scanning speed to be 1-50mV/s and the number of cycles to be 10-500 cycles; the constant current charge-discharge method sets the lower limit of the voltage window to be-0.5-0V, the upper limit of the voltage window to be 0.8-1.5V and the current to be 0.5-10mA.
A third aspect of the invention provides the use of said bimetallic ion doped manganese dioxide electrode in a capacitor.
According to the application, the invention provides a super capacitor which comprises the bimetal ion doped manganese dioxide electrode.
Compared with the prior art, the invention has the following beneficial effects:
(1) The bimetal ion doped manganese dioxide electrode comprises a substrate and manganese-based oxide nano-sheets loaded on the surface of the substrate, wherein the manganese-based oxide nano-sheets comprise manganese oxide and bimetal ions doped in the manganese oxide; the alkali metal ions or alkaline earth metal ions are doped in the manganese oxide layered structure, which is favorable for reducing the diffusion resistance of electrolyte ions in the manganese oxide layered structure, promoting the kinetic process of energy storage, and simultaneously passing through the transition metal ions and Mn 2+ The metal oxyacid salt is formed, and the dissolution behavior of manganese can be effectively inhibited. The invention relates to a bimetal ion doped dioxideThe manganese electrode has excellent rate capability and cycle stability, the specific capacity under the condition of 1A/g reaches 270-405F/g, the specific capacity retention rate under the condition of 20A/g reaches 65-70F/g, and the capacity retention rate after 1000 times of cycle charge and discharge reaches 94-98%.
(2) The invention utilizes the manganese oxide precursor electrode to remove Mn under the drive of electrochemical oxidation 2+ Providing vacancies for intercalation of other metal cations while deintercalating Mn 2+ The manganese dioxide is bonded with transition metal acid ions, and the one-step doping of manganese dioxide and different bimetallic ions can be skillfully realized by regulating and controlling the types of the metal ions, so that the preparation method is simple and easy to operate, safe and pollution-free, and has high efficiency.
(3) According to the invention, a cyclic voltammetry or constant current charge-discharge method is adopted, so that the one-step doping of the bimetallic ions in the manganese oxide is realized, and the morphology of the nanosheets can be regulated and controlled through the concentration of the transition metal acid ions. Transition metal ion and Mn 2+ The formation of the nano-sheets is controlled by the bi-metallate formed by bonding, by affecting the oxidation efficiency of the manganese oxide precursor electrode, resulting in different nano-sheet dimensions.
Drawings
FIG. 1 is a surface scanning electron microscope image of an electrode prepared in example 1 of the present invention;
FIG. 2 is a surface scanning electron microscope image of the electrode prepared in example 2 of the present invention;
FIG. 3 is a surface scanning electron microscope image of the electrode prepared in example 3 of the present invention;
FIG. 4 is a surface Raman spectrum of the electrode prepared in example 1 of the present invention;
FIG. 5 is a surface element distribution diagram of an electrode prepared in example 1 of the present invention;
FIG. 6 is a cyclic voltammogram and constant current charge-discharge plot of an electrode prepared in example 1 of the present invention;
FIG. 7 is a cyclic voltammogram and constant current charge-discharge graph of an electrode prepared in comparative example 1 of the present invention;
FIG. 8 is a cyclic voltammogram and constant current charge-discharge plot of an electrode prepared in comparative example 2 of the present invention;
fig. 9 is a graph showing comparison of the cyclic charge and discharge stability of the electrodes prepared in example 1 and comparative example 2 according to the present invention.
Detailed Description
In order to make the technical solutions of the present invention more apparent to those skilled in the art, the following examples will be presented. It should be noted that the following examples do not limit the scope of the invention.
The components, reagents or apparatus used in the examples below are all commercially available from conventional sources or may be obtained by methods known in the art unless otherwise specified.
Example 1
A bimetal ion doped manganese dioxide electrode comprises a foam nickel substrate and manganese-based oxide nano-sheets loaded on the surface of the foam nickel substrate, wherein the manganese-based oxide nano-sheets comprise manganese dioxide and Na ions and Mo ions doped in the manganese dioxide.
The preparation method of the bimetal ion doped manganese dioxide electrode comprises the following steps:
na of 0.5mol/L 2 SO 4 Solution and 0.04mmol/L Na 2 MoO 4 Mixing the solutions to obtain a mixed solution;
dissolving manganese acetate in a mixed solution of deionized water, absolute ethyl alcohol and ethylene glycol, and aging for 3 days to obtain manganese salt aging solution;
placing the foam nickel substrate in a reaction kettle filled with manganese salt aging liquid, and reacting for 2-10 hours at 150-250 ℃ to obtain a manganous oxide precursor electrode;
in the three-electrode system, an electrochemical workstation is utilized, a constant current charge-discharge mode is adopted, the set voltage range is 0.1-0.9V, the current is 1mA, the number of circulation turns is 300, and the Na and Mo bimetal ion doped manganese dioxide electrode is obtained.
Referring to fig. 1, fig. 1 (a) and (b) are respectively surface scanning electron microscope images of the bimetal ion doped manganese dioxide electrode of the embodiment under different resolutions, and as can be seen from fig. 1, the bimetal ion doped manganese dioxide obtained in the embodiment has a nano-sheet structure, a plurality of nano-sheets are stacked together, and white strips in fig. 1 are edges of the nano-sheets, and some Xu Juanqu are arranged.
Referring to FIG. 4, 504cm- 1 The sum of the small shoulders of (2) is 570-650cm -1 The large broad peak of (2) is the characteristic peak of birnessite type manganese dioxide.
Referring to fig. 5, it can be seen that Na, mo, mn, and O elements are uniformly distributed in the electrode material.
From a combination of the analyses of FIGS. 1, 4 and 5, it can be seen that the Na and Mo bimetallic ion doped manganese dioxide electrode was successfully prepared in this example.
Electrochemical testing was performed on the electrode obtained in this example: the bimetallic ion doped manganese dioxide electrode prepared in the embodiment is used as a working electrode, a Pt sheet electrode is used as a counter electrode and Ag/AgCl is used as a reference electrode, and 0.5mol/L Na is used as a reference electrode 2 SO 4 In a three-electrode system formed by the aqueous electrolyte, cyclic voltammetry curves at different scanning rates and constant current charge-discharge curves at different current densities are tested, and test results are shown in fig. 6.
Fig. 6 (a) shows cyclic voltammograms at different scan rates, and it can be seen that the curves are rectangular and generally symmetrical, and the area increases with increasing scan rate, indicating that the electrode has ideal capacitive characteristics, and a reversible charge storage process occurs.
Fig. 6 (b) shows constant current charge and discharge curves at different current densities, and it can be seen that the curves are straight and symmetrical, indicating that the reaction process is reversible.
By calculation, the electrode specific capacities were 401, 371, 337, 309 and 276F/g under the conditions of 1, 2, 5, 10 and 20A/g, respectively. At a high current of 20A/g, the specific capacity of 69% is still maintained, indicating that the electrode has excellent rate capability.
Example 2
A bimetal ion doped manganese dioxide electrode comprises a foam nickel substrate and manganese-based oxide nano-sheets loaded on the surface of the foam nickel substrate, wherein the manganese-based oxide nano-sheets comprise manganese dioxide and Na ions and Mo ions doped in the manganese dioxide.
The preparation method of the bimetal ion doped manganese dioxide electrode comprises the following steps:
na of 0.5mol/L 2 SO 4 Solution and 0.06mmol/L Na 2 MoO 4 Mixing the solutions to obtain a mixed solution;
dissolving manganese acetate in a mixed solution of deionized water, absolute ethyl alcohol and ethylene glycol, and aging for 3 days to obtain manganese salt aging solution;
placing the foam nickel substrate in a reaction kettle filled with manganese salt aging liquid, and reacting for 2-10 hours at 150-250 ℃ to obtain a manganous oxide precursor electrode;
in the three-electrode system, an electrochemical workstation is utilized, a constant current charge-discharge mode is adopted, the set voltage range is 0.1-0.9V, the current is 1mA, the number of circulation turns is 300, and the Na and Mo bimetal ion doped manganese dioxide electrode is obtained.
Referring to fig. 2, fig. 2 (c) and (d) are respectively surface scanning electron microscope images of the bimetal ion doped manganese dioxide electrode of the embodiment under different resolutions, and as can be seen from fig. 2, the bimetal ion doped manganese dioxide obtained in the embodiment has a nano-sheet structure, a plurality of nano-sheets are stacked together, and white strips in fig. 2 are edges of the nano-sheets, and some Xu Juanqu are arranged.
Example 3
A bimetal ion doped manganese dioxide electrode comprises a foam nickel substrate and manganese-based oxide nano-sheets loaded on the surface of the foam nickel substrate, wherein the manganese-based oxide nano-sheets comprise manganese dioxide and Na ions and Mo ions doped in the manganese dioxide.
The preparation method of the bimetal ion doped manganese dioxide electrode comprises the following steps:
na of 0.5mol/L 2 SO 4 Solution and 0.2mmol/L Na 2 MoO 4 Mixing the solutions to obtain a mixed solution;
dissolving manganese acetate in a mixed solution of deionized water, absolute ethyl alcohol and ethylene glycol, and aging for 3 days to obtain manganese salt aging solution;
placing the foam nickel substrate in a reaction kettle filled with manganese salt aging liquid, and reacting for 2-10 hours at 150-250 ℃ to obtain a manganous oxide precursor electrode;
in the three-electrode system, an electrochemical workstation is utilized, a constant current charge-discharge mode is adopted, the set voltage range is 0.1-0.9V, the current is 1mA, the number of circulation turns is 300, and the Na and Mo bimetal ion doped manganese dioxide electrode is obtained.
Referring to fig. 3, fig. 3 (e) and (f) are respectively surface scanning electron microscope images of the bimetal ion doped manganese dioxide electrode of the embodiment under different resolutions, and as can be seen from fig. 3, the bimetal ion doped manganese dioxide obtained in the embodiment has a nano-sheet structure, a plurality of nano-sheets are stacked together, and white strips in fig. 3 are edges of the nano-sheets, and some Xu Juanqu are arranged.
Comparing fig. 1, 2 and 3, it can be seen that the lateral dimensions of the nanoplatelets decrease with increasing concentration of molybdate ions in the electrolyte, and the mutually agglomerated portions between the nanoplatelets form a spherical structure.
Example 4
A bimetal ion doped manganese dioxide electrode comprises a foam nickel substrate and manganese-based oxide nano-sheets loaded on the surface of the foam nickel substrate, wherein the manganese-based oxide nano-sheets comprise manganese dioxide and Na ions and W ions doped in the manganese dioxide.
The preparation method of the bimetal ion doped manganese dioxide electrode comprises the following steps:
na of 0.5mol/L 2 SO 4 Solution and 0.06mmol/L Na 2 WO 4 Mixing the solutions to obtain a mixed solution;
dissolving manganese acetate in a mixed solution of deionized water, absolute ethyl alcohol and ethylene glycol, and aging for 3 days to obtain manganese salt aging solution;
placing the foam nickel substrate in a reaction kettle filled with manganese salt aging liquid, and reacting for 2-10 hours at 150-250 ℃ to obtain a manganous oxide precursor electrode;
in the three-electrode system, an electrochemical workstation is utilized, a constant current charge-discharge mode is adopted, the set voltage range is 0.1-0.9V, the current is 1mA, the number of circulation turns is 300, and the Na and Mo bimetal ion doped manganese dioxide electrode is obtained.
Comparative example 1 (differing from example 1 in that the surface of the substrate is free of manganese-based oxide nanoplatelets)
The preparation method of the electrode of the comparative example comprises the following steps:
na of 0.5mol/L 2 SO 4 Solution and 0.04mmol/L Na 2 MoO 4 Mixing the solutions to obtain a mixed solution;
in the three-electrode system, an electrochemical workstation is utilized, a constant current charge-discharge mode is adopted, the set voltage range is 0.1-0.9V, the current is 1mA, and the cycle number is 300, so that the electrode is obtained.
The electrode obtained in this comparative example was subjected to electrochemical test in the same manner as in example 1, and the test results are shown in fig. 7.
FIG. 7 (a) is a cyclic voltammogram of the electrode obtained in comparative example 1 at 10mV/s, and FIG. 7 (b) is a charge-discharge diagram at 1mA current. The electrode cyclic voltammogram of comparative example 1 detected a very small current value compared to the electrode of example 1, and the charge-discharge time was very short, indicating that the electrode had no capacitive contribution.
Comparative example 2 (differing from example 1 in that the metal ion doped in the manganese oxide is a single metal ion)
The preparation method of the electrode of the comparative example comprises the following steps:
preparation of 0.5mol/L Na 2 SO 4 A solution;
dissolving manganese acetate in a mixed solution of deionized water, absolute ethyl alcohol and ethylene glycol, and aging for 3 days to obtain manganese salt aging solution;
placing the foam nickel substrate in a reaction kettle filled with manganese salt aging liquid, and reacting for 2-10 hours at 150-250 ℃ to obtain a manganous oxide precursor electrode;
taking a manganous oxide precursor electrode as a working electrode, a Pt sheet electrode as a counter electrode and Ag/AgCl as a reference electrode, and simultaneously taking the Na as a reference electrode 2 SO 4 In the three-electrode system, an electrochemical workstation is used, a constant current charge-discharge mode is adopted, the voltage range is set to be 0.1-0.9V, the current is 1mA, the number of cycles is 300, and the Na ion doped manganese dioxide electrode is obtained.
The electrode obtained in this comparative example was subjected to electrochemical test in the same manner as in example 1, and the test results are shown in fig. 8.
FIG. 8 (a) is a cyclic voltammogram at different scan rates; fig. 8 (b) is a constant current charge-discharge curve at different current densities. By calculation, the electrode specific capacities were 347, 317, 288, 265 and 236F/g at 1, 2, 5, 10 and 20A/g, respectively. Compared with the electrode of example 1, the electrode of this comparative example has a reduced specific capacity due to doping with only a single metal ion.
Referring to fig. 9, fig. 9 is a graph showing comparison of the cyclic charge and discharge stability of the electrodes prepared in example 1 and comparative example 2. As can be seen from the graph, the specific capacity retention value of the electrode of example 1 reaches 94% after 1000 cycles of charge and discharge, while the electrode of comparative example 2 only retains 63%, thus showing that the doping of the bimetal ions can significantly improve the cycle stability of the electrode.
The main electrochemical performance indexes achievable by the electrodes prepared in examples 1 to 4 and comparative examples 1 to 2 described above are shown in table 1.
TABLE 1
Figure BDA0003261958130000081
As can be seen from the data in Table 1, the electrodes prepared in examples 1-4 have significantly higher capacity retention after 1000 cycles of charge and discharge than the electrodes prepared in comparative examples 1-2, and the electrochemical comprehensive performance is significantly better than that of comparative examples 1-2. As is clear from the comparison of the data between examples 1 to 3, the specific capacity of the finally obtained electrode is reduced with the increase of the concentration of the molybdate ions in the electrolyte, but the cycle stability is improved, and in order to obtain a higher specific capacity and a better cycle stability, the concentration of the molybdate ions in the electrolyte needs to be controlled, and the comprehensive performance of example 1 is optimal, namely, when the concentration of the molybdate ions in the electrolyte is 0.04mmol/L, the comprehensive performance of the electrode is optimal.
While the preferred embodiments of the present invention have been illustrated and described, the present invention is not limited to the embodiments, and various equivalent modifications and substitutions can be made by one skilled in the art without departing from the spirit of the present invention, and these are intended to be included in the scope of the present invention as defined in the appended claims.

Claims (10)

1. An electrode, comprising a substrate and manganese-based oxide nanoplatelets supported on the surface of the substrate, the manganese-based oxide nanoplatelets comprising manganese oxide and a bi-metal ion doped in the manganese oxide, the bi-metal ion comprising an alkali metal ion or an alkaline earth metal ion, and a transition metal ion, the transition metal ion not comprising a manganese ion; the alkali metal ions or alkaline earth metal ions are doped in the layered structure of the manganese oxide; the transition metal ion and Mn 2+ Forming a oxometalate.
2. The electrode of claim 1, wherein the manganese-based oxide nanoplatelets have a width of 20-500nm and a thickness of 1-20nm.
3. The electrode of claim 1, wherein the alkali or alkaline earth metal ions comprise Li, na, K, ca or Mg ions; the transition metal ion includes Cr ion, mo ion, W ion, V ion, or Nb ion.
4. The electrode of claim 1, wherein the manganese oxide comprises manganese monoxide, manganese dioxide, manganese sesquioxide or manganese tetraoxide.
5. The electrode according to claim 1, wherein the atomic percentage of the alkali metal ion or alkaline earth metal ion in the manganese-based oxide nanoplatelets is 0.01 to 20%; the atom percentage content of the transition metal ions is 0.01-5%.
6. The electrode of claim 1, wherein the substrate comprises nickel foam, carbon paper, carbon cloth, or titanium foil.
7. A method of producing an electrode as claimed in any one of claims 1 to 6, comprising the steps of:
preparing a mixed solution containing the alkali metal ions or alkaline earth metal ions and the transition metal ions;
reacting the substrate with manganese salt to obtain a manganese oxide precursor electrode;
and immersing the manganese oxide precursor electrode in the mixed solution, and carrying out oxidation doping to obtain the electrode.
8. The method of manufacturing according to claim 7, wherein the manganese oxide precursor electrode comprises a trimanganese tetraoxide precursor electrode or a manganese monoxide precursor electrode; in the mixed solution, the concentration of the alkali metal ions or alkaline earth metal ions is 0.1-10mol/L, and the concentration of the transition metal ions is 0.01-5mmol/L; the oxidation doping adopts a cyclic voltammetry or constant current charge-discharge method; the lower limit of the cyclic voltammetry set voltage window is-0.5-0V, the upper limit is 0.8-1.5V, the scanning speed is 1-50mV/s, and the number of cycles is 10-500; the constant current charge-discharge method sets the lower limit of the voltage window to be-0.5-0V, the upper limit of the voltage window to be 0.8-1.5V and the current to be 0.5-10mA.
9. Use of an electrode according to any one of claims 1-6 in a capacitor.
10. A supercapacitor comprising an electrode as claimed in any one of claims 1 to 6.
CN202111075403.9A 2021-09-14 2021-09-14 Bimetal ion doped manganese dioxide electrode and preparation method and application thereof Active CN113936925B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111075403.9A CN113936925B (en) 2021-09-14 2021-09-14 Bimetal ion doped manganese dioxide electrode and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111075403.9A CN113936925B (en) 2021-09-14 2021-09-14 Bimetal ion doped manganese dioxide electrode and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN113936925A CN113936925A (en) 2022-01-14
CN113936925B true CN113936925B (en) 2023-05-30

Family

ID=79275747

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111075403.9A Active CN113936925B (en) 2021-09-14 2021-09-14 Bimetal ion doped manganese dioxide electrode and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN113936925B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116759562B (en) * 2023-08-16 2024-01-05 中石油深圳新能源研究院有限公司 Double-cation doped positive electrode material and preparation method and application thereof

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101546651B (en) * 2009-05-07 2011-04-20 哈尔滨工程大学 Nano graphite sheet/manganese dioxide doped composite material and preparation method thereof
US11233241B2 (en) * 2017-11-13 2022-01-25 The University Of New Hampshire Preparation of: I. intercalative metal oxide/conductive polymer composites as electrode materials for rechargeable batteries; II. sodium rich manganese oxide hydrate with capacity for aqueous Na-ion electrochemical energy storage
CN110729462B (en) * 2019-10-22 2021-05-25 湖北大学 Manganese oxide electrode material with metal cation intercalation structure and preparation method and application thereof
CN112952083A (en) * 2021-02-01 2021-06-11 燕山大学 Mn containing doped metal2O3Electrode material, preparation method thereof and application of electrode material as positive electrode material of zinc ion battery

Also Published As

Publication number Publication date
CN113936925A (en) 2022-01-14

Similar Documents

Publication Publication Date Title
Wang et al. A new concept hybrid electrochemical surpercapacitor: Carbon/LiMn2O4 aqueous system
CN107093741B (en) A kind of preparation method of high magnification nickel cobalt lithium aluminate cathode material
Gao et al. Spherical porous VN and NiOx as electrode materials for asymmetric supercapacitor
CN110642236B (en) Zinc-based aqueous battery negative electrode material and preparation method thereof
US10483595B2 (en) Tungsten-based material super battery and supercapacitor
CN109659542A (en) A kind of high voltage lithium cobalt oxide anode of core-shell structure and preparation method thereof
Guo et al. High performance Li–O2 battery using γ-MnOOH nanorods as a catalyst in an ionic-liquid based electrolyte
EP3319152A1 (en) Doped conductive oxide and improved electrochemical energy storage device polar plate based on same
Luo et al. A novel LiTi2 (PO4) 3/MnO2 hybrid supercapacitor in lithium sulfate aqueous electrolyte
CN110416530A (en) A kind of flower-shaped manganese dioxide/carbon composite material and preparation method and application
CN113936925B (en) Bimetal ion doped manganese dioxide electrode and preparation method and application thereof
CN115347182A (en) Long-cycle stable and high-rate sodium-ion battery positive electrode material
CN115172709A (en) High-performance strontium-doped ternary sodium-ion battery positive electrode material and preparation method thereof
CN101399120A (en) Novel hybrid supercapacitor
CN108987125B (en) Perovskite stannate supercapacitor electrode material, preparation method and application
CN113097577A (en) Water-based zinc ion battery electrolyte for inhibiting vanadium dissolution of vanadium-based positive electrode, and preparation method and application thereof
CN115083792B (en) Nickel-vanadium-manganese oxide positive electrode material and preparation method and application thereof
CN115995351A (en) Preparation method of transition metal nickel doped manganese dioxide electrode material
CN111029556A (en) Multi-modified nickel-rich ternary material and preparation method and application thereof
CN115642241A (en) High-stability layered oxide sodium-ion battery positive electrode active material and preparation method thereof
CN114792606A (en) Carbon-loaded manganese-doped sodium titanate energy storage material, preparation method and application thereof, and negative electrode plate
CN115241435A (en) Layered Na 3 M 2 XO 6 Oxide-coated modified sodium manganate cathode material and preparation method thereof
CN114597077A (en) Application of pre-lithiated carbon negative electrode material in sodium ion capacitor and potassium ion capacitor
CN106684383A (en) Mesoporous molybdenum nitride nanowire, and preparation method and application thereof
CN112420401A (en) Bismuth oxide/manganese oxide composite supercapacitor and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant