CN115692954A - High-temperature-resistant lithium-carbon dioxide battery and preparation method thereof - Google Patents
High-temperature-resistant lithium-carbon dioxide battery and preparation method thereof Download PDFInfo
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- CN115692954A CN115692954A CN202211309885.4A CN202211309885A CN115692954A CN 115692954 A CN115692954 A CN 115692954A CN 202211309885 A CN202211309885 A CN 202211309885A CN 115692954 A CN115692954 A CN 115692954A
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Abstract
The invention provides a high-temperature-resistant lithium-carbon dioxide battery and a preparation method thereof. The lithium-carbon dioxide battery prepared by the invention takes a metal lithium sheet as a negative electrode; lithium salt dissolved in imidazole ionic liquid is used as electrolyte; taking a high-temperature resistant porous membrane as a diaphragm; taking a porous conductive substrate supported catalyst as a positive electrode; and the metal mesh is used as a positive electrode current collector. The battery can be used at 80 deg.C and high temperature of 1000 mA.g ‑1 Current density of (1) and 1000 mAh.g ‑1 The cut-off capacity of the capacitor exceeds 240 circles stably, and a high discharge plateau of-2.69V and a low charge voltage of-4.22V are shown; in addition, the high temperature effectively promotes the reduction and precipitation reaction dynamic process of carbon dioxide in the lithium-carbon dioxide battery, and greatly improves the charge and discharge stability of the battery under high current densityStill show a high discharge plateau of 2.39V and a low charge plateau of 4.45V at a high temperature of 80 ℃ and a large current density of 5000mA · g < -1 >, and show excellent rate and cycling stability in a high-temperature environment.
Description
Technical Field
The invention relates to the technical field of new energy batteries, in particular to a high-temperature-resistant lithium-carbon dioxide battery and a preparation method thereof.
Background
The lithium-carbon dioxide battery has higher energy density (1876 Wh/kg) and higher discharge platform (2.8V vs. Li/Li +), and shows very wide application prospect in the aspects of carbon dioxide fixation and energy storage. In recent years, researchers have developed a series of high-performance cathode catalysts and novel quasi-solid/solid electrolytes, and the rate performance and the cycling stability of the lithium-carbon dioxide battery are remarkably improved. The electrolyte is an important component of the lithium-carbon dioxide battery and has a decisive influence on the rate capability, the cycling stability and the operable temperature range of the battery. The organic liquid electrolyte has the characteristics of high ionic conductivity and ionic mobility, high electrochemical stability, high carbon dioxide solubility and the like, is widely applied to lithium-carbon dioxide batteries and shows excellent battery performance.
It is worth noting that the lithium-carbon dioxide battery using the organic liquid electrolyte is easy to volatilize and leak at high temperature (40-80 ℃), easy to be flammable, easy to be decomposed at high charging voltage, and unstable to byproducts of the lithium-carbon dioxide battery reaction, such as superoxide radical and the like, which seriously affects the stability and safety of the lithium-carbon dioxide battery and cannot meet the practical application of the lithium-carbon dioxide battery in high temperature environment. It is therefore necessary to design and implement a lithium-carbon dioxide battery that can operate in a high temperature environment for a long time.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a high-temperature-resistant lithium-carbon dioxide battery and a preparation method thereof, which solve the problems that the lithium-carbon dioxide battery using an organic liquid electrolyte in the prior art is easy to volatilize, leak and flammable when the electrolyte is at high temperature.
The technical purpose of the invention is realized by the following technical scheme:
a high temperature resistant lithium-carbon dioxide battery comprising the following components: taking a metal lithium sheet as a negative electrode; dissolving lithium salt in imidazole ionic liquid to serve as electrolyte; taking a high-temperature resistant porous membrane as a diaphragm; taking a porous conductive substrate supported catalyst as a positive electrode; and the metal mesh is used as a positive electrode current collector.
The invention is further configured to: in the electrolyte, the lithium salt is one or a mixture of more of lithium bistrifluoromethanesulfonylimide, lithium hexafluorophosphate, lithium trifluoromethanesulfonate, lithium bis (trifluoromethanesulfonyl) imidazolium, lithium bisoxalato borate, lithium tetrafluoroborate, lithium perchlorate and lithium nitrate.
The invention is further configured to: in the electrolyte, imidazole ionic liquid is used as a solvent, wherein cations are one or a mixture of more than one of 1-alkyl-3-methylimidazole (wherein alkyl comprises ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl and octadecyl), and anions are one or a mixture of more than one of tetrafluoroborate, hexafluorophosphate, bistrifluoromethanesulfonimide, perchlorate and trifluoromethanesulfonate.
The invention is further configured to: the high-temperature resistant porous membrane is any one of a polyethylene membrane, a polypropylene membrane, an organic silicon polydimethylsiloxane membrane, a glass microfiber membrane, a polyimide membrane, an aramid fiber membrane and a polyethylene terephthalate membrane.
The invention is further configured to: the anode catalyst is one or a mixture of more of graphene, multi-walled carbon nanotubes, nitrogen-doped carbon nanotubes, graphite alkyne, fluorine-substituted graphite alkyne, iridium carbon, ruthenium carbon, platinum carbon and palladium carbon; the porous flexible substrate loaded with the anode catalyst is any one of foamed nickel, foamed stainless steel, conductive carbon paper, carbon fiber cloth, a graphene film, a reduced graphene oxide film and a carbon nanotube film.
The invention is further configured to: the positive current collector is any one of a titanium mesh, a nickel mesh and a stainless steel mesh.
The invention also provides a preparation method of the high-temperature-resistant lithium-carbon dioxide battery, which is characterized by comprising the following steps: the method comprises the following steps:
step one, preparing electrolyte;
fully dissolving lithium salt in ionic liquid solvent, wherein the concentration of the lithium salt is 0.5-2.0 mol.L -1 Adding lithium strips and stirring for 3-7 days before use to fully remove residual water;
preparing a gas anode of the lithium-carbon dioxide battery;
mixing the anode catalyst and polyvinylidene fluoride binder according to the mass ratio of 6:1-10 -1 Uniformly coating the dispersion liquid on a porous conductive substrate, drying the obtained pole piece in a vacuum oven at 80 ℃ for 8-24 h, wherein the loading amount of a catalyst on the porous conductive substrate is 0.10-1.0 mg-cm -2 ；
Step three, assembling the lithium-carbon dioxide battery;
in a glove box with water and oxygen contents less than 1ppm, a metal lithium sheet is taken as a negative electrode, imidazole ionic liquid dissolved lithium salt is taken as electrolyte, a high-temperature resistant porous membrane is taken as a diaphragm, a porous conductive substrate loaded with a catalyst is taken as a positive electrode, and a metal net is taken as a positive electrode current collector, and the lithium-carbon dioxide battery can be prepared by assembly.
In the invention, due to the extremely low vapor pressure and excellent thermal stability of the ionic liquid, the prepared lithium-carbon dioxide battery can still be stably charged and discharged circularly at the high temperature of 80 ℃. And the high temperature can also effectively promote the reduction and precipitation reaction kinetic process of the carbon dioxide at the anode, and greatly improve the charge-discharge stability of the battery under the high current density.
Drawings
FIG. 1 is a cyclic voltammogram of a lithium-carbon dioxide battery prepared in example 1 in a carbon dioxide atmosphere at different temperatures;
FIG. 2 is a linear sweep voltammogram of the lithium-carbon dioxide cell prepared in example 1 at various temperatures;
FIG. 3 is an electrochemical impedance spectrum of a lithium-carbon dioxide battery prepared in example 1 at various temperatures;
FIG. 4 shows the lithium-carbon dioxide batteries prepared in example 1 and comparative example 1 at a high temperature of 80 ℃ and 1000mA g -1 Current density of (1) and 1000mAh g -1 A comparison graph of cycle performance under the cut-off capacity condition of (a);
fig. 5 is a discharge-charge curve of the lithium-carbon dioxide battery manufactured in example 1 at a high temperature of 80 c and different current densities;
FIG. 6 shows the lithium-carbon dioxide battery prepared in example 1 at a high temperature of 80 ℃ and 1000mA · g -1 Multiple discharge-charge curves at current density of (a).
Detailed Description
The technical solution of the present invention is further explained with reference to the drawings and the embodiments.
Example 1:
a preparation method of a high-temperature resistant lithium-carbon dioxide battery comprises the following steps,
(1) Preparing an electrolyte:
fully dissolving lithium bistrifluoromethanesulfonimide into 1-butyl-3-methylimidazolium bistrifluoromethanesulfonimide ionic liquid, wherein the concentration of lithium salt is 1 mol.L -1 And obtaining the high-temperature-resistant lithium-carbon dioxide battery electrolyte. Adding a lithium bar into the ionic liquid before use, and stirring for 3-7 days to fully remove residual water.
(2) Preparing a gas positive electrode of the lithium-carbon dioxide battery:
fluorine substituted graphite alkyne is used as a positive electrode catalyst, mixed with polyvinylidene fluoride binder in a mass ratio of 9:1 and fully ground in a nitrogen methyl pyrrolidone solution to form a concentration of 0.5 mg/mL -1 The dispersion was then uniformly sprayed on carbon paper (TGP-H-060, toray), the carbon paper loaded with the fluorine-substituted graphite alkyne catalyst was dried in a vacuum oven at 80 ℃ for 24 hours and punched into a sheet having a diameter of 11mm, and the amount of active material loaded on the carbon paper was 0.20 mg/cm -2 。
(3) Assembling the lithium-carbon dioxide battery:
the lithium-carbon dioxide battery was assembled using a CR2032 type button cell case, and a hole (1 mm in diameter) was punched in the positive electrode case of the battery for carbon dioxide gas diffusion. The cell assembly was completed in a glove box with water oxygen content less than 1 ppm. Lithium sheets (diameter 15.6mm, thickness 0.45 mm) and microglass fiber membranes (Whatman, GF/D, diameter 18 mm) were used as battery negative electrodes and separators, respectively. All parts of the battery are stacked from bottom to top according to the sequence of a negative electrode shell, a stainless steel gasket, a lithium sheet, a diaphragm for dripping electrolyte, a positive electrode sheet, a metal mesh current collector and a positive electrode shell, and then are packaged by a button cell packaging machine.
Performance testing of lithium-carbon dioxide batteries: and transferring the assembled lithium-carbon dioxide battery device into a self-made gas battery test box, introducing high-purity carbon dioxide gas into the test box, sealing the test box, transferring the test box into a high-temperature incubator, and testing the constant current charge-discharge curve of the battery at high temperature by using a blue battery test system.
Referring to fig. 1, the peak current in the cyclic voltammogram at 80 ℃ of the lithium-carbon dioxide battery prepared in this example is significantly increased compared to that at 30 ℃, indicating that the increase in temperature effectively promotes the kinetics of the reduction and precipitation reaction of carbon dioxide on the surface of the positive electrode. Referring to fig. 2, the lithium-carbon dioxide battery prepared in this example does not show a significant potential window narrowing at a high temperature of 80 ℃, and shows excellent electrochemical and thermal stability; referring to fig. 3, the charge transfer resistance in the cell decreased significantly as the temperature increased to 80 ℃, indicating that the ion migration and diffusion rates in the electrolyte increased dramatically with increasing temperature, effectively reducing the degree of polarization at high current density in the cell.
As shown in FIG. 4, the lithium-carbon dioxide battery prepared by the present invention was operated at a high temperature of 80 ℃ and 1000mA · g -1 Current density of (1) and 1000mAh g -1 Can stabilize 240 cycles of charge and discharge cycles under the condition of the cut-off capacity of (3). In addition, the high temperature can effectively promote the reduction and precipitation reaction kinetic process of carbon dioxide at the positive electrode, and greatly improve the charge and discharge stability of the battery under the heavy current density, as shown in figure 5, the battery is at the high temperature of 80 ℃ and the temperature of 5000 mA-g -1 Still shows a high discharge plateau of-2.39V and a low charge plateau of-4.45V at high current density of (2); as shown in FIG. 6, the temperature was elevated at 80 ℃ and 1000mA · g -1 The first discharge capacity and the charge capacity of the battery under the current density are 16399 mAh.g -1 And 16038mAh g -1 The 3 rd charge-discharge still has 15148mAh g -1 Discharge capacity of 13352mAh g -1 The charging capacity of (1).
Comparative example 1:
this comparative example 1 provides a method for preparing a lithium-carbon dioxide battery, which comprises the same steps as in example 1, except that the ionic liquid of 1-butyl-3-methylimidazolium bis (trifluoromethanesulfonimide) was changed to Tetraglyme (TEGDME), thereby preparing a lithium-carbon dioxide battery.
As seen from FIG. 4, the lithium-carbon dioxide battery prepared in comparative example 1 was poor in stability at a high temperature of 80 ℃ and at 1.0A. G -1 Current density of (1) and 1000mAh g -1 Can perform only 26 charge-discharge cycles under the condition of the cut-off capacity of (2).
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.
Claims (7)
1. A high temperature resistant lithium-carbon dioxide battery, characterized by: the method comprises the following components: taking a metal lithium sheet as a negative electrode; dissolving lithium salt in imidazole ionic liquid to serve as electrolyte; taking a high-temperature resistant porous membrane as a diaphragm; taking a porous conductive substrate supported catalyst as a positive electrode; and the metal mesh is used as a positive electrode current collector.
2. A high temperature resistant lithium-carbon dioxide battery as claimed in claim 1, wherein: in the electrolyte, the lithium salt is one or a mixture of more of lithium bistrifluoromethanesulfonylimide, lithium hexafluorophosphate, lithium trifluoromethanesulfonate, lithium bis (trifluoromethanesulfonyl) imidazolium, lithium bis (oxalato) borate, lithium tetrafluoroborate, lithium perchlorate and lithium nitrate.
3. A high temperature resistant lithium-carbon dioxide battery as claimed in claim 1, wherein: in the electrolyte, imidazole ionic liquid is used as a solvent, wherein cations are one or a mixture of more than one of 1-alkyl-3-methylimidazole (wherein alkyl comprises ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl and octadecyl), and anions are one or a mixture of more than one of tetrafluoroborate, hexafluorophosphate, bistrifluoromethanesulfonimide, perchlorate and trifluoromethanesulfonate.
4. A high temperature resistant lithium-carbon dioxide battery as claimed in claim 1, wherein: the high-temperature resistant porous membrane is any one of a polyethylene membrane, a polypropylene membrane, an organic silicon polydimethylsiloxane membrane, a glass microfiber membrane, a polyimide membrane, an aramid fiber membrane and a polyethylene terephthalate membrane.
5. A high temperature resistant lithium-carbon dioxide battery as claimed in claim 1, wherein: the anode catalyst is one or a mixture of more of graphene, multi-walled carbon nanotubes, nitrogen-doped carbon nanotubes, graphite alkyne, fluorine-substituted graphite alkyne, iridium carbon, ruthenium carbon, platinum carbon and palladium carbon; the porous flexible substrate loaded with the anode catalyst is any one of foamed nickel, foamed stainless steel, conductive carbon paper, carbon fiber cloth, a graphene film, a reduced graphene oxide film and a carbon nanotube film.
6. A high temperature resistant lithium-carbon dioxide battery as claimed in claim 1, wherein: the positive current collector is any one of a titanium mesh, a nickel mesh and a stainless steel mesh.
7. A method of manufacturing a high temperature resistant lithium-carbon dioxide battery according to claims 1-6, characterized in that: the method comprises the following steps:
step one, preparing electrolyte;
fully dissolving lithium salt in an ionic liquid solvent, wherein the concentration of the lithium salt is 0.5-2.0 mol.L < -1 >, adding a lithium strip before use, and stirring for 3-7 days to fully remove residual water;
preparing a gas anode of the lithium-carbon dioxide battery;
mixing the anode catalyst and polyvinylidene fluoride binder according to the mass ratio of 6:1-10 -1 Uniformly coating the dispersion liquid on a porous conductive substrate, drying the obtained pole piece in a vacuum oven at 80 ℃ for 8-24 h, wherein the loading amount of a catalyst on the porous conductive substrate is 0.10-1.0 mg-cm -2 ；
Step three, assembling the lithium-carbon dioxide battery;
in a glove box with water and oxygen contents less than 1ppm, a metal lithium sheet is taken as a negative electrode, imidazole ionic liquid dissolved lithium salt is taken as electrolyte, a high-temperature resistant porous membrane is taken as a diaphragm, a porous conductive substrate loaded with a catalyst is taken as a positive electrode, and a metal net is taken as a positive electrode current collector, and the lithium-carbon dioxide battery can be prepared by assembly.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116960377A (en) * | 2023-09-20 | 2023-10-27 | 中石油深圳新能源研究院有限公司 | Working electrode for sodium-carbon dioxide battery and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116960377A (en) * | 2023-09-20 | 2023-10-27 | 中石油深圳新能源研究院有限公司 | Working electrode for sodium-carbon dioxide battery and preparation method thereof |
| CN116960377B (en) * | 2023-09-20 | 2024-01-05 | 中石油深圳新能源研究院有限公司 | Working electrode for sodium-carbon dioxide battery and preparation method thereof |
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