CN109193030B - Lithium oxygen battery electrolyte taking molybdenum pentachloride as redox medium and preparation and application thereof - Google Patents
Lithium oxygen battery electrolyte taking molybdenum pentachloride as redox medium and preparation and application thereof Download PDFInfo
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- CN109193030B CN109193030B CN201811004815.1A CN201811004815A CN109193030B CN 109193030 B CN109193030 B CN 109193030B CN 201811004815 A CN201811004815 A CN 201811004815A CN 109193030 B CN109193030 B CN 109193030B
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- H—ELECTRICITY
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
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Abstract
The invention relates to a lithium-oxygen battery electrolyte taking molybdenum pentachloride as a redox medium, and preparation and application thereof. The electrolyte comprises soluble lithium salt as solute, aprotic solvent and additive molybdenum pentachloride; wherein the solute concentration in the electrolyte is 0.1-1 mol/L; the concentration of the molybdenum pentachloride in the electrolyte is 0.01-0.1 mol/L. The molybdenum pentachloride is used as the electrolyte additive to be applied to the lithium oxygen battery, which is beneficial to the formation of the annular lithium peroxide in the discharging process and plays a role in stabilizing the carbon electrode. The lithium peroxide discharge product can be effectively decomposed in the charging process, the charging voltage is reduced, the cycle life of the battery is prolonged, and the reversibility is good. Meanwhile, the molybdenum pentachloride is stable in a battery system and has no side reaction. Has the advantages of low price, easy obtaining, high efficiency and convenience.
Description
Technical Field
The invention relates to a lithium oxygen battery electrolyte taking molybdenum pentachloride as an oxidation-reduction medium, and preparation and application thereof, belonging to the technical field of electrochemical catalysis.
Background
The lithium oxygen battery directly uses oxygen as an active substance, so that the lithium oxygen battery has ultrahigh specific energy, has the advantages of stable discharge, high discharge plateau and the like, and is considered to be a secondary energy system with the highest development potential.
However, the lithium oxygen battery system still has many problems to be solved, for example, during the discharging process, the generated superoxide intermediate and its instability, superoxide radical ion attack carbon-based material or organic electrolyte to generate by-product, and in addition, the discharging product lithium peroxide is an insulator, which results in the charging overpotential increase during charging, and the faradaic efficiency is reduced.
Researchers have proposed many solutions to effectively decompose lithium peroxide. Such as noble metals (Nano Lett.2013, 13, 10, 4702-. However, the catalytic performance of these catalysts is not satisfactory. Subsequently, it is proposed to apply an organic redox mediator (Nat Chem 2013, 5, 489-494.) to a lithium-oxygen battery system, however, the organic compound is unstable and easy to decompose, which may further cause the battery performance to deteriorate. Therefore, the redox medium of the lithium-oxygen battery is applied to the lithium-oxygen battery, so that the battery system can be stabilized, the charging voltage can be reduced, and the energy efficiency can be improved. More importantly, the inorganic redox medium is cheap and easy to obtain, and has high application potential.
Disclosure of Invention
The invention aims to provide a lithium oxygen battery electrolyte taking molybdenum pentachloride as a redox medium, and preparation and application thereof. The addition of the molybdenum pentachloride improves the cycle life of the lithium oxygen stripping battery, and reduces the charging voltage.
The lithium oxygen battery electrolyte with molybdenum pentachloride as a redox medium comprises soluble lithium salt as a solute, an aprotic solvent and additive molybdenum pentachloride; wherein the solute concentration in the electrolyte is 0.1-1 mol/L; the concentration of the molybdenum pentachloride in the electrolyte is 0.01-0.1 mol/L;
the solute is selected from at least one of lithium bis (trifluoromethyl) sulfonyl imide, lithium bis (fluoro) sulfonyl imide, lithium triflate, lithium trifluoroacetate, lithium nitrate and lithium perchlorate.
The aprotic solvent is at least one selected from ethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, dimethyl sulfoxide and 1-butyl-1 methyl-pyrrole bis (trifluoromethyl sulfonyl) imine.
The preparation method of the lithium oxygen battery electrolyte taking molybdenum pentachloride as a redox medium comprises the following steps:
1) and (3) carrying out vacuum drying on the molybdenum pentachloride at the temperature of 90-150 ℃ for 12-24 hours, and carrying the dryer and the sample into a glove box after drying.
2) Mixing molybdenum pentachloride with solute and aprotic solvent of the lithium oxygen battery electrolyte according to the measurement, and fully stirring in a glove box for 24-48 hours to obtain the lithium oxygen battery electrolyte containing the molybdenum pentachloride.
The invention also provides the application of the lithium oxygen battery prepared by using the electrolyte taking molybdenum pentachloride as a redox medium, wherein the lithium oxygen battery comprises a lithium cathode, a carbon anode, a diaphragm, a current collector and a battery shell;
the carbon anode is one or more of Ketjen black, carbon nano tubes, graphene and carbon nitride sheets. The above materials were coated on carbon paper as the positive electrode.
The diaphragm is made of polytetrafluoroethylene or glass fiber.
The battery case of the lithium oxygen battery is a Schweilok (Swagelok) columnar battery case or a button battery case.
The invention provides a lithium oxygen battery electrolyte taking molybdenum pentachloride as an additive. The carbon-carbon composite material is applied to a lithium-oxygen battery, contributes to the formation of cyclic lithium peroxide in a discharging process, and also plays a role in stabilizing a carbon electrode. The lithium peroxide discharge product can be effectively decomposed in the charging process, the charging voltage is reduced, the cycle life of the battery is prolonged, and the reversibility is good. Meanwhile, the molybdenum pentachloride is stable in a battery system and has no side reaction. Has the advantages of low price, easy obtaining, high efficiency and convenience. In a word, the charging voltage can be reduced, the battery system can be stabilized, and the cycle life of the battery can be prolonged. At a current density of 400 mA/g, the charging voltage of the lithium oxygen battery was reduced to 4.0V. Meanwhile, the cycle is stable for 45 circles, and the battery is cycled for 25 circles under the current density of 800 mA/g. Meanwhile, under 400 mA/g, the first-cycle discharge specific capacity is 27951 mA h/g, and simultaneously, the high coulombic efficiency is realized, and the second-cycle discharge specific capacity can still maintain 15461 mA h/g.
Drawings
FIG. 1 is a charge and discharge curve of a lithium oxygen battery with added molybdenum pentachloride at a current density of 400 mA/g.
FIG. 2 is a graph of a lithium oxygen cell cycle with added molybdenum pentachloride at a current density of 400 mA/g.
FIG. 3 is a graph of a lithium oxygen cell cycle with added molybdenum pentachloride at a current density of 800 mA/g.
FIG. 4 is a graph of a lithium oxygen cell cycle without added molybdenum pentachloride at a current density of 400 mA/g.
Fig. 5 is an SEM image of the cell positive electrode after discharge after addition of molybdenum pentachloride.
Fig. 6 is an SEM image of the battery positive electrode after charging after addition of molybdenum pentachloride.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1:
drying molybdenum pentachloride in a vacuum dryer at 120 ℃ for 24 hours, and then dissolving the molybdenum pentachloride in the electrolyte of the tetraethylene glycol dimethyl ether with the concentration of 1 mol/L of bis (trifluoromethyl) sulfimide lithium in a glove box to obtain the electrolyte with the molybdenum pentachloride as a redox medium, wherein the concentration of the molybdenum pentachloride is 0.05 mol/L.
Example 2:
molybdenum pentachloride is dried in a vacuum drier at 120 ℃ for 24 hours, and then the molybdenum pentachloride is dissolved in the electrolyte of glycol dimethyl ether with 1 mol/L lithium trifluoromethanesulfonate concentration in a glove box, so that the electrolyte with the molybdenum pentachloride as a redox medium can be obtained, wherein the concentration of the molybdenum pentachloride is 0.05 mol/L.
Example 3:
drying molybdenum pentachloride in a vacuum dryer at 120 ℃ for 24 hours, and then dissolving the molybdenum pentachloride in electrolyte of tetraethylene glycol dimethyl ether with lithium trifluoroacetate concentration of 0.5 mol/L in a glove box to obtain the electrolyte with the molybdenum pentachloride as a redox medium, wherein the concentration of the molybdenum pentachloride is 0.05 mol/L.
FIG. 1 is a charge and discharge curve of a lithium oxygen battery with added molybdenum pentachloride at a current density of 400 mA/g. As can be seen from the figure, the first-week discharge capacity of the lithium oxygen battery containing the molybdenum pentachloride redox medium can reach 27951 mA h/g, the charging voltage can be reduced to 4.0V, the second-circle capacity can still reach 15731 mA h/g, the Faraday efficiency reaches more than 80%, and good reversibility is shown.
FIG. 2 is a graph of a lithium oxygen cell cycle with added molybdenum pentachloride at a current density of 400 mA/g. It can be seen from the figure that the lithium oxygen cell containing molybdenum pentachloride redox mediator can stably cycle for 45 cycles, the first cycle charging voltage is reduced to 4.0V, and the final charging voltage is less than 4.3V. Showing good cycling stability.
FIG. 3 is a graph of a lithium oxygen cell cycle with added molybdenum pentachloride at a current density of 800 mA/g. It can be seen from the figure that the lithium oxygen cell containing molybdenum pentachloride redox mediator can stably cycle for 25 cycles, and the first cycle charging voltage is reduced to 4.0V. Showing good rate performance.
FIG. 4 is a graph of a lithium oxygen cell cycle without added molybdenum pentachloride at a current density of 400 mA/g. It can be seen from the figure that the lithium oxygen cell without added molybdenum pentachloride redox mediator can only cycle for 13 weeks and the first cycle charge voltage rises to 4.6V. Therefore, the charging voltage can be reduced by adding molybdenum pentachloride into the lithium oxygen battery, the battery system is stabilized, and the cycle performance is improved.
Fig. 5 is an SEM image of the cell positive electrode after discharge after addition of molybdenum pentachloride. It can be seen from the figure that the positive electrode of the lithium oxygen cell with molybdenum pentachloride added has large blocks of annular lithium peroxide products formed after discharge, which indicates that the lithium oxygen cell can generate products from various directions after the addition, which indicates that the process is a liquid phase conversion process and thus can have high specific energy.
Fig. 6 is an SEM image of the battery positive electrode after charging after addition of molybdenum pentachloride. It can be seen from the figure that after charging, the discharge product has completely decomposed and the oxygen positive electrode has completely recovered to the original state, which again demonstrates the good reversibility of the lithium oxygen battery after addition of molybdenum pentachloride.
Claims (9)
1. A lithium oxygen battery electrolyte taking molybdenum pentachloride as a redox medium is characterized by comprising soluble lithium salt as a solute, an aprotic solvent and an additive molybdenum pentachloride; wherein the solute concentration in the electrolyte is 0.1-1 mol/L; the concentration of the molybdenum pentachloride in the electrolyte is 0.01-0.1 mol/L.
2. The lithium oxygen cell electrolyte with molybdenum pentachloride as a redox mediator according to claim 1, wherein the solute is selected from at least one of lithium bistrifluoromethylsulfonyl imide, lithium bistrifluorosulfonimide, lithium trifluoromethanesulfonate, lithium trifluoroacetate, lithium nitrate and lithium perchlorate.
3. The lithium oxygen battery electrolyte with molybdenum pentachloride as a redox mediator according to claim 1, wherein the aprotic solvent is selected from at least one of ethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, dimethyl sulfoxide, and 1-butyl-1 methyl-pyrrole bis (trifluoromethylsulfonyl) imide.
4. A lithium oxygen battery electrolyte taking molybdenum pentachloride as a redox medium is characterized by comprising soluble lithium salt as a solute, an aprotic solvent and an additive molybdenum pentachloride; wherein the solute concentration in the electrolyte is 0.5-1 mol/L; the concentration of molybdenum pentachloride in the electrolyte is 0.05 mol/L; the solute is bis (trifluoromethyl) sulfonyl imide lithium, lithium trifluoromethanesulfonate or lithium trifluoroacetate; the aprotic solvent is ethylene glycol dimethyl ether or tetraethylene glycol dimethyl ether.
5. The method of claim 1 for preparing a lithium oxygen battery electrolyte with molybdenum pentachloride as a redox mediator, comprising the steps of:
1) carrying out vacuum drying on molybdenum pentachloride at the temperature of 90-150 ℃ for 12-24 hours, and bringing a dryer and a sample into a glove box after drying;
2) mixing molybdenum pentachloride with solute and aprotic solvent of the lithium oxygen battery electrolyte according to the measurement, and fully stirring in a glove box for 24-48 hours to obtain the lithium oxygen battery electrolyte containing the molybdenum pentachloride.
6. The lithium oxygen cell prepared by using the electrolyte with molybdenum pentachloride as a redox medium in any one of claims 1 to 4, wherein the electrolyte comprises: a lithium negative electrode, a carbon positive electrode, a separator, a current collector, and a battery case.
7. The lithium oxygen battery as defined in claim 6, wherein the carbon positive electrode material is one or more selected from ketjen black, carbon nanotubes, graphene or carbon nitride sheets, and the carbon positive electrode material is coated on carbon paper to serve as a positive electrode.
8. The lithium oxygen cell of claim 6, wherein said separator is polytetrafluoroethylene or fiberglass.
9. The lithium oxygen cell of claim 6, wherein said lithium oxygen cell casing is a cylindrical battery casing or a button battery casing.
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