CN114068970A - Photo-assisted lithium-carbon dioxide battery and preparation method thereof - Google Patents
Photo-assisted lithium-carbon dioxide battery and preparation method thereof Download PDFInfo
- Publication number
- CN114068970A CN114068970A CN202111228969.0A CN202111228969A CN114068970A CN 114068970 A CN114068970 A CN 114068970A CN 202111228969 A CN202111228969 A CN 202111228969A CN 114068970 A CN114068970 A CN 114068970A
- Authority
- CN
- China
- Prior art keywords
- lithium
- film
- electrolyte
- solution
- battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
- H01M4/96—Carbon-based electrodes
-
- 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
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to the technical field of chemical power supplies, and particularly relates to a photo-assisted lithium-carbon dioxide battery and a preparation method thereof. The battery is formed by assembling a negative current collector, a lithium negative electrode, an electrolyte, a photocatalytic positive electrode, a positive current collector with an optical window and a positive protective layer; the photocatalysis anode is prepared by depositing graphite-phase carbon nitride material with photoelectric effect on the conductive carbon nanotube film by an in-situ chemical deposition method; the electrolyte is selected from organic solution electrolyte, gel quasi-solid electrolyte, molten salt electrolyte, ionic liquid electrolyte and the like; when illumination is radiated from one side of the photocatalytic positive electrode, the positive electrode can absorb photons and generate photoelectrons and holes to promote the discharge and charge reaction of the battery, so that the constructed lithium-carbon dioxide battery realizes the cycle efficiency of more than 90 percent and the cycle life of more than 100 circles. The battery has wide application prospect in the field of energy storage devices.
Description
Technical Field
The invention belongs to the technical field of chemical power supplies, and particularly relates to a photo-assisted lithium-carbon dioxide battery and a preparation method thereof.
Background
The lithium-carbon dioxide battery has CO2The dual functions of stationary and energy storage provide an economical and feasible strategy for addressing two crucial environmental issues, global warming and energy crisis. Furthermore, CO is utilized2The energy storage device has good application prospect in space navigation exploration by being used as a positive electrode raw material. Therefore, this energy storage system has attracted increasing research interest in recent years. However, it is limited by the positive electrode reaction raw material CO2And the slow kinetic conversion process between the solid-state discharge products, the energy storage system has very poor electrochemical performance and only stays at the concept stage. Although researchers have developed a number of electrocatalysts and soluble redox promoters to address this problem, the charge and discharge polarization of the cells remains very severe and the cycling stability is poor. Further, severe polarization voltage exacerbates side reactions such as electrolyte/electrode degradation, further resulting in degradation or complete failure of the battery. In view of the important theoretical and practical significance of this battery, it is very important, but also challenging, to implement a high efficiency and stable lithium carbon dioxide battery system.
As is well known, solar energy is an inexhaustible, green energy source. Recently, researchers have proposed an attractive photo-assisted catalytic strategy to reduce the polarization degree of the cell and improve the cycle efficiency. The design core of this strategy is to introduce a suitable photocatalyst into the air electrode as the photoelectrode. When radiation is applied to one side of the photoelectrode, the photocatalyst can absorb photons and generate a large number of photo-generated electron-hole pairs with strong oxidation and reduction capabilities, and the photo-generated carriers can effectively promote the discharge and charge reactions. At present, the design strategy is successfully applied to systems such as lithium ion batteries, zinc ion batteries, lithium air batteries, zinc air batteries and the like. This strategy may also be expected to improve the cycle efficiency and cycle life of lithium carbon dioxide batteries.
Disclosure of Invention
The invention aims to provide a photo-assisted lithium-carbon dioxide battery with high cycle efficiency, long cycle life and good rate capability and a preparation method thereof.
The photo-assisted lithium-carbon dioxide battery provided by the invention is in the form of a button battery, and consists of a negative current collector, a lithium negative electrode, an electrolyte, a photocatalytic positive electrode, a positive current collector with an optical window and a positive protective layer. Wherein:
the photocatalytic anode is prepared by depositing graphite-phase carbon nitride with a photoelectric effect on a carbon nano tube film by an in-situ chemical deposition method;
the electrolyte is one or a mixture of organic solution electrolyte, gel quasi-solid electrolyte, molten salt electrolyte, ionic liquid electrolyte and lithium salt;
the positive electrode protective layer adopts a high-molecular selective permeation membrane.
Further:
the gel quasi-solid electrolyte comprises but is not limited to organic solvent or ionic liquid dissolved with lithium salt and polymer matrix. Wherein the lithium salt is one or more of bis (trifluoromethane sulfonyl) imide lithium, lithium hexafluorophosphate, lithium trifluoromethanesulfonate, bis (trifluoromethane sulfonyl) imidazole lithium, lithium tetrafluoroborate, lithium perchlorate and lithium nitrate; the solvent is one or a mixture of more of 1, 3-dioxolane, 2-methyl-tetrahydrofuran, 2-dimethoxyethane, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 1-ethyl-3-methylimidazolium tetrafluoroborate and 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imidazole; the polymer matrix is one or a mixture of polyvinylidene fluoride-hexafluoropropylene, polymethyl methacrylate, polyacrylamide and polyurethane.
The polymer selective permeation membrane is one selected from a colorless transparent polymethylpentene membrane, a polyethylene membrane, an organic silicon polydimethylsiloxane membrane and a paraffin membrane.
The current collectors are common positive and negative current collector materials; the lithium sheet is a typical negative electrode lithium sheet material.
Under illumination, the photocatalytic anode can effectively absorb photons with specific energy to generate a large number of photo-generated electron-hole pairs, and photo-generated electrons and holes can be effectively separated and transmitted and participate in carbon dioxide reduction and precipitation reactions in the discharging and charging processes, so that the problem of slow charging and discharging kinetics process of the lithium-carbon dioxide battery can be solved. The battery has the advantages of cheap and easily-obtained synthetic raw materials, simple assembly process, high cycle efficiency, good rate performance, long cycle life and large-scale production and preparation, thereby having wide application prospect.
Specifically, when illumination is radiated from the positive electrode side, the photocatalytic positive electrode absorbs photons and excites electrons in the valence band to transition to the conduction band, generating photo-generated electron-hole pairs. In the light-assisted discharge process, photoelectrons with strong reducibility promote the conversion of carbon dioxide into discharge products, namely lithium carbonate and carbon, so that the cell shows a discharge voltage exceeding a thermodynamic equilibrium potential in the process, and the conversion of light energy into electric energy is realized. In the photo-assisted charging process, photo-generated holes with strong oxidizing property participate in the degradation of solid discharge products to effectively reduce the charging overpotential, and the conversion of light energy into chemical energy is realized in the process. Therefore, the photocatalytic anode can absorb photons to generate a large number of high-energy carriers to promote the discharge and charge processes of the battery, so that the cycle efficiency and the cycle life of the device are improved.
The invention provides a preparation method of a photo-assisted lithium-carbon dioxide battery, which comprises the following specific steps:
(1) preparing a photocatalytic positive electrode; sequentially cleaning a high-conductivity carbon nanotube film by using ethanol, acetone and deionized water, fully drying, transferring the film into a nitric acid solution with the volume fraction of 30-65%, heating at 60-140 ℃ for 1-12h, taking out the carbon nanotube film after acid treatment, fully cleaning and drying by using deionized water, immersing the carbon nanotube film subjected to hydrophilic treatment in an aqueous solution containing 0.5-2.0 g/mL guanidine hydrochloride and 1-10 mg/mL polyethylene glycol 4000, treating at 75-85 ℃ for 1-8h, taking out the film, flatly spreading the film in a crucible, fully drying, and transferring to a tubular furnace; argon is used as an inert gas source, inert gas is introduced for 10-40 min at the flow rate of 100-400 sccm to remove air, then the gas flow rate is adjusted to 50-200 sccm, the temperature is raised to 500-600 ℃ at the temperature rise speed of 1-20 ℃/min, thermal polymerization is carried out after 2-6h of heat preservation, and after the reaction is finished, the graphite-phase carbon nitride and carbon nanotube composite film is obtained after the temperature is cooled to room temperature at the temperature drop speed of 1-20 ℃/min;
(2) preparing a gel electrolyte; dissolving lithium salt in an organic solvent or ionic liquid in a glove box with oxygen and water contents lower than 1 ppm, wherein the concentration of the lithium salt is 0.1-2.0M, and adding a proper amount of lithium chips or a molecular sieve for drying to obtain a solution A; polyvinylidene fluoride-hexafluoropropylene was reacted with nitrogen methyl pyrrolidone at a molar ratio of 1: 4-1: 5 to prepare a solution B; reacting 2-hydroxy-2-methyl-1-phenyl-1-propanone with ethoxylated trimethylolpropane triacrylate at a molar ratio of 1: (295-305) to prepare a solution C, and mixing the solution A, the solution B and the solution C according to the mass ratio of (3.8-4.2): (4.8-5.2): (2.8-3.2) and fully stirring to obtain a viscous electrolyte precursor solution; dripping 0.2-0.5 mL of precursor solution on a diaphragm, and after the precursor solution is sufficiently and uniformly leveled, uniformly irradiating the diaphragm for 10-40 s by using ultraviolet light with the wavelength of 365 nm to prepare the gel electrolyte;
(3) assembling the lithium-carbon dioxide battery; and (3) sequentially placing the positive electrode current collector, the photocatalytic positive electrode obtained in the step (1), the gel electrolyte obtained in the step (2), the lithium sheet negative electrode, the gasket and the elastic sheet in a stainless button battery die with a net-shaped positive electrode shell from bottom to top in a glove box, applying pressure on a battery tablet press for fixing, and packaging a protective layer on the outer side of the positive electrode shell to obtain the photo-assisted lithium carbon dioxide battery.
The illumination light source which can be adopted in the actual test includes but is not limited to xenon lamp, ultraviolet lamp, sunlight and the like, and the illumination power is from 103–106W/m2。
The invention has the following advantages:
the invention utilizes cheap and easily available raw materials to prepare the carbon nano tube composite film loaded with the graphite phase carbon nitride material and utilizes the carbon nano tube composite film to construct the photo-assisted lithium-carbon dioxide battery with high cycle efficiency and excellent cycle stability, and the preparation cost is low, the reaction process is simple, and the process repeatability is good; the surface of the carbon nano tube which is uniformly grown by the synthesized graphite phase carbon nitride material has strong bonding force with the carbon nano tube; when the composite material is used for a battery photocatalytic electrode, the composite material can absorb photons with specific energy and generate high-activity photon-generated carriers to participate in battery reaction, so that the reaction kinetics of a positive electrode are improved; the photo-assisted lithium-carbon dioxide battery has the advantages of high cycle efficiency, long cycle life, good rate capability and the like; the assembled cell exhibited a cycling efficiency of over 90% under light and maintained a cycling efficiency of over 80% after 100 cycles; the invention has important application prospect in the fields of environmental protection, energy storage and flexible wearable electronic equipment.
Drawings
Fig. 1 is a schematic structural view of a lithium carbon dioxide battery constructed in example 1 of the present invention.
Fig. 2 is a scanning electron microscope and a transmission electron microscope photo of the highly conductive carbon nanotube film used in example 1 of the present invention.
Fig. 3 is a scanning electron microscope and a transmission electron microscope photograph of the graphite phase carbon nitride composite carbon nanotube film used in example 1 of the present invention.
Fig. 4 is a charging and discharging curve of the lithium-carbon dioxide battery constructed in example 1 of the present invention in light and dark.
Fig. 5 is a cycle charge and discharge curve of the lithium-carbon dioxide battery constructed in example 1 of the present invention in light and dark.
Fig. 6 is a charging and discharging curve of the lithium-carbon dioxide battery constructed in example 1 of the present invention when operated under light with different current densities and surface capacities.
Fig. 7 is a deep discharge curve of the lithium-carbon dioxide battery constructed in example 1 of the present invention in light and dark.
Fig. 8 is a scanning electron microscope photograph of the photocatalytic positive electrode after the lithium-carbon dioxide battery constructed in example 1 of the present invention was discharged and charged under illumination.
Fig. 9 is a charging and discharging curve of the lithium-carbon dioxide battery constructed in example 2 of the present invention in light and dark.
Fig. 10 shows the long-term cycle charge-discharge curves and energy efficiencies in light and dark for the lithium-carbon dioxide battery constructed in example 3 of the present invention.
Fig. 11 shows the long-term cycle charge-discharge curves and energy efficiency of the lithium-carbon dioxide battery constructed in example 4 of the present invention in light and dark.
Fig. 12 is a deep charge and discharge curve of the lithium-carbon dioxide battery constructed in example 5 of the present invention in light and dark.
Detailed Description
The present invention is further described with reference to the accompanying drawings and the specific embodiments, but the specific details of the embodiments are only for the purpose of illustrating the present invention and do not represent all the technical solutions under the inventive concept, therefore, the present invention should not be construed as being limited to the general technical solutions of the present invention, and some insubstantial additions and modifications, such as simple changes or substitutions with technical features having the same or similar effects, which are within the scope of the present invention will be apparent to the skilled person.
Example 1
Sequentially cleaning a high-conductivity carbon nanotube film for 10 min by using ethanol, acetone and deionized water, drying the film in a vacuum drying oven at 60 ℃, then transferring the film into a concentrated nitric acid solution to treat the film for 3h at 120 ℃, taking out the carbon nanotube film after acid treatment, fully cleaning and drying the film by using the deionized water, completely immersing the hydrophilic carbon nanotube film in an aqueous solution containing 1.0 g/mL guanidine hydrochloride and 2 mg/mL polyethylene glycol 4000 to treat the film for 3h at 80 ℃, spreading the film in a crucible, fully drying the film, and transferring the film to a tubular furnace. And introducing argon gas at the flow rate of 200 sccm for 20 min, adjusting the flow rate of the gas to 100sccm, starting a heating program, heating to 600 ℃ at the speed of 4 ℃/min, preserving the temperature for 4h, and cooling to room temperature at the cooling speed of 1 ℃/min to obtain the graphite-phase carbon nitride composite carbon nanotube film. The carbon nanotube film adopted in the experiment has a loose and porous interwoven network structure (figure 2), the prepared graphite phase carbon nitride composite carbon nanotube film still keeps the loose and porous interwoven network structure, and the carbon nitride layer is uniformly deposited on the surface of a single carbon nanotube (figure 3). The porous interwoven carbon nanotube network is beneficial to gas diffusion, substance transportation and discharge product deposition, and the carbon nanotube and carbon nitride interface is beneficial to quick separation and transmission of photon-generated carriers.
Dissolving lithium bis (trifluoromethanesulfonic) sulfonimide in 1-ethyl-3-methylimidazolium tetrafluoroborate in a glove box with oxygen and water contents lower than 1 ppm, wherein the concentration of lithium salt is 1.0M, and adding a proper amount of molecular sieve for drying for 12 hours to obtain a solution A; mixing polyvinylidene fluoride-hexafluoropropylene and azomethyl pyrrolidone in a mass ratio of 1:4 to prepare a solution B; reacting 2-hydroxy-2-methyl-1-phenyl-1-propanone with ethoxylated trimethylolpropane triacrylate at a molar ratio of 1: 300 to prepare a solution C; mixing solution A, solution B and solution C in a ratio of 4: 5: 3, and fully stirring to obtain a precursor solution of the gel electrolyte; and dripping 0.3 mL of precursor solution on a glass fiber diaphragm, after the solution is fully permeated and uniformly leveled, uniformly irradiating the precursor solution for 20 s by using an ultraviolet lamp with the wavelength of 365 nm, and curing to obtain the gel electrolyte.
In the glove box, a positive electrode current collector, a photocatalytic positive electrode, gel electrolyte, a lithium sheet, a gasket and an elastic sheet are sequentially placed in a CR2032 stainless steel button battery die with a net-shaped positive electrode shell from bottom to top, a battery is fixed on a battery tablet press, and a layer of polymethylpentene film is packaged on the outer side of the net-shaped positive electrode shell to serve as a positive electrode protective layer, so that the photo-assisted lithium carbon dioxide battery is obtained.
The assembled cell was taken out of the glove box and quickly transferred to a transparent glass test bottle, to which highly pure carbon dioxide was continuously introduced at a flow rate of 100sccm for 1h to replace the residual air in the bottle. For the test under the illumination condition, a 350W xenon lamp is used for vertically irradiating the photocatalysis anode, and the illumination intensity is 40 mW/cm2. For testing under dark conditions, the test vials were placed in a light-tight environment. After the battery is stabilized for 3 hours under the open-circuit voltage, the flow rate of the carbon dioxide is adjusted to 20 sccm and then the battery is startedAnd (5) performing a dynamic test program.
The prepared lithium-carbon dioxide battery has lower charging and discharging overpotential and excellent energy efficiency, and the charging and discharging overpotential is 0.02 mA-cm under illumination-2The voltage plateau can reach 3.24V and 3.29V respectively when the current density of the capacitor is discharged and charged (figure 4), and the voltage plateau can reach 0.02 mAh cm-2The cut-off capacity of (A) is stable and the charge and the discharge are cycled for 100 circles (figure 5), and simultaneously, excellent rate performance (figure 6) and the maximum value of 15.77 mAh & cm are realized-2The face volume of (fig. 7). The catalytic positive electrodes before and after charging and discharging under illumination are observed by using a field emission scanning electron microscope (SEM, Hitachi FESEM S4800, working voltage 5 kV), and research shows that a large amount of granular discharge products are generated on the catalytic positive electrodes after discharging, and the discharge products can be completely decomposed after charging (figure 7), which shows that the battery has good cycle reversibility.
Example 2
Sequentially cleaning a high-conductivity carbon nanotube film for 10 min by using ethanol, acetone and deionized water, drying the film at 60 ℃ in a vacuum drying oven, transferring the film into a nitric acid solution with the volume fraction of 65% to perform reflux treatment at 120 ℃ for 3h, taking out the carbon nanotube film after acid treatment, fully cleaning and drying the film by using the deionized water, completely immersing the hydrophilic carbon nanotube film in an aqueous solution containing 0.5 g/mL guanidine hydrochloride and 1 mg/mL polyethylene glycol 4000 to perform treatment at 80 ℃ for 6h, then spreading the film in a crucible, fully drying the film and transferring the film to a tubular furnace. Introducing argon at the flow rate of 100sccm for 20 min to remove air, adjusting the flow rate to 100sccm, starting a heating program, heating to 600 ℃ at the speed of 10 ℃/min, preserving heat for 4h, and cooling to room temperature at the cooling speed of 10 ℃/min to obtain the graphite-phase carbon nitride composite carbon nanotube film.
Dissolving lithium bistrifluoromethane sulfonic acid sulfimide into tetraethylene glycol dimethyl ether in a glove box with oxygen and water contents lower than 1 ppm, wherein the concentration of lithium salt is 1.0M, and adding a proper amount of molecular sieve for drying to obtain a solution A; mixing polyvinylidene fluoride-hexafluoropropylene and azomethyl pyrrolidone in a mass ratio of 1:4 to prepare a solution B; reacting 2-hydroxy-2-methyl-1-phenyl-1-propanone with ethoxylated trimethylolpropane triacrylate at a molar ratio of 1: 300 to prepare a solution C; mixing solution A, solution B and solution C in a ratio of 4: 5: 3, mixing and fully stirring to obtain a gel electrolyte precursor solution; and (3) dropwise coating 0.3 mL of precursor solution on a glass fiber diaphragm, and after the solution fully permeates the diaphragm and is uniformly leveled, uniformly irradiating the precursor solution for 20 s by using an ultraviolet lamp with the wavelength of 365 nm to obtain the gel electrolyte.
In the glove box, a positive electrode current collector, a photocatalytic positive electrode, gel electrolyte, a lithium sheet, a gasket and an elastic sheet are sequentially placed in a CR2032 stainless steel button battery die with a net-shaped positive electrode shell from bottom to top, a battery is fixed on a battery tablet press, and a layer of polymethylpentene film is packaged on the outer side of the net-shaped positive electrode shell to serve as a positive electrode protective layer, so that the photo-assisted lithium carbon dioxide battery is obtained.
The assembled cell was quickly removed from the glove box and transferred to a transparent test vial into which high purity carbon dioxide was continuously introduced at a flow rate of 100sccm to replace residual air in the vial. For the test under the illumination condition, a 500W xenon lamp is used for transmitting a test bottle to vertically irradiate the photocatalysis anode, and the illumination intensity is controlled to be 40W/cm2. For testing under dark conditions, the test vials were placed in the dark. And when the battery is stabilized for 3 hours under the open-circuit voltage, adjusting the flow rate of the carbon dioxide to be 20 sccm, and starting a test program. The prepared lithium-carbon dioxide battery has lower charging and discharging overpotential and excellent energy efficiency, and the charging and discharging overpotential is 0.02 mA-cm under illumination-2The voltage plateau reached 2.90V and 3.03V for discharging and charging, respectively (fig. 9).
Example 3
Sequentially cleaning a high-conductivity carbon nanotube film by using ethanol, acetone and deionized water for 10 min, drying at 60 ℃, then transferring the film into a concentrated nitric acid solution with the volume fraction of 60%, treating the film at 60 ℃ for 3h, taking out the carbon nanotube film after acid treatment, fully cleaning and drying by using the deionized water, then immersing the hydrophilic carbon nanotube film in an aqueous solution containing 1.0 g/mL guanidine hydrochloride and 2 mg/mL polyethylene glycol 4000, treating the film at 80 ℃ for 3h, then flatly paving the film in a crucible, fully drying, and transferring the film to a tubular furnace. Argon gas is used as an inert gas source, the inert gas is introduced for 20 min at the flow rate of 200 sccm to remove air, then the gas flow rate is adjusted to 100sccm, the temperature is raised to 600 ℃ at the temperature rise speed of 4 ℃/min, the temperature is kept for 4h to carry out thermal polymerization reaction, and after the reaction is finished, the graphite-phase carbon nitride composite carbon nanotube film is obtained after the reaction is cooled to the room temperature at the temperature drop speed of 1 ℃/min.
Dissolving lithium bis (trifluoromethanesulfonic) sulfonimide in dimethyl sulfoxide (DMSO) in a glove box with oxygen and water contents lower than 1 ppm, wherein the concentration of lithium salt is 1.0M, and adding a proper amount of molecular sieve for drying to obtain a solution A; mixing polyvinylidene fluoride-hexafluoropropylene and azomethyl pyrrolidone in a mass ratio of 1:4 to prepare a solution B; reacting 2-hydroxy-2-methyl-1-phenyl-1-propanone with ethoxylated trimethylolpropane triacrylate at a molar ratio of 1: 300 to prepare a solution C; mixing solution A, solution B and solution C in a ratio of 4: 5: 3, and fully stirring to obtain a precursor solution of the gel electrolyte; and (3) dropwise coating 0.3 mL of precursor solution on a glass fiber diaphragm, and after the solution fully permeates the diaphragm and is uniformly leveled, uniformly irradiating the precursor solution for 20 s by using an ultraviolet lamp with the wavelength of 365 nm to obtain the gel electrolyte.
In the glove box, a positive current collector, a photocatalytic positive electrode, gel electrolyte, a lithium sheet, a gasket and an elastic sheet are sequentially placed in a CR2032 stainless steel button battery die with a net-shaped positive electrode shell from bottom to top, a battery is fixed on a battery tablet press, and a polyethylene film is packaged on the outer side of the net-shaped positive electrode shell to serve as a positive protective layer, so that the photo-assisted lithium carbon dioxide battery is obtained.
The assembled cell was removed from the glove box and quickly transferred to a glass test vial into which high purity carbon dioxide was continuously introduced at a flow rate of 100 sccm. For the test under the illumination condition, the photocatalytic anode was vertically irradiated with a 500W ultraviolet lamp. For testing under dark conditions, the glass test vials were placed in a dark environment. And after the battery is stabilized for 3 hours in an open-circuit voltage state, adjusting the flow rate of the carbon dioxide to 20 sccm, and then starting a test program. The prepared lithium-carbon dioxide battery has high cycling stability and can be irradiated by 0.02 mA-cm-2Current density of0.02 mAh·cm-2The off capacity of (2) is stable and the charge and discharge are cycled for 100 cycles (fig. 10).
Example 4
Sequentially cleaning a carbon nano tube film for 10 min by using ethanol, acetone and deionized water, drying the carbon nano tube film in a vacuum drying oven at 60 ℃, then transferring the carbon nano tube film into a nitric acid solution with the volume fraction of 60%, treating the carbon nano tube film for 6h at 80 ℃, taking out the carbon nano tube film after acid treatment, fully cleaning and drying the carbon nano tube film by using the deionized water, immersing the carbon nano tube film after hydrophilic treatment in an aqueous solution of 1.0 g/mL guanidine hydrochloride and 2 mg/mL polyethylene glycol 4000 for treating for 3h at 80 ℃, taking out the film, spreading the film in a crucible, fully drying the film and transferring the film to a tubular furnace. And introducing argon gas at the flow rate of 200 sccm for 20 min, adjusting the flow rate of the argon gas to 100sccm, heating to 550 ℃ at the speed of 1 ℃/min, preserving the heat for 4h, and cooling to room temperature at the cooling speed of 1 ℃/min to obtain the graphite-phase carbon nitride composite carbon nanotube film.
Dissolving lithium trifluoromethanesulfonate in dimethyl sulfoxide in a glove box with oxygen and water contents lower than 1 ppm, wherein the concentration of lithium salt is 1.0M, and adding a proper amount of molecular sieve for fully drying to obtain a solution A; mixing polyvinylidene fluoride-hexafluoropropylene and azomethyl pyrrolidone in a mass ratio of 1:4 to prepare a solution B; reacting 2-hydroxy-2-methyl-1-phenyl-1-propanone with ethoxylated trimethylolpropane triacrylate at a molar ratio of 1: 300 to prepare a solution C; mixing solution A, solution B and solution C in a ratio of 4: 5: 3, and fully stirring to obtain a precursor solution of the gel electrolyte; and (3) dripping 0.2 mL of precursor solution on a polypropylene diaphragm, and after the solution fully permeates the diaphragm and is uniformly leveled, uniformly irradiating the precursor solution for 20 s by using an ultraviolet lamp with the wavelength of 365 nm to obtain the gel electrolyte.
In the glove box, a positive current collector, a photocatalytic positive electrode, gel electrolyte, a lithium sheet, a gasket and an elastic sheet are sequentially placed in a CR2032 stainless steel button battery die with a net-shaped positive electrode shell from bottom to top, the die is fixed on a battery tablet press, and a layer of paraffin film is packaged outside the positive electrode shell to serve as a positive protective layer, so that the photo-assisted lithium-carbon dioxide battery is obtained.
Will assemble the battery from handThe sample was taken out from the kit and quickly transferred to a transparent glass test bottle, and high-purity carbon dioxide was continuously introduced into the test bottle at a flow rate of 100 sccm. For the test under the illumination condition, a 1000W xenon lamp is used for vertically irradiating the photocatalysis anode, and the illumination intensity is controlled to be 100 mW/cm2. For testing under dark conditions, the test vials were placed in a light-tight environment. And after the battery is stabilized for 3 hours under the open-circuit voltage, adjusting the flow rate of the carbon dioxide to 20 sccm and then starting a test program. The prepared lithium-carbon dioxide battery has lower charging and discharging overpotential and excellent energy efficiency, and the charging and discharging overpotential is 0.02 mA-cm under illumination-2Current density of 0.02 mAh cm-2Stable charge and discharge cycle for 100 cycles at the cut-off capacity of (2) (FIG. 11).
Example 5
Sequentially cleaning the high-conductivity carbon nanotube film by using ethanol, acetone and deionized water for 10 min, drying the film in a vacuum drying oven at 60 ℃, transferring the film into a nitric acid solution with the volume fraction of 30%, treating the film for 3h at 80 ℃, completely immersing the hydrophilic carbon nanotube film in an aqueous solution containing 1.5 g/mL guanidine hydrochloride and 3 mg/mL polyethylene glycol 4000 for treating the film for 3h at 80 ℃, paving the film in a crucible, fully drying the film, and transferring the film to a tubular furnace. And introducing argon gas at the flow rate of 200 sccm for 20 min, adjusting the flow rate of the gas to 100sccm, heating to 550 ℃ at the speed of 4 ℃/min, preserving the heat for 4h, and cooling to room temperature at the cooling speed of 1 ℃/min to obtain the graphite-phase carbon nitride composite carbon nanotube film.
In a glove box with oxygen and water contents lower than 1 ppm, dissolving lithium perchlorate in a mixed solvent (volume fraction ratio is 1: 1) of 1-ethyl-dimethyl imidazole tetrafluoroborate and dimethyl sulfoxide, wherein the concentration of lithium salt is 0.5M, and adding a proper amount of molecular sieve for fully drying to obtain a solution A; mixing polyvinylidene fluoride-hexafluoropropylene and azomethyl pyrrolidone in a mass ratio of 1:4 to prepare a solution B; reacting 2-hydroxy-2-methyl-1-phenyl-1-propanone with ethoxylated trimethylolpropane triacrylate at a molar ratio of 1: 300 to prepare a solution C; mixing solution A, solution B and solution C in a ratio of 4: 5: 3, and fully stirring to obtain a precursor solution of the gel electrolyte; and (3) putting 0.1 mL of precursor solution on a polypropylene diaphragm, and after the solution fully permeates the diaphragm and is uniformly leveled, uniformly irradiating the precursor solution for 30 s by using an ultraviolet lamp with the wavelength of 365 nm to obtain the gel electrolyte.
In the glove box, a positive electrode current collector, a photocatalytic positive electrode, a gel electrolyte, a lithium sheet, a gasket and an elastic sheet are sequentially placed in a CR2032 button battery with a positive electrode with a pore diameter of 7 mm from bottom to top, pressure is applied on a battery tablet press to fix the battery, and a colorless transparent ethylene film is packaged on the outer side of a reticular positive electrode shell to serve as a positive electrode protective layer, so that the photo-assisted lithium-carbon dioxide battery is obtained. The assembled cell was quickly removed from the glove box and transferred to a clear glass test vial to which high purity carbon dioxide was continuously introduced at a flow rate of 100sccm to replace the air in the vial. For the test under the illumination condition, a 500W ultraviolet lamp is used for vertically irradiating the photocatalysis anode through a transparent test bottle, and the illumination intensity is controlled to be 60 mW/cm2. For testing under dark conditions, the test vials were placed in a light-tight environment. And after the battery is stabilized for at least 3 hours under the open circuit voltage, adjusting the flow rate of the carbon dioxide to be 20 sccm, and then starting a test program. The prepared lithium-carbon dioxide battery has lower charging and discharging overpotential and excellent energy efficiency, and the charging and discharging overpotential is 0.02 mA-cm under illumination-2The current density of (2) and the off-voltage of 1.5V achieve a high surface capacity when discharging (fig. 12).
Claims (4)
1. A photo-assisted lithium-carbon dioxide battery is a button battery and is characterized by consisting of a negative current collector, a lithium sheet negative electrode, an electrolyte, a photocatalytic positive electrode, a positive current collector with an optical window and a positive protective layer; wherein:
the photocatalytic anode is prepared by depositing a graphite-phase carbon nitride material with a photoelectric effect on a conductive carbon nanotube film by an in-situ chemical deposition method;
the electrolyte is one or a mixture of organic solution electrolyte, gel quasi-solid electrolyte, molten salt electrolyte, ionic liquid electrolyte and lithium salt;
the positive electrode protective layer adopts a high-molecular selective permeation membrane.
2. The photo-assisted lithium carbon dioxide battery of claim 1, wherein the gel quasi-solid electrolyte consists of an organic solvent or ionic liquid dissolved with a lithium salt and a polymer matrix; wherein the lithium salt is one or more of bis (trifluoromethanesulfonyl) imide lithium, lithium hexafluorophosphate, lithium trifluoromethanesulfonate, bis (trifluoromethanesulfonyl) imidazolium, lithium tetrafluoroborate, lithium perchlorate and lithium nitrate; the solvent is one or a mixture of more of 1, 3-dioxolane, 2-methyl-tetrahydrofuran, 2-dimethoxyethane, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 1-ethyl-3-methylimidazolium tetrafluoroborate and 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imidazole; the polymer matrix is one or a mixture of polyvinylidene fluoride-hexafluoropropylene, polymethyl methacrylate, polyacrylamide and polyurethane.
3. The photo-assisted lithium-carbon dioxide battery according to claim 1, wherein the polymer selectively permeable film is one selected from a colorless transparent polymethylpentene film, a polyethylene film, an organic silicone polydimethylsiloxane film and a paraffin film.
4. A method for preparing a photo-assisted lithium carbon dioxide battery according to any one of claims 1 to 3, comprising the following steps:
(1) preparation of photocatalytic cathode
Sequentially cleaning a high-conductivity carbon nanotube film by using ethanol, acetone and deionized water, fully drying, transferring the film into a concentrated nitric acid solution with the volume fraction of 60-65%, heating and treating the film at 80-140 ℃ for 1-4 h, immersing the carbon nanotube film subjected to hydrophilic treatment in an aqueous solution containing 0.5-2.0 g/mL guanidine hydrochloride and 1-10 mg/mL polyethylene glycol 4000, treating the film at 75-85 ℃ for 2.5-3.5 h, taking out the film, flatly spreading the film in a crucible, fully drying the film, and transferring the film to a tubular furnace; argon is used as an inert gas source, inert gas is introduced for 10-40 min at the flow rate of 100-400 sccm to remove air, then the gas flow rate is adjusted to 50-200 sccm, the temperature is raised to 500-600 ℃ at the temperature rise speed of 1-20 ℃/min, thermal polymerization is carried out after 2-6h of heat preservation, and after the reaction is finished, the graphite-phase carbon nitride and carbon nanotube composite film is obtained and used as a photocatalytic anode after being cooled to room temperature at the temperature drop speed of 1-20 ℃/min;
(2) preparation of gel electrolyte
Dissolving lithium salt in an organic solvent or ionic liquid in a glove box with oxygen and water contents lower than 1 ppm, wherein the concentration of the lithium salt is 0.1-2.0M, and adding a proper amount of lithium chips or a molecular sieve for drying to obtain a solution A; polyvinylidene fluoride-hexafluoropropylene was reacted with nitrogen methyl pyrrolidone at a molar ratio of 1: 4-1: 5 to prepare a solution B; reacting 2-hydroxy-2-methyl-1-phenyl-1-propanone with ethoxylated trimethylolpropane triacrylate at a molar ratio of 1: (295-305) mixing the components in the mass ratio to prepare a solution C; mixing the solution A, the solution B and the solution C in the ratio of (3.8-4.2): (4.8-5.2): (2.8-3.2) and fully stirring to obtain a viscous electrolyte precursor solution; dripping 0.2-0.5 mL of precursor solution on a glass fiber or polypropylene diaphragm, and after the precursor solution is sufficiently and uniformly leveled, uniformly irradiating for 10-40 s by using ultraviolet light with the wavelength of 365 nm to prepare the gel electrolyte;
(3) assembly of lithium carbon dioxide battery
And (3) sequentially placing the positive electrode current collector, the photocatalytic positive electrode obtained in the step (1), the gel electrolyte obtained in the step (2), the lithium sheet negative electrode, the gasket and the elastic sheet in a stainless button battery die with a net-shaped positive electrode shell from bottom to top in a glove box, applying pressure on a battery tablet press for fixing, and packaging a protective layer on the outer side of the positive electrode shell to obtain the photo-assisted lithium carbon dioxide battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111228969.0A CN114068970B (en) | 2021-10-22 | 2021-10-22 | Light-assisted lithium carbon dioxide battery and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111228969.0A CN114068970B (en) | 2021-10-22 | 2021-10-22 | Light-assisted lithium carbon dioxide battery and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114068970A true CN114068970A (en) | 2022-02-18 |
| CN114068970B CN114068970B (en) | 2023-08-01 |
Family
ID=80235143
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111228969.0A Active CN114068970B (en) | 2021-10-22 | 2021-10-22 | Light-assisted lithium carbon dioxide battery and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114068970B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4336602A1 (en) * | 2022-09-12 | 2024-03-13 | L & T Technology Services Limited | Methane-assisted metal ion battery |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103480406A (en) * | 2013-08-30 | 2014-01-01 | 中国科学技术大学 | Nitrogen-doped graphene/nitrogen-doped carbon nanotube/tricobalt tetraoxide composite paper and preparation method thereof |
| CN108448119A (en) * | 2018-03-12 | 2018-08-24 | 中国工程物理研究院化工材料研究所 | Flexible fiber shape lithium-carbon dioxide battery of low charging voltage and preparation method thereof |
| CN110492203A (en) * | 2019-07-08 | 2019-11-22 | 南京航空航天大学 | A kind of preparation of novel lithium-carbon dioxide battery and its positive electrode |
| CN111446522A (en) * | 2020-03-21 | 2020-07-24 | 复旦大学 | Lithium-carbon dioxide battery capable of working at low temperature and preparation method thereof |
-
2021
- 2021-10-22 CN CN202111228969.0A patent/CN114068970B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103480406A (en) * | 2013-08-30 | 2014-01-01 | 中国科学技术大学 | Nitrogen-doped graphene/nitrogen-doped carbon nanotube/tricobalt tetraoxide composite paper and preparation method thereof |
| CN108448119A (en) * | 2018-03-12 | 2018-08-24 | 中国工程物理研究院化工材料研究所 | Flexible fiber shape lithium-carbon dioxide battery of low charging voltage and preparation method thereof |
| CN110492203A (en) * | 2019-07-08 | 2019-11-22 | 南京航空航天大学 | A kind of preparation of novel lithium-carbon dioxide battery and its positive electrode |
| CN111446522A (en) * | 2020-03-21 | 2020-07-24 | 复旦大学 | Lithium-carbon dioxide battery capable of working at low temperature and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| DE-HUI GUAN等: "Light/Electricity Energy Conversion and Storage for a Hierarchical Porous In2S3@CNT/SS Cathode towards a Flexible Li-CO2 Battery", ANGEW. CHEM. INT. ED. * |
| YANAN JIAO等: "Recent progress and prospects of Li-CO2 batteries: Mechanisms, catalysts and electrolytes", ENERGY STORAGE MATERIALS * |
| YINCHUAN LI等: "Highly Surface-Wrinkled and N-Doped CNTs Anchored on Metal Wire: A Novel Fiber-Shaped Cathode toward High-Performance Flexible Li–CO2 Batteries", ADV. FUNCT. MATER. * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4336602A1 (en) * | 2022-09-12 | 2024-03-13 | L & T Technology Services Limited | Methane-assisted metal ion battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114068970B (en) | 2023-08-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Hou et al. | SnO 2-microtube-assembled cloth for fully flexible self-powered photodetector nanosystems | |
| CN108565464B (en) | Sulfur-carrying MOF @ conductive polymer material and preparation method and application thereof | |
| CN110459755B (en) | Sulfur/polypyrrole/graphene/carbon nanotube composite film, preparation method and application thereof | |
| CN112490446B (en) | Preparation method of Co-CNT @ CF three-dimensional self-supporting lithium-sulfur battery positive electrode material | |
| CN112563586B (en) | Method for improving performance of zinc-iodine battery based on halogen bond effect | |
| CN111313111A (en) | Heteroatom-doped carbon/CoS based on metal organic framework derivation2Functional material and application thereof | |
| CN109273672B (en) | Na-K liquid alloy electrode coated with in-situ SEI film as well as preparation method and application thereof | |
| CN112635764A (en) | CoS/Co9S8Preparation method of @ C core-shell structure nano composite sodium ion battery cathode material | |
| CN113299928A (en) | Preparation method of high-performance flexible secondary zinc-silver-zinc-air hybrid battery positive electrode material | |
| CN109346723A (en) | The preparation method of the lithium ion battery of molybdenum disulfide nano sheet array structure based on molybdenum foil load | |
| Gong et al. | Anchoring high-mass iodine to nanoporous carbon with large-volume micropores and rich pyridine-N sites for high-energy-density and long-life Zn-I2 aqueous battery | |
| CN109755552B (en) | Carbon-encapsulated titanium oxynitride nanoparticle composite material and preparation method and application thereof | |
| CN114068970B (en) | Light-assisted lithium carbon dioxide battery and preparation method thereof | |
| CN113571841B (en) | Lithium-sulfur battery composite diaphragm and preparation method thereof | |
| Dong et al. | Photoassisted Li-ion de-intercalation and Niδ+ valence conversion win-win boost energy storage performance in Ni/CdS@ Ni3S2-based Li-ion battery | |
| Chen et al. | An organic-halide perovskite-based photo-assisted Li-ion battery for photoelectrochemical storage | |
| CN113210002A (en) | Cobalt-nitrogen-doped graded porous catalytic material and preparation method and application thereof | |
| CN116003717B (en) | Nitrogen-sulfur doped two-dimensional covalent organic framework material, preparation method thereof, lithium-sulfur battery positive electrode and lithium-sulfur battery | |
| CN112467068A (en) | Battery negative electrode material and preparation method and application thereof | |
| CN109888198B (en) | Metal intercalation molybdenum oxide material and preparation method and application thereof | |
| CN116040611A (en) | Lithium ion battery film negative electrode material, preparation method and application | |
| CN111180705A (en) | Lithium-sulfur battery electrode material with ultralow self-discharge and preparation method thereof | |
| CN116161698A (en) | Zinc-based battery positive electrode material and preparation method and use method thereof | |
| CN113206226B (en) | Double-transition metal carbide compound and preparation method and application thereof | |
| CN110416512B (en) | Based on Bi4Ti3O12Preparation method of @ C/S composite material, composite material and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |