CN113936925A - 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 PDFInfo
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 150000002500 ions Chemical class 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title abstract description 11
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 83
- 239000011572 manganese Substances 0.000 claims abstract description 26
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 24
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910001428 transition metal ion Inorganic materials 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 17
- 229910001413 alkali metal ion Inorganic materials 0.000 claims abstract description 16
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 claims abstract description 16
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002135 nanosheet Substances 0.000 claims description 31
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 30
- 239000011259 mixed solution Substances 0.000 claims description 17
- 239000002243 precursor Substances 0.000 claims description 17
- 150000002696 manganese Chemical class 0.000 claims description 15
- 229910052759 nickel Inorganic materials 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 14
- 239000002585 base Substances 0.000 claims description 13
- 238000002484 cyclic voltammetry Methods 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 12
- VASIZKWUTCETSD-UHFFFAOYSA-N oxomanganese Chemical compound [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 claims description 10
- 229910001415 sodium ion Inorganic materials 0.000 claims description 7
- 239000003990 capacitor Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229910001424 calcium ion Inorganic materials 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims description 2
- 229910001416 lithium ion Inorganic materials 0.000 claims description 2
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 2
- 229910001437 manganese ion Inorganic materials 0.000 claims description 2
- 239000002055 nanoplate Substances 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- LQKOJSSIKZIEJC-UHFFFAOYSA-N manganese(2+) oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Mn+2].[Mn+2].[Mn+2].[Mn+2] LQKOJSSIKZIEJC-UHFFFAOYSA-N 0.000 claims 1
- TYTHZVVGVFAQHF-UHFFFAOYSA-N manganese(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Mn+3].[Mn+3] TYTHZVVGVFAQHF-UHFFFAOYSA-N 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 11
- 238000004146 energy storage Methods 0.000 abstract description 7
- 230000014759 maintenance of location Effects 0.000 abstract description 7
- 238000009792 diffusion process Methods 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 238000004090 dissolution Methods 0.000 abstract description 4
- 230000001737 promoting effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 21
- 230000032683 aging Effects 0.000 description 19
- 229910021645 metal ion Inorganic materials 0.000 description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 17
- 238000007599 discharging Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000007832 Na2SO4 Substances 0.000 description 7
- 229910052938 sodium sulfate Inorganic materials 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000010277 constant-current charging Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 230000009977 dual effect Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229940071125 manganese acetate Drugs 0.000 description 6
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000001351 cycling effect Effects 0.000 description 5
- 239000006260 foam Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229910052750 molybdenum Inorganic materials 0.000 description 5
- 229910004619 Na2MoO4 Inorganic materials 0.000 description 4
- -1 molybdate ions Chemical class 0.000 description 4
- 239000011684 sodium molybdate Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 238000007600 charging Methods 0.000 description 3
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- 239000007772 electrode material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
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- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229910020350 Na2WO4 Inorganic materials 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
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- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
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- 230000001105 regulatory effect Effects 0.000 description 1
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- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
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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
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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
- H01G11/84—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
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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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Abstract
The invention discloses a bimetal ion doped manganese dioxide electrode and a preparation method and application thereof. The electrode of the invention is doped in the manganese oxide layered structure through alkali metal ions or alkaline earth metal ions, which is beneficial to reducing the resistance of electrolyte ions in the diffusion of the electrolyte ions and promoting the kinetic process of energy storage, and simultaneously, transition metal ions pass through the manganese oxide layered structure and are mixed with Mn2+The formed oxometallate can effectively inhibit the manganese dissolution behavior, has excellent rate performance and cycle stability, 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％。
Description
Technical Field
The invention belongs to the technical field of energy storage, and particularly relates to a bimetallic ion doped manganese dioxide electrode and a preparation method and application thereof.
Background
The super capacitor serving as a novel electrochemical energy storage device has the advantages of short charging and discharging time, long cycle service life, safety, cleanness and the like, and can supplement the technical blank of secondary chemical batteries. Currently, the mainstream of electrode materials of the supercapacitor comprises carbon materials, conductive polymers and transition metal oxides. The manganese oxide has rich resource content, environmental protection, high electrochemical activity and high theoretical capacitance (1370F/g), and is a super capacitor electrode material with great application prospect. The capacity of the manganese oxide is contributed by three processes of physical electrostatic adsorption of electrolyte ions on the surface of the manganese oxide, faradaic redox reaction on the surface and near the surface of the manganese oxide and intercalation and deintercalation in crystal lattices. However, manganese oxide has the problems of low conductivity and poor ion diffusion, electrons and ions are difficult to freely transport in the material, the utilization rate of active sites is not high, and the actual capacitance of the electrode is far lower than the theoretical value. Currently, the capacity of manganese dioxide electrodes prepared by the tablet process 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 manganese oxide, the most widely applied solution at present is to perform coating treatment by using a carbon material with better conductivity and stability. Although the method can improve the conductivity and stability of the manganese oxide, the method is not beneficial to the diffusion of electrolyte ions in the solid phase of the manganese oxide and reduces the energy storage kinetic process.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the invention provides a bimetallic 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 rate performance and cycle stability.
The invention provides a bimetal ion doped manganese dioxide electrode, which comprises a substrate and manganese-based oxide nanosheets loaded on the surface of the substrate, wherein the manganese-based oxide nanosheets comprise manganese oxide and bimetal ions doped in the manganese oxide, and the bimetal ions comprise alkali metal ions or alkaline earth metal ions and transition metal ions, and the transition metal ions do not comprise manganese ions.
The applicant of the invention finds in 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 metal ion doping can effectively improve the conductivity of the manganese oxide, and the alkali metal ions or alkaline earth metal ions are doped in the manganese oxide layered structure, so that the diffusion resistance of electrolyte ions in the manganese oxide layered structure is reduced, and the kinetic process of energy storage is promoted; simultaneous passage of transition metal ions with Mn2+The oxometallate is formed, so that the manganese dissolution behavior can be effectively inhibited, and the rate capability and the cycle stability are improved.
Preferably, the manganese-based oxide nanosheets have a width of 20-500nm and a thickness of 1-20 nm.
Preferably, the alkali metal ion or alkaline earth metal ion includes Li ion, Na ion, K ion, Ca ion, or Mg ion; the transition metal ions include Cr ions, Mo ions, W ions, V ions, or Nb ions.
Preferably, the manganese oxide comprises manganese monoxide, manganese dioxide, manganic oxide or manganic oxide.
Preferably, in the manganese-based oxide nanosheets, the atomic percentage of the alkali metal ions or alkaline earth metal ions is 0.01-20%; the atomic percentage content of the transition metal ions is 0.01-5%.
Preferably, the substrate comprises foamed nickel, carbon paper, carbon cloth or titanium foil.
The second aspect of the present invention provides a method for preparing the bi-metal ion doped manganese dioxide electrode, comprising the following steps:
preparing a mixed solution containing the alkali metal ions or the alkaline earth metal ions and the transition metal ions;
reacting the base material with manganese salt to obtain a manganese oxide precursor electrode;
and soaking the manganese oxide precursor electrode in the mixed solution, and carrying out in-situ electrochemical drive oxidation doping treatment in a three-electrode device by utilizing an electrochemical workstation mode to obtain the double-metal 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 the alkaline earth metal ions is 0.1-10mol/L, and the concentration of the transition metal ions is 0.01-5 mmol/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 0.2 mmol/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 0.06 mmol/L.
Preferably, the preparation method of the trimanganese tetroxide precursor electrode comprises the following steps:
and placing the base material in a reaction kettle filled with a manganese salt aging solution, and heating and reacting for a certain time to obtain the manganese salt aging liquid. Further, the manganese salt aging solution is obtained by dissolving manganese acetate in a mixed solution of deionized water, absolute ethyl alcohol and ethylene glycol and aging for 3 days; the heating reaction temperature is 150-250 ℃, and the reaction time is 2-10h, so as to obtain the trimanganese tetroxide precursor electrode.
Preferably, the preparation method of the manganese monoxide precursor electrode comprises the following steps:
and (3) placing the trimanganese tetroxide precursor electrode in a tube furnace, introducing argon, and carrying out high-temperature annealing treatment for a certain time to obtain the trimanganese tetroxide electrode. Further, the high temperature is 800-.
Preferably, the electrochemical workstation mode comprises cyclic voltammetry or galvanostatic charging and discharging.
Preferably, the lower limit of the voltage window of the cyclic voltammetry is-0.5-0V, the upper limit is 0.8-1.5V, the scanning rate is 1-50mV/s, and the number of cycles is 10-500; the constant current charge and discharge method sets the lower limit of a voltage window to be-0.5-0V, the upper limit to be 0.8-1.5V and the current to be 0.5-10 mA.
A third aspect of the invention provides the use of said bi-metal 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 base material and manganese-based oxide nanosheets loaded on the surface of the base material, wherein the manganese-based oxide nanosheets 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 beneficial to reducing the diffusion resistance of electrolyte ions in the manganese oxide layered structure and promoting the kinetic process of energy storage, and simultaneously, transition metal ions pass through Mn2+Forming metal oxometallate, which can effectively inhibit the manganese dissolution behavior. The bimetallic ion doped manganese dioxide electrode has excellent rate performance and cycling 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 cyclic charge and discharge reaches 94-98%.
(2) The method utilizes a manganese oxide precursor electrode to remove Mn under the drive of electrochemical oxidation2+Mn which provides vacancies for the insertion of other metal cations and is simultaneously removed2+The manganese dioxide is bonded with transition metal acid ions, and one-step doping of manganese dioxide and different bimetallic ions can be skillfully realized by regulating the types of the metal ions.
(3) The invention adopts cyclic voltammetry or constant current charge-discharge method, not only realizes one-step doping of bimetallic ions in manganese oxide, but also can regulate and control the morphology of the nanosheet through the concentration of transition metal acid ions. Transition metal ion and Mn2+A double metal acid salt formed by bonding, the formation of the nano-sheet is controlled by influencing the oxidation efficiency of the manganese oxide precursor electrode, so as toResulting in different nanoplate dimensions.
Drawings
FIG. 1 is a surface scanning electron micrograph of an electrode prepared in example 1 of the present invention;
FIG. 2 is a surface scanning electron micrograph of an electrode prepared in example 2 of the present invention;
FIG. 3 is a surface scanning electron micrograph of an 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 a galvanostatic charge-discharge curve for the electrode prepared in example 1 of the present invention;
FIG. 7 is a cyclic voltammogram and a galvanostatic charge-discharge curve of the electrode prepared in comparative example 1 according to the present invention;
FIG. 8 is a cyclic voltammogram and a galvanostatic charge-discharge curve of the electrode prepared in comparative example 2 of the present invention;
fig. 9 is a graph comparing the charge and discharge stability of the electrodes prepared in example 1 of the present invention and comparative example 2.
Detailed Description
In order to make the technical solutions of the present invention more apparent to those skilled in the art, the following examples are given for illustration. It should be noted that the following examples are not intended to limit the scope of the claimed invention.
The components, reagents or devices used in the following examples are conventionally commercially available or can be obtained by conventionally known methods, unless otherwise specified.
Example 1
A bimetal ion doped manganese dioxide electrode comprises a foamed nickel base material and manganese-based oxide nanosheets loaded on the surface of the foamed nickel base material, wherein the manganese-based oxide nanosheets 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:
adding 0.5mol/L of Na2SO4Solution and 0.04mmol/L Na2MoO4Mixing 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 a manganese salt aging solution;
placing the foam nickel substrate in a reaction kettle filled with a manganese salt aging liquid, and reacting for 2-10h at the temperature of 150-;
and in the three-electrode system, an electrochemical workstation is utilized, a constant current charging and discharging 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 and Mo dual-metal ion doped manganese dioxide electrode is obtained.
Referring to fig. 1, (a) and (b) in fig. 1 are scanning electron microscope images of the surface of the dual metal ion doped manganese dioxide electrode in the present embodiment under different resolutions, respectively, as can be seen from fig. 1, the dual metal ion doped manganese dioxide obtained in the present embodiment is a nanosheet structure, a plurality of nanosheets are stacked together, and the white strip in fig. 1 is the edge of the nanosheet and has some curl.
Referring to FIG. 4, 504cm-1Small shoulder peak and 570-650cm-1The large broad peak of the manganese dioxide is the characteristic peak of birnessite type manganese dioxide.
Referring to fig. 5, it can be seen that the elements Na, Mo, Mn and O are uniformly distributed in the electrode material.
By combining the analyses shown in fig. 1, 4 and 5, it can be seen that the Na and Mo bi-metal ion doped manganese dioxide electrode is successfully prepared in this example.
The electrodes obtained in this example were subjected to electrochemical tests: the bimetallic ion doped manganese dioxide electrode prepared in the example is used as a working electrode, a Pt sheet electrode is used as a counter electrode, Ag/AgCl is used as a reference electrode, and 0.5mol/L of Na2SO4Testing cyclic voltammetry curves at different scanning rates in a three-electrode system consisting of aqueous electrolyteAnd constant current charge and discharge curves at different current densities, the test results are shown in fig. 6.
Fig. 6(a) is a cyclic voltammogram at different scan rates, and it can be seen that the curves are all rectangular and approximately symmetrical, and the area increases with increasing scan rate, indicating that the electrode has ideal capacitance characteristics and a reversible charge storage process occurs.
Fig. 6(b) is a constant current charge and discharge curve at different current densities, and it can be seen that the curve is linear and symmetrical, indicating that the reaction process is reversible.
By calculation, under the conditions of 1, 2, 5, 10 and 20A/g, the specific capacities of the electrodes are 401, 371, 337, 309 and 276F/g respectively. When the large current is 20A/g, 69% of specific capacity is still maintained, and the electrode has excellent rate performance.
Example 2
A bimetal ion doped manganese dioxide electrode comprises a foamed nickel base material and manganese-based oxide nanosheets loaded on the surface of the foamed nickel base material, wherein the manganese-based oxide nanosheets 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:
adding 0.5mol/L of Na2SO4Solution and 0.06mmol/L Na2MoO4Mixing 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 a manganese salt aging solution;
placing the foam nickel substrate in a reaction kettle filled with a manganese salt aging liquid, and reacting for 2-10h at the temperature of 150-;
and in the three-electrode system, an electrochemical workstation is utilized, a constant current charging and discharging 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 and Mo dual-metal ion doped manganese dioxide electrode is obtained.
Referring to fig. 2, (c) and (d) in fig. 2 are scanning electron microscope images of the surface of the dual metal ion doped manganese dioxide electrode in the present embodiment under different resolutions, respectively, as can be seen from fig. 2, the dual metal ion doped manganese dioxide obtained in the present embodiment is a nanosheet structure, a plurality of nanosheets are stacked together, and the white strip in fig. 2 is the edge of the nanosheet and has some curl.
Example 3
A bimetal ion doped manganese dioxide electrode comprises a foamed nickel base material and manganese-based oxide nanosheets loaded on the surface of the foamed nickel base material, wherein the manganese-based oxide nanosheets 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:
adding 0.5mol/L of Na2SO4Solution and 0.2mmol/L Na2MoO4Mixing 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 a manganese salt aging solution;
placing the foam nickel substrate in a reaction kettle filled with a manganese salt aging liquid, and reacting for 2-10h at the temperature of 150-;
and in the three-electrode system, an electrochemical workstation is utilized, a constant current charging and discharging 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 and Mo dual-metal ion doped manganese dioxide electrode is obtained.
Referring to fig. 3, (e) and (f) in fig. 3 are scanning electron microscope images of the surface of the dual metal ion doped manganese dioxide electrode in the present embodiment under different resolutions, respectively, as can be seen from fig. 3, the dual metal ion doped manganese dioxide obtained in the present embodiment is a nanosheet structure, a plurality of nanosheets are stacked together, and the white strip in fig. 3 is the edge of the nanosheet and has some curl.
Comparing fig. 1, fig. 2 and fig. 3, it can be seen that the transverse dimension of the nanosheets decreases with the increase of the concentration of molybdate ions in the electrolyte, and the agglomerated parts of the nanosheets form a spherical structure.
Example 4
A bimetal ion doped manganese dioxide electrode comprises a foamed nickel base material and manganese-based oxide nanosheets loaded on the surface of the foamed nickel base material, wherein the manganese-based oxide nanosheets 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:
adding 0.5mol/L of Na2SO4Solution and 0.06mmol/L Na2WO4Mixing 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 a manganese salt aging solution;
placing the foam nickel substrate in a reaction kettle filled with a manganese salt aging liquid, and reacting for 2-10h at the temperature of 150-;
and in the three-electrode system, an electrochemical workstation is utilized, a constant current charging and discharging 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 and Mo dual-metal ion doped manganese dioxide electrode is obtained.
Comparative example 1 (different from example 1 in that the surface of the substrate is free of manganese-based oxide nanosheets)
The method for producing the electrode of this comparative example includes the steps of:
adding 0.5mol/L of Na2SO4Solution and 0.04mmol/L Na2MoO4Mixing the solutions to obtain a mixed solution;
in the three-electrode system, an electrochemical workstation is utilized, a constant current charging and discharging mode is adopted, the voltage range is set to be 0.1-0.9V, the current is set to be 1mA, and the number of cycles is set to be 300 cycles, so that the electrode is obtained.
The electrode obtained in this comparative example was subjected to electrochemical tests 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 curve under a current of 1 mA. The cyclic voltammetry curve of the electrode of comparative example 1 detected a small current value and a very short charging and discharging time compared to the electrode of example 1, indicating that the electrode did not contribute to capacitance.
Comparative example 2 (different from example 1 in that the metal ion doped in the manganese oxide is a single metal ion)
The method for producing the electrode of this comparative example includes the steps of:
0.5mol/L of Na is prepared2SO4A solution;
dissolving manganese acetate in a mixed solution of deionized water, absolute ethyl alcohol and ethylene glycol, and aging for 3 days to obtain a manganese salt aging solution;
placing the foam nickel substrate in a reaction kettle filled with a manganese salt aging liquid, and reacting for 2-10h at the temperature of 150-;
taking a trimanganese tetroxide 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 Na2SO4The solution is used as electrolyte, in the three-electrode system, an electrochemical workstation is utilized, a constant current charging and discharging mode is adopted, the voltage range is set to be 0.1-0.9V, the current is 1mA, and the number of cycles is 300, so that the Na ion doped manganese dioxide electrode is obtained.
The electrode obtained in this comparative example was subjected to electrochemical tests 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 and discharge curve at different current densities. By calculation, under the conditions of 1, 2, 5, 10 and 20A/g, the specific capacity of the electrode is 347, 317, 288, 265 and 236F/g respectively. Compared with the electrode of example 1, the electrode of the comparative example is doped with only a single metal ion, so that the specific capacity is reduced.
Referring to fig. 9, fig. 9 is a graph comparing the charge and discharge stability of the electrodes prepared in example 1 and comparative example 2. It can be seen from the figure that after 1000 cycles of charge and discharge, the specific capacity retention value of the electrode of example 1 reaches 94%, while the specific capacity retention value of the electrode of comparative example 2 only retains 63%, thereby showing that the doping of the bimetallic ions can significantly improve the cycling stability of the electrode.
The main indexes of electrochemical performance 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
As can be seen from the data in Table 1, the capacity retention rate of the electrodes prepared in examples 1-4 after 1000 cycles of charge and discharge is significantly higher than that of the electrodes prepared in comparative examples 1-2, and the electrochemical comprehensive performance is obviously better than that of the electrodes prepared in comparative examples 1-2. As can be seen from the comparison of the data in examples 1 to 3, the specific capacity of the finally obtained electrode is reduced with the increase of the concentration of molybdate ions in the electrolyte, but the cycling stability is improved, and in order to obtain a higher specific capacity and a better cycling stability, the concentration of molybdate ions in the electrolyte needs to be controlled, so that the comprehensive performance of example 1 is optimal, that is, when the concentration of 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, it will be understood by those skilled in the art that the present invention is not limited to the details of the embodiments shown and described, but is capable of numerous equivalents and substitutions without departing from the spirit of the invention as set forth in the claims appended hereto.
Claims (10)
1. An electrode, comprising a substrate and manganese-based oxide nanosheets supported on a surface of the substrate, the manganese-based oxide nanosheets comprising a manganese oxide and a bimetallic ion doped in the manganese oxide, the bimetallic 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.
2. The electrode of claim 1, wherein the manganese-based oxide nanoplates have a width of 20-500nm and a thickness of 1-20 nm.
3. The electrode of claim 1, wherein the alkali metal ions or alkaline earth metal ions comprise Li ions, Na ions, K ions, Ca ions, or Mg ions; the transition metal ions include Cr ions, Mo ions, W ions, V ions, or Nb ions.
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 manganese-based oxide nanosheets have an atomic percent of the alkali metal ions or alkaline earth metal ions of 0.01-20%; the atomic percentage content of the transition metal ions is 0.01-5%.
6. The electrode of claim 1, wherein the substrate comprises foamed nickel, carbon paper, carbon cloth, or titanium foil.
7. A method of making an electrode according to any one of claims 1 to 6, comprising the steps of:
preparing a mixed solution containing the alkali metal ions or the alkaline earth metal ions and the transition metal ions;
reacting the base material with manganese salt to obtain a manganese oxide precursor electrode;
and soaking the manganese oxide precursor electrode in the mixed solution for oxidation doping to obtain the electrode.
8. The production method according to claim 7, wherein 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 the alkaline earth metal ions is 0.1-10mol/L, and the concentration of the transition metal ions is 0.01-5 mmol/L; the oxidation doping adopts a cyclic voltammetry method or a constant current charge-discharge method; the lower limit of a voltage window set by the cyclic voltammetry is-0.5-0V, the upper limit is 0.8-1.5V, the scanning rate is 1-50mV/s, and the number of cyclic cycles is 10-500 cycles; the constant current charge and discharge method sets the lower limit of a voltage window to be-0.5-0V, the upper limit to be 0.8-1.5V and the current to be 0.5-10 mA.
9. Use of an electrode according to any one of claims 1 to 6 in a capacitor.
10. A supercapacitor comprising an electrode according to any one of claims 1 to 6.
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