CN111326747A - Three-dimensional ordered mesoporous MnOyPreparation of lithium-air battery anode material catalyst - Google Patents
Three-dimensional ordered mesoporous MnOyPreparation of lithium-air battery anode material catalyst Download PDFInfo
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- CN111326747A CN111326747A CN202010161031.0A CN202010161031A CN111326747A CN 111326747 A CN111326747 A CN 111326747A CN 202010161031 A CN202010161031 A CN 202010161031A CN 111326747 A CN111326747 A CN 111326747A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
Abstract
Three-dimensional ordered mesoporous MnOyPreparation of a lithium-air battery anode material catalyst belongs to the technical field of lithium-air battery anode material catalysts. The method comprises the following steps: synthesis of KIT-6 hard template, meso-MnO preparation with KIT6 as hard templateyAdding meso-MnOyAnd dissolving conductive carbon black and PVDF in NMP according to the mass ratio of 15:30:8 to form slurry, stirring for 12h, coating on foamed nickel, and vacuum drying for 12h to form the air electrode. The invention is beneficial to the reaction and has more obvious catalytic effect.
Description
Technical Field
The invention relates to a three-dimensional ordered mesoporous MnOy(meso-MnOy) A preparation method of a lithium-air battery anode material catalyst belongs to the technical field of lithium-air battery anode material catalysts.
Technical Field
Along with the concept of environmental protection, the battery is used to replace the traditional fossil fuel as the energy sourceFor new trends. At present, lithium ion batteries are commonly used in electronic products and new energy automobiles, and the batteries have theoretical energy storage upper limits. In order to further improve the energy storage capacity of the battery, a substitute for the lithium ion battery is urgently needed, and the lithium air battery is an alternative direction. The concept of lithium air batteries, which have been generated in the last 70 th century, is based on the principle that the energy generated by the reaction of lithium with oxygen in air is directly converted into electrical energy. The lithium air battery can store energy more efficiently, and the theoretical energy density can reach 5200 Wh.kg-1Considering that oxygen used for the reaction is stored in the air outside the battery, the energy density can be increased to 11140 Wh.kg-1Therefore, the lithium-air battery can better adapt to the development trend of the future society. If the method can be finally applied to production, including the fields of new energy automobiles and the like, even aerospace, great social value and high social wealth can be created.
The lithium-air battery mainly comprises a metallic lithium negative electrode, a positive electrode material and an electrolyte. In operation, electrical energy is obtained by oxidizing lithium of the negative electrode with oxygen in the air. The specific energy of a lithium-air battery is higher because lithium itself is lighter and the oxidant is distributed throughout the air. However, since the electrode reaction itself is difficult, it is necessary to add an appropriate catalyst to the positive electrode to accelerate the reaction.
Disclosure of Invention
Aiming at the problems that the catalytic efficiency of the existing lithium-air battery anode material catalyst is low and the catalyst is not beneficial to being put into practical production, the invention provides three-dimensional ordered mesoporous MnOy(meso-MnOy) The preparation method of the lithium-air battery cathode material catalyst has low preparation cost and strong operability, and the prepared product can be used as the catalyst of the lithium-air battery. The method comprises the following steps:
1) synthesis of KIT-6 hard template
The method reported by Kleitz et al is adopted, and the specific operation steps are as follows:
6g P123, 9.83mL of concentrated hydrochloric acid and 7.41mL of n-butanol are sequentially added into 227mL of water, and after each addition, the mixture needs to be stirred for a period of time in a water bath at 50 ℃; then adjusting the water bath to 35 ℃, adding 13.8mL of tetraethoxysilane and stirring for 24 hours; placing the mixed solution in a muffle furnace, and keeping the temperature at 100 ℃ for 24 hours; and (3) carrying out suction filtration on the product, washing the product with water and ethanol for multiple times, drying the product at 60 ℃, putting the product in a muffle furnace, heating the product to 550 ℃ at the speed of 1 ℃/min, and preserving the temperature for 4 hours to obtain the three-dimensional orderly arranged silicon sphere template.
2)meso-MnOyPreparation of
KIT6 is used as a hard template, manganese nitrate is used as a manganese source, and a nano-casting method is adopted to prepare three-dimensional ordered mesoporous MnOy(meso-MnOy). The preparation method comprises mixing 1.0g Mn (NO)3)2.4H2Dissolving O in 10mL ethanol, adding 0.5g KIT-6, stirring the mixture at 65 deg.C until the liquid is evaporated to dryness, transferring the mixture to a crucible, placing in a muffle furnace, raising to 400 deg.C at a rate of 1 deg.C/min, roasting at the temperature for 4h, washing the obtained solid powder with hot NaOH aqueous solution, filtering for 2 times, washing with deionized water and ethanol for 2 times, and drying in an oven at 60 deg.C for 24h to obtain meso-MnOyAnd (3) a carrier.
3) Preparation of lithium-air battery
Adding meso-MnOyDissolving PVDF (polyvinylidene fluoride) in NMP (N-methyl pyrrolidone) according to the mass ratio of 15:30:8 to form slurry, stirring for 12 hours, coating the slurry on foamed nickel, and performing vacuum drying for 12 hours to form an air electrode; celgard 2400 as membrane, 1M lipF6And preparing the R2025 lithium-air battery in a pure argon glove box by using + EC/EMC/DEC (EC/EMC/DEC volume ratio of 1:1:1) as an electrolyte.
The catalytic performance of the catalyst is characterized by testing the discharge capacity, the cycle performance and the alternating current impedance performance of the battery.
The invention has the following advantages:
1. the method provided by the invention is simple to operate, the used raw materials are common chemical reagents, and the method is non-toxic, pollution-free, environment-friendly and suitable for industrial production.
2. The specific surface area of the three-dimensional ordered mesoporous structure is large, the reaction is facilitated, and the catalytic effect is more obvious.
Drawings
Fig. 1 is a voltage-discharge capacity curve of a lithium-air battery.
Fig. 2 cycle performance test curves for lithium-air batteries.
Voltage-capacity curve test conditions: charge and discharge were carried out at a rate of 70mA g-1. In the first cycle, the capacity of the cell is expressed as the value of electrical energy stored per gram of carbon in the electrode, under a pure oxygen environment at one standard atmosphere.
Cycle performance test conditions: charging was carried out at a rate of 70mA g-1 in a pure oxygen atmosphere at a standard atmospheric pressure.
Detailed description of the invention
The invention is further illustrated by the following specific examples in connection with the accompanying drawings, which are not intended to limit the invention solely to the examples below. The reagents and instrumentation used in the following examples are conventional raw materials and conventional equipment.
Example 1:
adding 6g P123 into 227mL of water, and stirring in a water bath at 50 ℃ for 20 min; adding 9.83mL of concentrated hydrochloric acid, and continuously stirring in a water bath at 50 ℃ for 20 min; adding 7.41mL of n-butanol, and stirring in a water bath at 50 ℃ for 50 min; adjusting the water bath to 35 ℃, dropwise adding 13.8mL of tetraethoxysilane after the temperature is stable, and keeping the water bath at 35 ℃ and stirring for 24 hours; transferring the uniformly stirred tetraethoxysilane mixed solution into a 100mL self-pressure kettle, filling the mixture to 80% of volume, and placing the mixture in a muffle furnace to keep the temperature at 100 ℃ for 24 hours; and (3) carrying out suction filtration on the obtained product, respectively washing the product with water and ethanol for multiple times, drying the product at 60 ℃, then placing the product in a muffle furnace, heating the product to 550 ℃ at the speed of 1 ℃/min, and carrying out heat preservation for 4 hours to obtain the three-dimensional orderly arranged silicon ball template. 1.0g
Dissolving in 10mL ethanol, adding 0.5g KIT-6, stirring the mixture at 65 deg.C until the liquid is evaporated to dryness, transferring the mixture to a crucible, placing in a muffle furnace, raising to 400 deg.C at a rate of 1 deg.C/min, calcining at the temperature for 4h, washing the obtained solid powder with hot NaOH aqueous solution, filtering for 2 times, washing with deionized water and ethanol for 2 times, and oven drying at 60 deg.C for 24h to obtain meso-MnOyAnd (3) a carrier.
Adding meso-MnOyDissolving PVDF (polyvinylidene fluoride) in NMP (N-methyl pyrrolidone) according to the mass ratio of 15:30:8 to form slurry, stirring for 12 hours, coating the slurry on foamed nickel, and performing vacuum drying for 12 hours to form an air electrode; celgard 2400 as membrane, 1M lipF6And the catalyst has the advantages that the positive EC/EMC/DEC (volume ratio of 1:1:1) is used as electrolyte, an R2025 lithium-air battery is prepared in a pure argon glove box, and the catalytic performance of the catalyst is characterized by testing the discharge capacity, the cycle performance and the alternating current impedance performance of the battery.
Adding meso-MnOyAnd respectively weighing the conductive carbon black and the PVDF according to the mass ratio of 15:30:8 for later use. Dissolving PVDF in NMP, and sequentially adding meso-MnOyAnd (3) stirring the conductive carbon black for 12 hours to form slurry, coating the slurry on foamed nickel, and performing vacuum drying at 120 ℃ for 2 hours to form the air electrode. The above procedure was repeated 2-3 times and weighed before and after each application. Celgard 2400 as membrane, 1M lipF6Preparing R2025 lithium-air battery in pure argon glove box by using + EC/EMC/DEC (volume ratio of 1:1:1) as electrolyte and controlling O in the process2And H2The O content is not more than 1ppm, and the mixture is kept stand for 12 hours after being sealed by an electric sealing machine. The catalytic performance of the catalyst is characterized by testing the discharge capacity, the cycle performance and the alternating current impedance performance of the battery.
Claims (2)
1. Three-dimensional ordered mesoporous MnOyThe preparation method of the lithium-air battery cathode material catalyst is characterized by comprising the following steps:
1) synthesizing a KIT-6 hard template;
2)meso-MnOypreparation of
KIT6 is used as a hard template, manganese nitrate is used as a manganese source, and a nano-casting method is adopted to prepare three-dimensional ordered mesoporous MnOy(meso-MnOy) (ii) a The preparation method comprises mixing 1.0g Mn (NO)3)2.4H2Dissolving O in 10mL ethanol, adding 0.5g KIT-6, stirring the mixture at 65 deg.C until the liquid is evaporated to dryness, transferring the mixture to a crucible, placing in a muffle furnace, raising to 400 deg.C at a rate of 1 deg.C/min and calcining at that temperature for 4h, washing the obtained solid powder with hot aqueous NaOH solution and filtering for 2 times, then washing with deionized water and ethanol for 2 timesDrying in a 60 ℃ oven for 24 hours to prepare meso-MnOyA carrier;
3) preparation of lithium-air battery
Adding meso-MnOyDissolving the conductive carbon black and the PVDF in the NMP according to the mass ratio of 15:30:8 to form slurry, stirring for 12h, coating the slurry on the foamed nickel, and drying in vacuum for 12h to form the air electrode.
2. The three-dimensional ordered mesoporous MnO of claim 1yThe preparation of the catalyst of the anode material of the lithium-air battery is characterized in that the catalyst is further prepared into the lithium-air battery, and meso-MnO is addedyDissolving conductive carbon black and PVDF in NMP according to the mass ratio of 15:30:8 to form slurry, stirring for 12h, coating the slurry on foamed nickel, performing vacuum drying for 12h to form an air electrode, and taking Celgard 2400 as a diaphragm and 1M lipF6And preparing the R2025 lithium-air battery in a pure argon glove box by using + EC/EMC/DEC (EC/EMC/DEC volume ratio of 1:1:1) as an electrolyte.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150064560A1 (en) * | 2013-08-30 | 2015-03-05 | Samsung Electronics Co., Ltd. | Electrode active material, electrode including the same, and lithium battery including the electrode |
| CN105870431A (en) * | 2016-06-21 | 2016-08-17 | 苏州帝瀚环保科技股份有限公司 | Preparation method of meso-porous MnO2/C |
| CN110124683A (en) * | 2019-06-19 | 2019-08-16 | 南开大学 | Mesoporous NiMn2O4The preparation method of catalyst, the catalyst thus prepared and application thereof |
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- 2020-03-10 CN CN202010161031.0A patent/CN111326747A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150064560A1 (en) * | 2013-08-30 | 2015-03-05 | Samsung Electronics Co., Ltd. | Electrode active material, electrode including the same, and lithium battery including the electrode |
| CN105870431A (en) * | 2016-06-21 | 2016-08-17 | 苏州帝瀚环保科技股份有限公司 | Preparation method of meso-porous MnO2/C |
| CN110124683A (en) * | 2019-06-19 | 2019-08-16 | 南开大学 | Mesoporous NiMn2O4The preparation method of catalyst, the catalyst thus prepared and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| ARJUN KUMAR THAPA等: "Mesoporous β-MnO2 Air Electrode Modified with Pd for Rechargeability in Lithium-Air Battery", 《JOURNAL OF THE ELECTROCHEMICAL SOCIETY》 * |
| JUN YANG等: "PtxCo/meso-MnOy: Highly efficient catalysts for low-temperature methanol combustion", 《CATALYSIS TODAY》 * |
| 曾晓苑 著: "《锂空气电池高性能催化剂的制备与应用》", 30 April 2019, 冶金工业出版社 * |
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Application publication date: 20200623 |