CN114300277B - Aluminum manganese oxide and application thereof as positive electrode material in water-based magnesium ion capacitor - Google Patents

Aluminum manganese oxide and application thereof as positive electrode material in water-based magnesium ion capacitor Download PDF

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CN114300277B
CN114300277B CN202111623713.XA CN202111623713A CN114300277B CN 114300277 B CN114300277 B CN 114300277B CN 202111623713 A CN202111623713 A CN 202111623713A CN 114300277 B CN114300277 B CN 114300277B
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aluminum
manganese oxide
magnesium ion
ion capacitor
positive electrode
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CN114300277A (en
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马天翼
丁亚西
张思文
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Liaoning University
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    • Y02E60/13—Energy storage using capacitors

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Abstract

The invention discloses an aluminum manganese oxide and application thereof as a positive electrode material in a water-based magnesium ion capacitor. Adding manganese sulfate, aluminum sulfate and potassium permanganate into deionized water, stirring and dissolving, adding sulfuric acid dropwise, continuing stirring for 24 hours, transferring the obtained mixed solution into a reaction kettle, and performing hydrothermal reaction to obtain the aluminum-manganese oxide. The aluminum-manganese oxide is used as a positive electrode material and applied to a water system magnesium ion capacitor, and the electrochemical test shows that the single aluminum-manganese oxide has a higher specific capacity. And after being assembled with activated carbon into a device, a higher capacitance can still be achieved. The invention has simple synthesis process, is economical and environment-friendly, has low price and is hopeful to become a novel energy storage device.

Description

Aluminum manganese oxide and application thereof as positive electrode material in water-based magnesium ion capacitor
Technical Field
The invention belongs to the technical field of materials, and particularly relates to an aluminum manganese oxide and application of the aluminum manganese oxide serving as a positive electrode material in a water-based magnesium ion capacitor.
Background
With the rapid development of renewable energy sources such as solar energy, biomass energy, water power, wind energy and the like, as well as the construction of smart grids, the development of micro-grid technologies and energy interconnection, energy storage technologies are new challenges, which will change the global energy pattern. Electrochemical energy storage is highly appreciated due to its flexibility of application, high conversion efficiency and high power density, and is considered as an important form of energy storage in the future. Among all electrochemical energy storage systems, batteries of different kinds and functions are widely used in daily life, and wireless revolution of mobile phones, notebook computers, and electronic devices is realized. Among the conventional batteries, lead-acid and nickel-hydrogen batteries exhibit low energy density, and their corresponding organic electrolytes also cause serious environmental pollution, thus not meeting the requirements for sustainable development. Although the lithium ion battery has higher power density and energy density, the corresponding organic electrolyte has high flammability and explosiveness, and threatens the public safety of human health and society. At the same time, the supply limitations and high cost of lithium resources have limited its widespread use. Therefore, green and safe energy storage systems and electrode materials suitable for the same have been the focus of battery research. Rechargeable magnesium ion battery systems are a promising system and have been extensively studied due to their similar electrochemical properties and low cost as lithium. Wherein, the magnesium ion battery has rich crust reserves (about 2.9 percent) and high theoretical capacity (about 3833 mAh/cm) due to the no-dendritic characteristic thereof 3 ) And low reduction voltages (-2.37V vs. standard hydrogen electrodes) are particularly attractive. Nevertheless, magnesium ion batteries still have a major problem, namelyThe strong electrostatic interaction between magnesium ions and the host causes slow solid state diffusion and strong polarization effects, so proper selection of electrode materials and electrolytes is required. Magnesium ions in organic electrolytes must be separated from solvated species prior to intercalation, severely affecting their diffusion kinetics. At the same time, the organic electrolyte is flammable and toxic, so that the rechargeable aqueous magnesium solution is obviously a better choice. However, only a few reports are available regarding aqueous rechargeable magnesium ion batteries.
Disclosure of Invention
The invention aims to provide an aluminum manganese oxide and application thereof as a positive electrode material in a water-based magnesium ion capacitor, and the specific capacitance of the water-based magnesium ion capacitor is remarkably improved.
The technical scheme adopted by the invention is as follows: the preparation method of the aluminum manganese oxide comprises the following steps: adding manganese sulfate, aluminum sulfate and potassium permanganate into deionized water, stirring and dissolving, adding sulfuric acid dropwise, continuing stirring for 24 hours, transferring the obtained mixed solution into a reaction kettle, and performing hydrothermal reaction to obtain the novel anode material aluminum-manganese oxide.
Preferably, the molar ratio of the aluminum manganese oxide to the aluminum sulfate to the potassium permanganate=1:0.24-3.6:0.8.
Preferably, the hydrothermal reaction of the aluminum manganese oxide is carried out at 180 ℃ for 24 hours.
The invention provides an application of aluminum manganese oxide as a positive electrode material in a water-based magnesium ion capacitor.
An aluminum-manganese oxide-based water system magnesium ion capacitor takes aluminum-manganese oxide as a positive electrode material, and the preparation method comprises the following steps:
1) Preparation of positive electrode: uniformly mixing aluminum-manganese oxide, a binder and a conductive material, dropwise adding a small amount of NMP as a solvent, uniformly mixing, directly coating on carbon paper of a substrate, drying in a vacuum drying oven, and taking out to obtain a positive electrode plate coated with aluminum-manganese oxide;
2) Preparation of the negative electrode: uniformly mixing active carbon, a binder and a conductive material, dropwise adding a small amount of NMP as a solvent, uniformly mixing, directly coating on carbon paper, drying in a vacuum drying oven, and taking out to obtain a negative electrode plate coated with the active carbon;
3) Preparation of a water-based magnesium ion capacitor: placing the positive electrode plate into a positive electrode shell, enabling one surface coated with aluminum-manganese oxide to contact a diaphragm, then placing the diaphragm, then dripping electrolyte, then placing the negative electrode plate above the diaphragm, enabling one surface coated with active carbon to contact the diaphragm, then sequentially placing a gasket and an elastic sheet, finally buckling the negative electrode shell, and packaging to obtain the water-based magnesium ion capacitor.
Preferably, the binder is PVDF or CMC.
Preferably, the conductive material is Super P or acetylene black.
Preferably, the electrolyte is one of an aqueous magnesium sulfate solution, an aqueous magnesium chloride solution, and an aqueous magnesium nitrate solution.
Preferably, the membrane is one of a cellulose membrane, a polypropylene membrane, a membrane paper and a polymeric semipermeable membrane.
The beneficial effects of the invention are as follows:
1. the invention designs a novel water system magnesium ion asymmetric capacitor, which uses aluminum manganese oxide and active carbon as anode and cathode materials respectively. Has the following advantages: first, metallic aluminum is an ideal doping element for metal oxides, which is cost effective and less toxic. More importantly, trivalent aluminum ions can combine with oxygen atoms to form stable Al-O chemical bonds. Second, due to Al 3+ Ion radius (53.5 pm) and Mn 4+ (53 pm) is very close, so Al 3+ Is a proper cation for replacing doping of manganese dioxide, and can easily reduce band gap, generate new molecular orbitals and introduce impurity energy levels into the manganese dioxide.
2. The discharge time of the novel aluminum manganese oxide after aluminum doping is increased by 2208 seconds, the specific capacitance is as high as 259.58F/g, and the discharge time is increased by about 1.8 times compared with that of the original manganese dioxide.
3. The selected material has good pseudocapacitance performance, and has the advantages of low cost, environmental protection and recoverability. Meanwhile, the electrolyte has high theoretical specific capacitance and good stability in electrolyte environment.
4. According to the invention, a novel combination of the anode material aluminum manganese oxide and the activated carbon is adopted, and the combination fully breaks through a conventional combination form. But also exhibits superior performance in terms of specific capacitance. The method has simple synthesis process and assembly process, is economical and environment-friendly, and has low price. Is expected to become ideal materials and devices in the future in energy storage.
Drawings
FIG. 1 is an XRD spectrum of manganese dioxide and aluminum manganese oxides prepared in accordance with the present invention.
Fig. 2 is an SEM spectrum of the aluminum manganese oxide prepared according to the present invention.
FIG. 3 is a cyclic voltammogram of an aluminum manganese oxide and activated carbon asymmetric aqueous magnesium ion capacitor prepared in accordance with the present invention.
FIG. 4 is a graph showing the specific capacitance of an aluminum manganese oxide and activated carbon asymmetric aqueous magnesium ion capacitor prepared according to the present invention.
Detailed Description
Example 1
The preparation method of the aluminum manganese oxide comprises the following steps:
weighing 0.01mol of manganese sulfate monohydrate, 0.0024mol of aluminum sulfate octadecanoate and 0.008mol of potassium permanganate, adding into 50mL of deionized water, stirring for dissolving, then dropwise adding 20mL of sulfuric acid with the concentration of 0.2mol/L, continuously stirring for 24 hours, transferring the obtained mixed solution into a reaction kettle, and performing hydrothermal reaction at 180 ℃ for 24 hours to obtain aluminum manganese oxide Al x MnO 2 。
(II) comparative example manganese dioxide was prepared as follows:
weighing 0.01mol of manganese sulfate monohydrate and 0.008mol of potassium permanganate, adding into 50mL of deionized water, stirring for dissolution, then dropwise adding 20mL of sulfuric acid with the concentration of 0.2mol/L, continuously stirring for 24 hours, transferring the obtained mixed solution into a reaction kettle, and performing hydrothermal reaction at 180 ℃ for 24 hours to obtain the manganese dioxide material.
(III) detection
FIG. 1 is an XRD spectrum of manganese dioxide and aluminum manganese oxides prepared in accordance with the present invention. Can be seen from FIG. 1As can be seen, the XRD patterns of the samples did not show significant changes after Al doping, and the shift of the individual peaks indicated that the Al ions were successfully doped into MnO 2 Is a kind of medium.
Fig. 2 is an SEM spectrum of the aluminum manganese oxide prepared according to the present invention. As can be seen from fig. 2, the samples gradually agglomerate from individual nanorods into clusters due to the combination of trivalent aluminum ions with oxygen atoms forming stable al—o chemical bonds.
Example 2
The preparation method of the aluminum manganese oxide comprises the following steps:
weighing 0.01mol of manganese sulfate monohydrate, 0.0192mol of aluminum sulfate octadecanoate and 0.008mol of potassium permanganate, adding into 50mL of deionized water, stirring for dissolving, then dropwise adding 20mL of sulfuric acid with the concentration of 0.2mol/L, continuously stirring for 24 hours, transferring the obtained mixed solution into a reaction kettle, and performing hydrothermal reaction at 180 ℃ for 24 hours to obtain aluminum manganese oxide Al x MnO 2 。
Example 3
The preparation method of the aluminum manganese oxide comprises the following steps:
weighing 0.01mol of manganese sulfate monohydrate, 0.024mol of aluminum sulfate octadecanoate and 0.008mol of potassium permanganate, adding into 50mL of deionized water, stirring for dissolving, then dropwise adding 20mL of sulfuric acid with the concentration of 0.2mol/L, continuously stirring for 24 hours, transferring the obtained mixed solution into a reaction kettle, and performing hydrothermal reaction at 180 ℃ for 24 hours to obtain aluminum manganese oxide Al x MnO 2 。
Example 4
The preparation method of the aluminum manganese oxide comprises the following steps:
weighing 0.01mol of manganese sulfate monohydrate, 0.0264mol of aluminum sulfate octadecanoate and 0.008mol of potassium permanganate, adding into 50mL of deionized water, stirring for dissolving, then dropwise adding 20mL of sulfuric acid with the concentration of 0.2mol/L, continuously stirring for 24 hours, transferring the obtained mixed solution into a reaction kettle, and performing hydrothermal reaction at 180 ℃ for 24 hours to obtain aluminum manganese oxide Al x MnO 2 。
Example 5
The preparation method of the aluminum manganese oxide comprises the following steps:
weighing 0.01mol of manganese sulfate monohydrate, 0.0288mol of aluminum sulfate octadecanoate and 0.0 mol ofAdding 08mol of potassium permanganate into 50mL of deionized water, stirring for dissolving, then dropwise adding 20mL of sulfuric acid with the concentration of 0.2mol/L, continuously stirring for 24h, transferring the obtained mixed solution into a reaction kettle, and performing hydrothermal reaction at 180 ℃ for 24h to obtain aluminum manganese oxide Al x MnO 2 。
Example 6
The preparation method of the aluminum manganese oxide comprises the following steps:
weighing 0.01mol of manganese sulfate monohydrate, 0.036mol of aluminum sulfate octadecanoate and 0.008mol of potassium permanganate, adding into 50mL of deionized water, stirring for dissolving, then dropwise adding 20mL of sulfuric acid with the concentration of 0.2mol/L, continuously stirring for 24 hours, transferring the obtained mixed solution into a reaction kettle, and performing hydrothermal reaction at 180 ℃ for 24 hours to obtain aluminum manganese oxide Al x MnO 2 。
Example 7
The preparation method of the water-based magnesium ion capacitor based on the aluminum-manganese oxide comprises the following steps:
1) Preparation of positive electrode: 80mg of the aluminum manganese oxide Al obtained in example 5 x MnO 2 Mixing with 10mg PVDF and 10mg Super P, adding a small amount of NMP as solvent dropwise, and making the binder fully contact with other substances to be uniformly distributed. And then directly smeared on the carbon paper substrate. Drying in a vacuum drying oven, and taking out to obtain a positive pole piece coated with aluminum-manganese oxide;
2) Preparation of the negative electrode: after 80mg of activated carbon, 10mg of PVDF and 10mg of Super P are uniformly mixed, a small amount of NMP is added dropwise as a solvent, so that the binder is fully contacted with other substances and uniformly distributed. And then directly smeared on the carbon paper substrate. Drying in a vacuum drying oven, and taking out to obtain a negative electrode plate coated with active carbon;
3) Preparation of a water-based magnesium ion capacitor: placing the positive electrode plate into a positive electrode shell, enabling one surface coated with aluminum manganese oxide to contact a diaphragm, then placing a cellulose diaphragm, then dripping magnesium sulfate electrolyte with the concentration of 0.5mol/L, then placing the negative electrode plate above the diaphragm, enabling one surface coated with active carbon to contact the diaphragm, then sequentially placing a gasket and an elastic sheet, finally buckling the negative electrode shell, and packaging the negative electrode shell into a button-type device with the thickness of 40 mu m, thus obtaining the water-based magnesium ion capacitor.
(II) Performance test
In the comparative example, a manganese dioxide material was used as a positive electrode material to prepare a manganese dioxide-containing aqueous magnesium ion capacitor as described above.
FIG. 3 is a cyclic voltammogram of an aluminum manganese oxide and activated carbon asymmetric aqueous magnesium ion capacitor prepared in accordance with the present invention. As can be seen from FIG. 3, al-Mn oxide Al is obtained in example 5 x MnO 2 After aluminum doping, the cyclic voltammetry curve does not show obvious hydrogen evolution trend at about 1.9V, has obvious voltage plateau, and can be seen that the capacity of the cyclic voltammetry curve is larger than that of the original MnO 2 An oxide.
FIG. 4 is a graph showing the specific capacitance of an aluminum manganese oxide and activated carbon asymmetric aqueous magnesium ion capacitor prepared according to the present invention. As can be seen from FIG. 4, al-Mn oxide Al is obtained in example 5 x MnO 2 After aluminum doping, the discharge time was increased by 2208 seconds, the specific capacitance was as high as 259.58F/g, and increased by approximately 1.8 times over the original manganese dioxide.

Claims (7)

1. The water system magnesium ion capacitor based on the aluminum manganese oxide is characterized in that the aluminum manganese oxide is used as a positive electrode material, and the preparation method comprises the following steps:
1) Preparation of positive electrode: uniformly mixing aluminum-manganese oxide, a binder and a conductive material, dropwise adding a small amount of NMP as a solvent, uniformly mixing, directly coating on carbon paper of a substrate, drying in a vacuum drying oven, and taking out to obtain a positive electrode plate coated with aluminum-manganese oxide;
the preparation method of the aluminum manganese oxide comprises the following steps: adding manganese sulfate, aluminum sulfate and potassium permanganate into deionized water, stirring and dissolving, then adding sulfuric acid dropwise, continuing stirring for 24 hours, transferring the obtained mixed solution into a reaction kettle, and performing hydrothermal reaction to obtain aluminum manganese oxide;
2) Preparation of the negative electrode: uniformly mixing active carbon, a binder and a conductive material, dropwise adding a small amount of NMP as a solvent, uniformly mixing, directly coating on carbon paper, drying in a vacuum drying oven, and taking out to obtain a negative electrode plate coated with the active carbon;
3) Preparation of a water-based magnesium ion capacitor: placing the positive electrode plate into a positive electrode shell, enabling one surface coated with aluminum-manganese oxide to contact a diaphragm, then placing the diaphragm, then dripping electrolyte, then placing the negative electrode plate above the diaphragm, enabling one surface coated with active carbon to contact the diaphragm, then sequentially placing a gasket and an elastic sheet, finally buckling the negative electrode shell, and packaging to obtain the water-based magnesium ion capacitor.
2. An aluminum manganese oxide based aqueous magnesium ion capacitor according to claim 1 wherein said binder is PVDF or CMC.
3. The aluminum manganese oxide-based aqueous magnesium ion capacitor according to claim 1, wherein the conductive material is Super P or acetylene black.
4. The aluminum manganese oxide-based aqueous magnesium ion capacitor of claim 1 wherein said electrolyte is one of an aqueous magnesium sulfate solution, an aqueous magnesium chloride solution and an aqueous magnesium nitrate solution.
5. The aluminum manganese oxide-based aqueous magnesium ion capacitor according to claim 1, wherein the separator is one of a cellulose separator, a polypropylene film, a separator paper, and a polymeric semipermeable membrane.
6. The aluminum-manganese oxide-based aqueous magnesium ion capacitor according to claim 1, wherein the molar ratio of manganese sulfate to aluminum sulfate to potassium permanganate=1 is 0.24 to 3.6 to 0.8.
7. An aluminum manganese oxide based aqueous magnesium ion capacitor according to claim 1 wherein said hydrothermal reaction is at 180 ℃ for 24 hours.
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