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CN115189076A - Wide-temperature-range solid-state metal-air battery and preparation method thereof - Google Patents

Wide-temperature-range solid-state metal-air battery and preparation method thereof Download PDF

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CN115189076A
CN115189076A CN202210527824.9A CN202210527824A CN115189076A CN 115189076 A CN115189076 A CN 115189076A CN 202210527824 A CN202210527824 A CN 202210527824A CN 115189076 A CN115189076 A CN 115189076A
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CN115189076B (en
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徐吉静
管德慧
王晓雪
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Jilin University
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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H—ELECTRICITY
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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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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
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    • H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
    • H01M6/181—Cells with non-aqueous electrolyte with solid electrolyte with polymeric electrolytes
    • H—ELECTRICITY
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    • H01—ELECTRIC ELEMENTS
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    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
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Abstract

The invention is suitable for the field of solid-state metal-air batteries, and provides a wide-temperature solid-state metal-air battery, which comprises: a C-IL @ MOF solid state positive electrode, an IL @ MOF solid state electrolyte, and a metal negative electrode; the C-IL @ MOF solid-state positive electrode is formed by compounding a conductive catalyst, a metal organic framework material and an ionic liquid; the IL @ MOF solid electrolyte is formed by compounding a metal organic framework material and an ionic liquid. A preparation method of a wide-temperature solid metal-air battery is characterized in that a C-IL @ MOF solid positive electrode, an IL @ MOF solid electrolyte and a metal negative electrode are packaged in the battery from top to bottom. The structure of the integrated solid electrolyte of IL @ MOF and the solid positive electrode of C-IL @ MOF is used for wide-temperature solid metal air batteries, and the structure shows rapid reaction kinetics, super ionic conductivity and electrochemical durability.

Description

Wide-temperature-range solid-state metal-air battery and preparation method thereof
Technical Field
The invention belongs to the field of solid metal-air batteries, and particularly relates to a wide-temperature solid metal-air battery and a preparation method thereof.
Background
In the inorganic solid electrolyte, since inorganic sulfide is unstable in the air environment, toxic hydrogen sulfide is generated, which is inconvenient to apply to the lithium air battery; in addition, perovskite-type and anti-perovskite-type solid electrolytes exhibit low ionic conductivity. Currently, sodium super-ionic conductors and garnet solid electrolytes having higher ionic conductivity are being studied more. However, the large interfacial resistance caused by the use of solid electrolytes limits the improvement in the performance of solid-state batteries. In the polymer electrolyte aspect, a gel polymer electrolyte composed of a polymer matrix and a liquid electrolyte has been used for a metal-air battery to solve the solid/solid interface problem. Although the gel polymer electrolyte exhibits high ion conductivity, which is close to that of the liquid electrolyte, the problem of volatilization is not solved because of the inclusion of a certain amount of the liquid electrolyte. Meanwhile, a novel flexible metal-air battery of a composite polymer electrolyte without a liquid electrolyte, which shows a long cycle life and a low overpotential at a high temperature (55 ℃), has been attempted. However, its practical application is hampered by the temperature dependence. Currently, solid state electrolytes combining high ionic conductivity, high stability and good interfacial contact are still sought for metal-air batteries.
The positive electrode of the metal-air battery is a main site of the battery reaction, and a reaction interface containing gas, electrons, and ions at the same time needs to be formed. At present, the common approach for constructing the solid-state positive electrode is to ball mill or co-sinter the solid-state electrolyte and the positive electrode catalyst, which causes three interface limitations to affect the performance of the solid-state battery. Therefore, it is also one of the current problems to construct a reasonable solid positive electrode of a metal-air battery.
To avoid the above technical problems, it is necessary to provide a wide temperature range solid metal-air battery and a method for manufacturing the same to overcome the above-mentioned drawbacks in the prior art.
Disclosure of Invention
The invention aims to provide a wide-temperature solid-state metal-air battery and a preparation method thereof, and aims to solve the technical problems of preparation of a solid-state electrolyte material with high ionic conductivity and high stability and a solid-state anode with a porous structure and good interface contact and continuous electron/ion transmission.
The present invention is thus achieved, a wide temperature solid state metal-air battery comprising:
a C-IL @ MOF solid state positive electrode, an IL @ MOF solid state electrolyte, and a metal negative electrode;
the C-IL @ MOF solid-state positive electrode is formed by compounding a conductive catalyst, a metal organic framework material and an ionic liquid;
the IL @ MOF solid electrolyte is formed by compounding a metal organic framework material and an ionic liquid.
In a further technical scheme, the MOF is single or multiple materials in MIL-101, uiO-66 and UiO-67.
According to a further technical scheme, the IL is a single or multiple materials in imidazole, pyridine and quaternary ammonium salt ionic liquid.
According to a further technical scheme, C in the C-IL @ MOF solid-state positive electrode is a single or multiple materials of carbon nano tubes, graphene and conductive carbon.
In a further technical scheme, the composite method is a grinding and mixing method.
According to a further technical scheme, the metal negative electrode is one of a lithium sheet, a sodium sheet, a potassium sheet, a zinc sheet, an iron sheet, a magnesium sheet or an aluminum sheet.
A preparation method of a wide-temperature solid metal-air battery is characterized in that a C-IL @ MOF solid positive electrode, an IL @ MOF solid electrolyte and a metal negative electrode are packaged in the battery from top to bottom.
The method specifically comprises the following steps;
s1, preparing MOF nano particles;
s2, encapsulating ionic liquid in the MOF nano particles prepared in the step S1 to obtain IL @ MOF nano particles;
s3, pressing the IL @ MOF nano particles in the S2 into a wafer and forming an IL @ MOF solid electrolyte;
s4, preparing C-MOF nanoparticles;
s5, encapsulating the ionic liquid in the C-MOF nano-particle obtained in the step S4 to obtain a C-IL @ MOF nano-particle;
s6, pressurizing the IL @ MOF nanoparticles obtained in the step S2 at 1-5 MPa for 1-5 minutes, and combining the C-IL @ MOF nanoparticles obtained in the step S51 with the IL @ MOF dense electrolyte layer in a spin coating or pressurizing mode to obtain a double-layer integrated IL @ MOF/C-IL @ MOF framework;
s7, assembling the positive current collector, the integrated IL @ MOF/C-IL @ MOF framework and the negative lithium sheet in the 2025 type button cell from top to bottom;
and S8, placing the battery obtained in the step S7 into a self-made sealed container, wherein the air in the container can be changed into different atmospheres, and the container can be placed at different ambient temperatures.
The self-made sealed container can be made of glass, quartz, acrylic glass and stainless steel;
the air is converted into different atmospheres, and the air is pumped and discharged by a two-way switch of the sealed container;
the different environmental temperatures refer to the environmental temperatures of-60 ℃ to 150 ℃.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides an IL @ MOF/C-IL @ MOF structure integrating an IL @ MOF solid electrolyte and a C-IL @ MOF solid-state positive electrode, which is used for a wide-temperature solid-state metal air battery and shows rapid reaction kinetics, super ionic conductivity and electrochemical durability.
(1) Il @ MOF exhibits exceptionally high ionic conductivities and high lithium ion transfer numbers at room temperature as a stable solid electrolyte, due to the strong interaction of the MOF framework with ionic liquids, which is effective in inhibiting the movement of anions.
(2) IL @ MOF exhibits very high ionic conductivity over a wide temperature range (-60 to 150 ℃) due to the encapsulation of IL in the MOF's unique porous structure.
(3) In addition, the C-IL @ MOF nano-reactor provides a continuous mass transfer channel and rich three-phase boundaries, and effectively accelerates the redox kinetics.
(4) Solid state metal-air cells exhibit ultra-low impedance, high round-trip efficiency, and good rate performance at room temperature, benefiting from the nano-wetting interface of il @ mof with the electrodes.
(5) The solid-state metal-air battery shows a super-wide working temperature window (-60 ℃ to 150 ℃), and is expected to be applied to complicated and variable environments.
This study is not limited to metal-air batteries, but can be applied to other battery systems, and constitutes an important step in practical application to all-solid-state metal-air batteries.
Drawings
FIG. 1 is a corresponding Arrhenius plot of the ionic conductivity from-60 ℃ to 150 ℃ of the IL @ MOF solid state electrolyte of example 1 of the present invention.
FIG. 2 is a DC polarization curve at room temperature for an IL @ MOF solid state electrolyte of example 1 of the present invention.
FIG. 3 is a scanning electron micrograph of a CNT-IL @ MOF solid state positive electrode of example 2 of the present invention.
FIG. 4 is a cyclic voltammogram of a CNT-IL @ MOF solid state positive electrode prepared in example 2 of the present invention.
Fig. 5 is an in-situ electrochemical impedance test of a wide temperature solid state lithium carbon dioxide battery prepared in accordance with example 3 of the present invention during charging and discharging.
Fig. 6 is a charge and discharge voltage curve of the wide temperature solid state lithium carbon dioxide battery prepared in example 3 of the present invention at-60 c to 150 c.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
Specific implementations of the present invention are described in detail below with reference to specific embodiments.
A wide temperature solid state metal air cell comprising:
a C-IL @ MOF solid state positive electrode, an IL @ MOF solid state electrolyte, and a metal negative electrode;
the C-IL @ MOF solid-state positive electrode is formed by compounding a conductive catalyst, a metal organic framework material and an ionic liquid; the C-IL @ MOF solid-state positive electrode has the advantages of electronic conductivity, high ionic conductivity and high redox kinetics;
the IL @ MOF solid electrolyte is formed by compounding a metal organic framework material and an ionic liquid, and has the advantages of high ionic conductivity, high stability and good interface contact.
The MOF comprises single or multiple materials of MIL-101, uiO-66, uiO-67 and the like, and the MOF is preferably MIL-101 (Cr).
The IL comprises imidazole, pyridine, quaternary ammonium salt and other ionic liquids, and preferably 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide.
The C in the C-IL @ MOF solid-state positive electrode comprises a conductive catalyst such as Carbon Nano Tubes (CNT), graphene and conductive carbon; the C is preferably a carbon nanotube.
The compounding method is a grinding and mixing method.
The metal cathode is a lithium sheet.
A preparation method of a wide-temperature solid metal-air battery is characterized in that a C-IL @ MOF solid positive electrode, an IL @ MOF solid electrolyte and a metal negative electrode are packaged in the battery from top to bottom.
Example 1
Preparation of IL @ MOF solid electrolyte:
1. 2.5mmol of Cr (NO) 3 ) 3 ·9H 2 O and 2.5mmol of terephthalic acid were added to 10mL of deionized water. After sonication, the solution was transferred to a reaction kettle and heated to 200 ℃ for 24 hours. After allowing the solution to cool, the product was centrifuged. The product was placed in N, N-dimethylformamide and stirred at 100 ℃ for 24 hours. Finally filtering the obtained green product and drying the green product in vacuum at 120 ℃ to obtain green powder MOF nano particles;
2. 1M IL was prepared by dissolving lithium bis (trifluoromethanesulfonyl) imide into 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide. Uniformly mixing IL and green powder MOF nanoparticles according to a ratio of 1;
3. filling the IL @ MOF nano particles into a circular tabletting mould with the diameter of 16mm, and pressurizing for 5 minutes under the pressure of 5MPa to obtain the IL @ MOF solid electrolyte;
the solid state electrolyte IL @ MOF prepared in example 1 of the invention was characterized.
Referring to FIG. 1, the corresponding Arrhenius plots of ionic conductivity of IL @ MOF solid state electrolyte from-60 ℃ to 150 ℃.
As can be seen from FIG. 1, the solid electrolyte of IL @ MOF prepared by the present invention shows very high ionic conductivity in a wide temperature range (-60 ℃ to 150 ℃), and the ionic conductivity can reach 1.0mS cm at room temperature -1 。
Referring to FIG. 2, FIG. 2 is a DC polarization curve at room temperature for an IL @ MOF solid electrolyte in the present invention.
From the graph of fig. 2, it can be seen that the number of lithium ion transfers of the il @ MOF solid state electrolyte prepared by the present invention is as high as 0.8, which is attributed to the MOF framework that can effectively limit the internal ionic liquid anion movement.
Example 2
Preparation of CNT-IL @ MOF solid state positive electrode:
1. mixing 1g Cr (NO) 3 ) 3 ·9H 2 O and 0.415g terephthalic acid were added to 10mL deionized water, stirred to a clear solution and then CNT was added. After sonication, the solution was transferred to a reaction kettle and heated to 200 ℃ for 24 hours. After allowing the solution to cool, the product was centrifuged. The product was taken up in N, N-dimethylformamide and stirred at 100 ℃ for 24 hours. Finally filtering the obtained green product and drying the green product in vacuum at 120 ℃ to obtain green powder MOF nano particles;
2. lithium bis (trifluoromethanesulfonyl) imide was dissolved in 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide to prepare 1MIL. Uniformly mixing IL and black CNT-MOF nanoparticles according to a ratio of 1;
3. filling the CNT-IL @ MOF nano particles into a circular tabletting mould with the diameter of 16mm, and pressurizing for 5 minutes at 3MPa to obtain a CNT-IL @ MOF solid-state positive electrode;
the CNT-IL @ MOF solid state positive electrode prepared in example 2 of the present invention.
Referring to FIG. 3, FIG. 3 is a scanning electron micrograph of a CNT-IL @ MOF solid state positive electrode prepared according to the present invention.
As can be seen from FIG. 3, the CNT-IL @ MOF solid state positive electrode forms a continuous electron ion conduction network and has a rich three-phase reaction interface.
Referring to FIG. 4, FIG. 4 is a cyclic voltammogram of a CNT-IL @ MOF solid state positive electrode prepared according to the present invention.
As can be seen from FIG. 4, MOF with CNT-IL @ exhibits higher reduction and oxidation currents and a more pronounced redox peak compared to CNT-IL. As the CNT-IL @ MOF positive electrode has more effective electrochemical active sites, the kinetics of the reduction and precipitation reaction process of carbon dioxide can be obviously improved.
Example 3
Preparing a wide-temperature solid lithium-carbon dioxide battery:
1. the obtained IL @ MOF nanoparticles were pressurized at 5MPa for 5 minutes, and black CNT-IL @ MOF nanoparticles were combined with the IL @ MOF dense electrolyte layer by spin coating or pressurization to obtain a double-layer integrated IL @ MOF/CNT-IL @ MOF framework.
2. Assembling a positive electrode current collector, an integrated IL @ MOF/CNT-IL @ MOF framework and a negative electrode lithium piece in the 2025 type button cell from top to bottom; the wide-temperature solid lithium-carbon dioxide battery is tested under different temperatures (-60 ℃ to 150 ℃) respectively.
The wide temperature solid state lithium carbon dioxide battery prepared in example 3 of the present invention was characterized.
Referring to fig. 5, fig. 5 is an in-situ electrochemical impedance test of the wide-temperature solid lithium-carbon dioxide battery prepared according to the present invention during charging and discharging.
As can be seen from fig. 5, the total resistance of the solid-state lithium carbon dioxide battery is 100 Ω due to the nano-wetting of the electrolyte and electrode interfaces. Due to the fast carbon dioxide reduction/precipitation reaction process kinetics, the solid-state lithium carbon dioxide battery remains at 100 Ω after the charge-discharge process.
Referring to fig. 6, fig. 6 is a charge and discharge voltage curve of the wide-temperature solid lithium-carbon dioxide battery prepared according to the present invention at-60 ℃ to 150 ℃.
As can be seen from fig. 6, the wide temperature solid state lithium carbon dioxide battery can normally operate even at-60 ℃. When the operating temperature is increased from 30 ℃ to 150 ℃, ultra-high round-trip efficiencies of up to 90% are achieved. When the temperature is restored to 25 ℃, the overpotential of the wide-temperature solid-state lithium-carbon dioxide battery can be almost restored to the original overpotential. In sharp contrast, a liquid lithium carbon dioxide battery with a positive electrode using an ionic liquid electrolyte and a CNT was not able to operate at-40 ℃. When the temperature returns to 25 ℃, the overpotential of the liquid lithium carbon dioxide battery cannot be recovered. These results demonstrate that the solid-state lithium carbon dioxide battery using IL @ MOF/CNT-IL @ MOF has excellent environmental suitability, and exhibits remarkable heat and freeze resistance.
We propose and prepare a novel wide-temperature solid-state metal-air battery for the first time, which comprises a metal cathode, an IL @ MOF solid-state electrolyte and a C-IL @ MOF solid-state anode. The solid metal-air battery with a reasonable structure can realize high-efficiency operation and stably work under a wide temperature window.
(1) The mobility of the IL encapsulated in the MOF lattice is limited, which may well avoid the risk of electrolyte leakage; MOFs provide a stable three-dimensional open rigid solid framework to ensure the dynamic properties of the interface, thereby achieving high ionic conductivity and high lithium ion transfer number.
(2) C-IL @ MOF meets three criteria for solid state anodes, namely high electronic conductivity, high ionic conductivity, and high redox kinetics.
(3) Solid state metal-air batteries exhibit ultra-low resistance, high round-trip efficiency, and good rate performance at room temperature, benefiting from the nano-wetting interface of il @ mof with the electrodes. Meanwhile, the solid-state metal-air battery shows an ultra-wide working temperature window (-60 ℃ to 150 ℃), and is expected to be applied to complex and variable environments.
Solid state metal-air batteries of reasonable design show broad promise for safe use of energy storage devices over a complex wide temperature range.
In conclusion, the key breakthrough of the solid electrolyte and the solid anode provides guarantee for the safety and stability of the lithium-carbon dioxide battery with high energy density, and also provides a feasible strategy for other metal-air batteries and secondary energy storage systems.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.

Claims (7)

1. A wide temperature solid state metal-air battery, comprising:
a C-IL @ MOF solid state positive electrode, an IL @ MOF solid state electrolyte, and a metal negative electrode;
the C-IL @ MOF solid-state positive electrode is formed by compounding a conductive catalyst, a metal organic framework material and an ionic liquid;
the IL @ MOF solid electrolyte is formed by compounding a metal organic framework material and an ionic liquid.
2. The wide temperature solid state metal air battery of claim 1, wherein the MOF is a single or multiple materials of MIL-101, uiO-66, uiO-67.
3. The wide temperature solid-state metal-air battery of claim 1, wherein the IL is a single or multiple materials in an imidazole, pyridine, or quaternary ammonium ionic liquid.
4. The wide temperature solid-state metal-air battery of claim 1, wherein the C in the C-il @ mof solid-state positive electrode is a single or multiple materials of carbon nanotubes, graphene, conductive carbon.
5. The wide temperature solid state metal air battery of claim 1, wherein the composite process is a mill mix process.
6. The wide temperature solid state metal-air battery of claim 1, wherein the metal negative electrode is one of a lithium, sodium, potassium, zinc, iron, magnesium, or aluminum sheet.
7. A method of making a wide temperature range solid state metal-air battery as claimed in any of claims 1 to 6, wherein the C-IL @ MOF solid state positive electrode, the IL @ MOF solid state electrolyte and the metal negative electrode are encapsulated in the battery from top to bottom.
CN202210527824.9A 2022-05-16 2022-05-16 Wide-temperature solid metal-air battery and preparation method thereof Active CN115189076B (en)

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