CN114068970B - Light-assisted lithium carbon dioxide battery and preparation method thereof - Google Patents
Light-assisted lithium carbon dioxide battery and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of chemical power supplies, and particularly relates to a light-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 photocatalytic anode is prepared by depositing graphite-phase carbon nitride with photoelectric effect on a conductive carbon nano tube 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 light irradiates from one side of the photocatalytic anode, the anode can absorb photons and generate photoelectrons and holes to promote the discharge and charge reactions of the battery, so that the constructed lithium carbon dioxide battery realizes the cycle efficiency of more than 90% 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 light-assisted lithium carbon dioxide battery and a preparation method thereof.
Background
Lithium carbon dioxide battery with CO 2 Fixing andthe dual function of energy storage provides an economical and viable strategy for addressing both global warming and energy crisis critical environmental issues. In addition, CO is utilized 2 The energy storage device also has good application prospect in aerospace exploration by being used as a positive electrode raw material. Therefore, this energy storage system has attracted more and more research interest in recent years. However, it is limited by the cathode reaction raw material CO 2 The slow kinetic conversion process with solid discharge products, this energy storage system has very poor electrochemical performance and stays in the conceptual phase only. Although researchers have developed a large number of electrocatalysts and soluble redox promoters to address this problem, batteries remain very severely charged and discharged and have poor cycling stability. Further, severe polarization voltages exacerbate side reactions such as electrolyte/electrode degradation, further leading to degradation of battery performance or even complete failure. Considering the important theoretical and practical significance of this battery, it is very important, but challenging, to achieve an efficient and stable lithium carbon dioxide battery system.
Solar energy is well known as an inexhaustible green energy source. Recently, researchers have proposed an attractive photo-assisted catalytic strategy to reduce the polarization of the cell and increase the cycling efficiency. The core of the design of this strategy is to introduce a suitable photocatalyst into the air electrode as a photoelectrode. When irradiation 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. Currently, this design strategy has been successfully applied to lithium ion batteries, zinc ion batteries, lithium air batteries, zinc air batteries, and the like. This strategy may also be desirable for improving the cycle efficiency and cycle life of lithium carbon dioxide batteries.
Disclosure of Invention
The invention aims to provide a light-assisted lithium carbon dioxide battery with high cycle efficiency, long cycle life and good multiplying power performance and a preparation method thereof.
The invention provides a light-assisted lithium carbon dioxide battery which is in the form of a button battery, and comprises 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 photoelectric effect on a carbon nano tube film by an in-situ chemical deposition method;
the electrolyte is one or more of organic solution electrolyte, gel quasi-solid electrolyte, molten salt electrolyte, ionic liquid electrolyte and lithium salt;
the positive electrode protective layer adopts a polymer selective permeable membrane.
Further:
the gel quasi-solid electrolyte includes, but is not limited to, an organic solvent or ionic liquid in which lithium salts are dissolved and a polymer matrix. Wherein the lithium salt is one or more of lithium bis (trifluoromethanesulfonyl) imide, lithium hexafluorophosphate, lithium trifluoromethanesulfonate, lithium bis (trifluoromethanesulfonyl) imidazole, lithium tetrafluoroborate, lithium perchlorate and lithium nitrate; the solvent is one or more of 1, 3-dioxolane, 2-methyl-tetrahydrofuran, 2-dimethoxyethane, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 1-ethyl-3-methylimidazole tetrafluoroborate and 1-ethyl-3-methylimidazole bis (trifluoromethanesulfonyl) imidazole; the polymer matrix is one or more of polyvinylidene fluoride-hexafluoropropylene, polymethyl methacrylate, polyacrylamide and polyurethane.
The polymer selectively permeable membrane is selected from one of colorless transparent polymethylpentene membrane, polyethylene membrane, organosilicon polydimethylsiloxane membrane and paraffin membrane.
The current collectors are common positive and negative current collector materials; the lithium sheet is a general negative electrode lithium sheet material.
Under illumination, the photocatalysis positive electrode can effectively absorb photons with specific energy to generate a large number of photo-generated electron hole pairs, and the photo-generated electrons and the 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 dynamics process of the lithium carbon dioxide battery can be solved. The battery has the advantages of low cost and easy acquisition of synthetic raw materials, simple assembly process, high cycle efficiency, good multiplying power performance, long cycle life and large-scale production and preparation, thereby having wide application prospect.
Specifically, when light is irradiated 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 lithium carbonate and carbon, so that the battery displays discharge voltage exceeding 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 degradation of solid discharge products to effectively reduce the charge overpotential, and the conversion from light energy to chemical energy is realized in the process. Therefore, the photocatalysis anode can absorb photons to generate a large amount 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 light-assisted lithium carbon dioxide battery, which comprises the following specific steps:
(1) Preparing a photocatalysis anode; sequentially cleaning a high-conductivity carbon nano tube film by using ethanol, acetone and deionized water, fully drying, transferring the high-conductivity carbon nano tube film into a nitric acid solution with the volume fraction of 30% -65%, heating the nitric acid solution at 60-140 ℃ for 1-12 hours, taking out the carbon nano tube film after acid treatment, fully cleaning and drying the carbon nano tube film by using deionized water, immersing the hydrophilically treated carbon nano tube film in an aqueous solution containing 0.5-2.0 g/mL guanidine hydrochloride and 1-10 mg/mL polyethylene glycol 4000, treating the carbon nano tube film at 75-85 ℃ for 1-8 hours, taking out the film, spreading the film in a crucible, fully drying the film, and transferring the film to a tube furnace; argon is used as an inert gas source, inert gas is firstly introduced at a flow rate of 100-400 sccm for 10-40 min to remove air, then the gas flow rate is adjusted to 50-200 sccm, the temperature is raised to 500-600 ℃ at a heating rate of 1-20 ℃/min, the heat is preserved for 2-6h for thermal polymerization reaction, and after the reaction is finished, the graphite-phase carbon nitride and carbon nano tube composite film is obtained after cooling to room temperature at a cooling rate of 1-20 ℃/min;
(2) Preparing a gel electrolyte; in a glove box with oxygen and water content lower than 1 ppm, dissolving lithium salt in an organic solvent or ionic liquid, wherein the concentration of the lithium salt is 0.1-2.0M, adding a proper amount of lithium scraps or molecular sieves, and drying to obtain a solution A; polyvinylidene fluoride-hexafluoropropylene and azamethylpyrrolidone were mixed at 1:4-1:5, mixing the materials according to the mass ratio to prepare a solution B; 2-hydroxy-2-methyl-1-phenyl-1-propanone was reacted with ethoxylated trimethylol propane triacrylate at 1: mixing (295-305) in a mass ratio to prepare a solution C, and mixing the solution A, the solution B and the solution C according to (3.8-4.2): (4.8-5.2): (2.8-3.2) mixing and fully stirring to obtain a viscous electrolyte precursor solution; dripping 0.2-0.5. 0.5 mL precursor solution on the diaphragm, uniformly leveling, and uniformly irradiating 10-40 s with ultraviolet light with the wavelength of 365 nm to obtain gel electrolyte;
(3) Assembling a lithium carbon dioxide battery; in a glove box, the anode current collector, the photocatalysis anode obtained in the step (1), the gel electrolyte obtained in the step (2), the lithium sheet cathode, the gasket and the elastic sheet are sequentially placed in a stainless steel button cell mold with a net-shaped anode shell from bottom to top, pressure is applied on a cell tablet press for fixation, and then a layer of protective layer is packaged outside the anode shell, so that the light-assisted lithium carbon dioxide cell is obtained.
The illumination source which can be used in practical test comprises, but is not limited to, xenon lamp, ultraviolet lamp, sunlight and the like, and the illumination power is 10 3 –10 6 W/m 2 。
The invention has the following advantages:
the invention prepares the carbon nano tube composite film of the graphite-phase carbon nitride material by using cheap and easily available raw materials, and constructs the light-assisted lithium carbon dioxide battery with high cycle efficiency and excellent cycle stability by using the carbon nano tube composite film, thus having low preparation cost, simple reaction process and good process repeatability; 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 an anode is improved; the light-assisted lithium carbon dioxide battery has the advantages of high cycle efficiency, long cycle life, good multiplying power performance and the like; the assembled battery exhibits a cycle efficiency of more than 90% under illumination and maintains a cycle efficiency of more than 80% after 100 cycles; the invention has important application prospect in the environment protection field, the energy storage field and the flexible wearable electronic equipment field.
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 photograph 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 a graphite phase carbon nitride composite carbon nanotube film used in example 1 of the present invention.
Fig. 4 is a charge-discharge 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-discharge curve of the lithium carbon dioxide battery constructed in example 1 of the present invention in light and dark.
Fig. 6 is a charge-discharge curve of the lithium carbon dioxide battery constructed in example 1 of the present invention when operated with different current densities and capacities under light.
Fig. 7 is a deep discharge curve of the lithium carbon dioxide battery constructed in example 1 of the present invention under light and dark.
Fig. 8 is a scanning electron micrograph of a photocatalytic anode after discharging and charging under light of a lithium carbon dioxide battery constructed in example 1 of the present invention.
Fig. 9 is a charge-discharge curve of the lithium carbon dioxide battery constructed in example 2 of the present invention in light and dark.
Fig. 10 is a long-term cyclic charge-discharge curve and energy efficiency of the lithium carbon dioxide battery constructed in example 3 of the present invention in light and dark.
Fig. 11 is a long-term cyclic charge-discharge curve 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-discharge curve of the lithium carbon dioxide battery constructed in example 5 of the present invention in light and darkness.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and specific embodiments, but the specific details of the embodiments are only for the purpose of illustrating the invention, and are not to be construed as limiting the general technical scope of the invention, and some insubstantial additions and modifications, such as simple changes or substitutions of technical features with the same or similar effects, which do not depart from the scope of the invention as disclosed herein, are considered to be within the scope of the invention.
Example 1
Sequentially cleaning a high-conductivity carbon nano tube film by using ethanol, acetone and deionized water for 10 min, drying at 60 ℃ in a vacuum drying oven, transferring the high-conductivity carbon nano tube film into a concentrated nitric acid solution for treatment at 120 ℃ for 3h, taking out the carbon nano tube film after acid treatment, fully cleaning and drying by using deionized water, fully immersing the hydrophilic carbon nano tube film in an aqueous solution containing 1.0 g/mL guanidine hydrochloride and 2 mg/mL polyethylene glycol 4000 for treatment at 80 ℃ for 3h, tiling the film in a crucible, fully drying and transferring the film into a tube furnace. Argon is introduced at the flow rate of 200 sccm for 20 min, the gas flow rate is regulated to 100sccm, then a heating program is started, the temperature is raised to 600 ℃ at the speed of 4 ℃/min, the temperature is kept for 4h, and the graphite-phase carbon nitride composite carbon nano tube film is obtained after cooling to the room temperature at the cooling speed of 1 ℃/min. The carbon nanotube film adopted in the experiment has a loose and porous interweaved network structure (figure 2), and the prepared graphite-phase carbon nitride composite carbon nanotube film still maintains the loose and porous interweaved network structure, and a carbon nitride layer is uniformly deposited on the surface of a single carbon nanotube (figure 3). The porous interweaved carbon nanotube network is favorable for gas diffusion, substance delivery and deposition of discharge products, and the interface of the carbon nanotube and the carbon nitride is favorable for rapid separation and transmission of photo-generated carriers.
In a glove box with oxygen and water content lower than 1 ppm, dissolving lithium bistrifluoromethane sulfonyl imide in 1-ethyl-3-methylimidazole tetrafluoroborate, adding a proper amount of molecular sieve, and drying 12h to obtain a solution A, wherein the lithium salt concentration is 1.0M; mixing polyvinylidene fluoride-hexafluoropropylene and nitrogen methyl pyrrolidone according to a mass ratio of 1:4 to prepare a solution B; 2-hydroxy-2-methyl-1-phenyl-1-propanone was reacted with ethoxylated trimethylol propane triacrylate at 1:300 mass ratio, and preparing into solution C; solution a, solution B, solution C were mixed with 4:5:3, mixing and fully stirring the mixture to obtain a precursor solution of the gel electrolyte; and (3) dripping 0.3. 0.3 mL precursor solution on the glass fiber diaphragm, uniformly irradiating the precursor solution 20 s by using an ultraviolet lamp with the wavelength of 365 nm after the solution is fully permeated and uniformly leveled, and curing to obtain the gel electrolyte.
In a glove box, sequentially placing a positive current collector, a photocatalytic positive electrode, a gel electrolyte, a lithium sheet, a gasket and an elastic sheet into a CR2032 stainless steel button battery mold with a net-shaped positive electrode shell from bottom to top, fixing a battery on a battery tablet press, and packaging a layer of polymethylpentene film outside the net-shaped positive electrode shell as a positive electrode protection layer to obtain the light-assisted lithium carbon dioxide battery.
The assembled battery was removed from the glove box and rapidly transferred to a clear glass test bottle, into which high purity carbon dioxide was continuously introduced at a flow rate of 100sccm for 1 hour to replace the residual air in the bottle. For the test under the illumination condition, the photocatalysis positive electrode is vertically irradiated by using a 350W xenon lamp, and the illumination intensity is 40 mW/cm 2 . For testing in dark conditions, the test vials were placed in a light-protected environment. After the cell had stabilized at an open circuit voltage of 3h, the test procedure was started after adjusting the carbon dioxide flow rate to 20 sccm.
The prepared lithium carbon dioxide battery has lower charge and discharge overpotential and excellent energy efficiency, and the lithium carbon dioxide battery is irradiated with 0.02 mA cm -2 The voltage levels during discharging and charging can reach 3.24V and 3.29V (FIG. 4), respectively, and can reach 0.02 mAh cm -2 Is charged and discharged in stable circulation by the cut-off capacity of (2)100 turns (FIG. 5), while also achieving excellent rate capability (FIG. 6) and up to 15.77 mAh cm -2 Is shown (fig. 7). The catalytic anode before and after charge and discharge under illumination was observed by using a field emission scanning electron microscope (SEM, hitachi FESEM S4800, operating voltage 5 kV), and research shows that a large amount of granular discharge products are generated on the catalytic anode after discharge, and the discharge products can be completely decomposed after charge (fig. 7), indicating that the battery has good cycle reversibility.
Example 2
Sequentially cleaning the high-conductivity carbon nano tube film by using ethanol, acetone and deionized water for 10 min, drying at 60 ℃ in a vacuum drying oven, transferring the high-conductivity carbon nano tube film into a nitric acid solution with the volume fraction of 65%, carrying out reflux treatment at 120 ℃ for 3h, taking out the carbon nano tube film after acid treatment, fully cleaning and drying by using deionized water, fully immersing the hydrophilic carbon nano tube film in an aqueous solution containing 0.5 g/mL guanidine hydrochloride and 1 mg/mL polyethylene glycol 4000, carrying out treatment at 80 ℃ for 6h, flatly laying the film in a crucible, and transferring the film into a tubular furnace after full drying. Argon is introduced at a flow rate of 100sccm for 20 min to remove air, the flow rate is regulated to 100sccm, a heating program is started, the temperature is raised to 600 ℃ at a speed of 10 ℃/min and is kept for 4h, and the graphite-phase carbon nitride composite carbon nano tube film is obtained after cooling to room temperature at a cooling speed of 10 ℃/min.
In a glove box with oxygen and water content lower than 1 ppm, dissolving lithium bistrifluoromethane sulfonyl imide in tetraethylene glycol dimethyl ether, adding a proper amount of molecular sieve to obtain solution A, and drying the solution A, wherein the concentration of lithium salt is 1.0M; mixing polyvinylidene fluoride-hexafluoropropylene and nitrogen methyl pyrrolidone according to a mass ratio of 1:4 to prepare a solution B; 2-hydroxy-2-methyl-1-phenyl-1-propanone was reacted with ethoxylated trimethylol propane triacrylate at 1:300 mass ratio, and preparing into solution C; solution a, solution B, solution C were mixed with 4:5:3, mixing and fully stirring the mixture to obtain gel electrolyte precursor solution; and (3) dripping 0.3-mL precursor solution on the glass fiber diaphragm, uniformly radiating the precursor solution 20 s by an ultraviolet lamp with the wavelength of 365 nm after the solution fully permeates the diaphragm and is uniformly leveled, and thus obtaining the gel electrolyte.
In a glove box, sequentially placing a positive current collector, a photocatalytic positive electrode, a gel electrolyte, a lithium sheet, a gasket and an elastic sheet into a CR2032 stainless steel button battery mold with a net-shaped positive electrode shell from bottom to top, fixing a battery on a battery tablet press, and packaging a layer of polymethylpentene film outside the net-shaped positive electrode shell as a positive electrode protection layer to obtain the light-assisted lithium carbon dioxide battery.
The assembled battery was quickly removed from the glove box and transferred to a transparent test flask, into which high purity carbon dioxide was continuously introduced at a flow rate of 100sccm to replace the residual air in the flask. For the test under the illumination condition, a 500W xenon lamp is utilized to vertically irradiate the photocatalytic anode through a test bottle, and the illumination intensity is controlled to be 40W/cm 2 . For testing in dark conditions, the test vials were placed in the dark. And after the battery is stabilized for 3 hours under the open circuit voltage, the flow speed of the carbon dioxide is adjusted to be 20 sccm, and a test procedure is started. The prepared lithium carbon dioxide battery has lower charge and discharge overpotential and excellent energy efficiency, and the lithium carbon dioxide battery is irradiated with 0.02 mA cm -2 The voltage plateau can reach 2.90V and 3.03V when discharging and charging, respectively (fig. 9).
Example 3
The high-conductivity carbon nano tube film is sequentially cleaned by ethanol, acetone and deionized water for 10 min and dried at 60 ℃, then the high-conductivity carbon nano tube film is transferred into a concentrated nitric acid solution with the volume fraction of 60 percent and is treated at 60 ℃ for 3h, the carbon nano tube film after acid treatment is taken out and is fully cleaned and dried by deionized water, then the hydrophilic carbon nano tube film is immersed in an aqueous solution containing guanidine hydrochloride of 1.0 g/mL and polyethylene glycol 4000 of 2 mg/mL for 3h at 80 ℃, and then the film is spread in a crucible and is transferred into a tube furnace after being fully dried. Argon gas is used as an inert gas source, inert gas is introduced at a flow rate of 200 sccm for 20 min to remove air, then the gas flow rate is adjusted to 100sccm, the temperature is raised to 600 ℃ at a heating rate of 4 ℃/min, the thermal polymerization reaction is carried out for 4h, and after the reaction is finished, the graphite-phase carbon nitride composite carbon nano tube film is cooled to room temperature at a cooling rate of 1 ℃/min.
In a glove box with oxygen and water content lower than 1 ppm, dissolving lithium bistrifluoromethane sulfonyl imide in dimethyl sulfoxide, wherein the concentration of lithium salt is 1.0M, adding a proper amount of molecular sieve, and drying to obtain a solution A; mixing polyvinylidene fluoride-hexafluoropropylene and nitrogen methyl pyrrolidone according to a mass ratio of 1:4 to prepare a solution B; 2-hydroxy-2-methyl-1-phenyl-1-propanone was reacted with ethoxylated trimethylol propane triacrylate at 1:300 mass ratio, and preparing into solution C; solution a, solution B, solution C were mixed with 4:5:3, mixing and fully stirring the mixture to obtain a precursor solution of the gel electrolyte; and (3) dripping 0.3-mL precursor solution on the glass fiber diaphragm, uniformly radiating the precursor solution 20 s by an ultraviolet lamp with the wavelength of 365 nm after the solution fully permeates the diaphragm and is uniformly leveled, and thus obtaining the gel electrolyte.
In a glove box, sequentially placing a positive current collector, a photocatalytic positive electrode, a gel electrolyte, a lithium sheet, a gasket and an elastic sheet into a CR2032 stainless steel button battery mold with a net-shaped positive electrode shell from bottom to top, fixing a battery on a battery tablet press, and packaging a layer of polyethylene film outside the net-shaped positive electrode shell as a positive electrode protection layer to obtain the light-assisted lithium carbon dioxide battery.
The assembled battery was removed from the glove box and quickly transferred to a glass test flask, to which high purity carbon dioxide was continuously fed at a flow rate of 100 sccm. For the test under illumination conditions, the photocatalytic anode was irradiated vertically with a 500W uv lamp. For testing in dark conditions, glass test vials were placed in a light-protected environment. After the cell had stabilized 3h at open circuit voltage, the test procedure was started after the carbon dioxide flow rate was adjusted to 20 sccm. The prepared lithium carbon dioxide battery has higher cycle stability and can be used for preparing a lithium carbon dioxide battery with the concentration of 0.02 mA cm under illumination -2 And a current density of 0.02 mAh cm -2 Is charged and discharged for 100 cycles (fig. 10).
Example 4
Sequentially cleaning a carbon nano tube film by using ethanol, acetone and deionized water for 10 min, drying at 60 ℃ in a vacuum drying oven, transferring the carbon nano tube film into a nitric acid solution with the volume fraction of 60% to be treated at 80 ℃ for 6h, taking out the carbon nano tube film after acid treatment, fully cleaning and drying by using 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 to be treated at 80 ℃ for 3h, taking out the film, spreading the film in a crucible, fully drying the film, and transferring the film to a tubular furnace. And (3) introducing argon at the flow rate of 200 sccm for 20 min, adjusting the flow rate of the argon to 100sccm, heating to 550 ℃ at the speed of 1 ℃/min, preserving heat for 4h, and cooling to room temperature at the cooling speed of 1 ℃/min to obtain the graphite-phase carbon nitride composite carbon nano tube film.
In a glove box with oxygen and water content lower than 1 ppm, dissolving lithium trifluoromethane sulfonate in dimethyl sulfoxide, adding a proper amount of molecular sieve to obtain solution A, and fully drying to obtain lithium salt with concentration of 1.0M; mixing polyvinylidene fluoride-hexafluoropropylene and nitrogen methyl pyrrolidone according to a mass ratio of 1:4 to prepare a solution B; 2-hydroxy-2-methyl-1-phenyl-1-propanone was reacted with ethoxylated trimethylol propane triacrylate at 1:300 mass ratio, and preparing into solution C; solution a, solution B, solution C were mixed with 4:5:3, mixing and fully stirring the mixture to obtain a precursor solution of the gel electrolyte; and (3) dripping 0.2. 0.2 mL precursor solution on the polypropylene diaphragm, and uniformly radiating the precursor solution 20 s by an ultraviolet lamp with the wavelength of 365 nm after the solution fully permeates the diaphragm and is uniformly leveled to obtain the gel electrolyte.
In a glove box, sequentially placing a positive current collector, a photocatalytic positive electrode, a gel electrolyte, a lithium sheet, a gasket and an elastic sheet into a CR2032 stainless steel button battery mold with a net-shaped positive electrode shell from bottom to top, fixing on a battery tablet press, and packaging a paraffin film outside the positive electrode shell as a positive electrode protection layer to obtain the light-assisted lithium carbon dioxide battery.
The assembled battery was removed from the glove box and rapidly transferred to a clear glass test flask, to which high purity carbon dioxide was continuously fed at a flow rate of 100 sccm. For the test under the illumination condition, a 1000W xenon lamp is used for vertically irradiating the photocatalytic anode, and the illumination intensity is controlled to be 100 mW/cm 2 . For testing in dark conditions, the test vials were placed in a light-protected environment. To be at the batteryThe open circuit voltage was stabilized at 3h, and the carbon dioxide flow rate was adjusted to 20 sccm, after which the test procedure was started. The prepared lithium carbon dioxide battery has lower charge and discharge overpotential and excellent energy efficiency, and the lithium carbon dioxide battery is irradiated with 0.02 mA cm -2 And a current density of 0.02 mAh cm -2 Is charged and discharged for 100 cycles (fig. 11) under the cut-off capacity of (c).
Example 5
The high-conductivity carbon nano tube film is sequentially cleaned by ethanol, acetone and deionized water for 10 min and dried in a vacuum drying oven at 60 ℃, then the high-conductivity carbon nano tube film is transferred into a nitric acid solution with the volume fraction of 30 percent and treated for 3h at 80 ℃, the hydrophilic carbon nano tube film is completely immersed in an aqueous solution containing guanidine hydrochloride of 1.5 g/mL and polyethylene glycol 4000 of 3 mg/mL for 3h at 80 ℃, and then the film is spread in a crucible, fully dried and then transferred into a tubular furnace. Argon is introduced at the flow rate of 200 sccm for 20 min, the gas flow rate is regulated to 100sccm, the temperature is raised to 550 ℃ at the speed of 4 ℃/min, the temperature is kept for 4h, and the graphite phase carbon nitride composite carbon nano tube film is obtained after cooling to the room temperature at the cooling speed of 1 ℃/min.
In a glove box with oxygen and water content lower than 1 ppm, dissolving lithium perchlorate in a mixed solvent of 1-ethyl-dimethyl imidazole tetrafluoroborate and dimethyl sulfoxide (volume fraction ratio is 1:1), wherein the concentration of lithium salt is 0.5 and M, adding a proper amount of molecular sieve, and fully drying to obtain a solution A; mixing polyvinylidene fluoride-hexafluoropropylene and nitrogen methyl pyrrolidone according to a mass ratio of 1:4 to prepare a solution B; 2-hydroxy-2-methyl-1-phenyl-1-propanone was reacted with ethoxylated trimethylol propane triacrylate at 1:300 mass ratio, and preparing into solution C; solution a, solution B, solution C were mixed with 4:5:3, mixing and fully stirring the mixture to obtain a precursor solution of the gel electrolyte; and (3) taking 0.1 mL precursor solution on the polypropylene diaphragm, and uniformly radiating the precursor solution 30 s by an ultraviolet lamp with the wavelength of 365 nm after the solution fully permeates the diaphragm and is uniformly leveled, thus obtaining the gel electrolyte.
In a glove box, a positive electrode current collector, a photocatalysis positive electrode, a gel electrolyte, a lithium sheet, a gasket and an elastic sheet are sequentially arranged on the positive electrode from bottom to top, wherein the positive electrode has 7 mmIn the CR2032 button battery with the aperture, the battery is fixed by applying pressure on a battery tablet press, and a colorless transparent ethylene film is encapsulated outside a net-shaped positive electrode shell to serve as a positive electrode protection layer, so that the light-assisted lithium carbon dioxide battery is obtained. The assembled battery was quickly removed from the glove box and transferred to a clear glass test flask, into which high purity carbon dioxide was continuously introduced at a flow rate of 100sccm to replace air in the flask. For the test under illumination, a 500W ultraviolet lamp is utilized to vertically irradiate the photocatalysis positive electrode through a transparent test bottle, and the illumination intensity is controlled to be 60 mW/cm 2 . For testing in dark conditions, the test vials were placed in a light-protected environment. After the cell had stabilized at an open circuit voltage of at least 3h, the test procedure was started after adjusting the carbon dioxide flow rate to 20 sccm. The prepared lithium carbon dioxide battery has lower charge and discharge overpotential and excellent energy efficiency, and the lithium carbon dioxide battery is irradiated with 0.02 mA cm -2 A higher surface capacity is achieved when discharging with a cut-off voltage of 1.5V (fig. 12).
Claims (4)
1. A photo-assisted lithium carbon dioxide battery is a button battery and is characterized by comprising a negative current collector, a lithium sheet negative electrode, an electrolyte, a photo-catalytic positive electrode, a positive current collector with an optical window and a positive protective layer; wherein:
the photocatalysis anode is prepared by depositing graphite phase carbon nitride material with photoelectric effect on a conductive carbon nano tube film by an in-situ chemical deposition method;
the electrolyte is gel quasi-solid electrolyte or a mixture of gel quasi-solid electrolyte and lithium salt;
the positive electrode protective layer adopts a macromolecule selective permeable membrane.
2. The light-assisted lithium carbon dioxide cell of claim 1, wherein the gel quasi-solid electrolyte consists of an organic solvent or ionic liquid with dissolved lithium salt and a polymer matrix; wherein the lithium salt is one or more of lithium bis (trifluoromethanesulfonyl) imide, lithium hexafluorophosphate, lithium trifluoromethanesulfonate, lithium bis (trifluoromethanesulfonyl) imidazole, lithium tetrafluoroborate, lithium perchlorate and lithium nitrate; the solvent is one or more of 1, 3-dioxolane, 2-methyl-tetrahydrofuran, 2-dimethoxyethane, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 1-ethyl-3-methylimidazole tetrafluoroborate and 1-ethyl-3-methylimidazole bis (trifluoromethanesulfonyl) imidazole; the polymer matrix is one or more of polyvinylidene fluoride-hexafluoropropylene, polymethyl methacrylate, polyacrylamide and polyurethane.
3. The light-assisted lithium carbon dioxide cell of claim 1, wherein the polymeric permselective membrane is selected from one of a colorless transparent polymethylpentene membrane, a polyethylene membrane, a silicone polydimethylsiloxane membrane, and a paraffin membrane.
4. A method for preparing a light-assisted lithium carbon dioxide battery according to any one of claims 1 to 3, comprising the following steps:
(1) Preparation of photocatalytic anode
Sequentially cleaning a high-conductivity carbon nano tube film by using ethanol, acetone and deionized water, fully drying, transferring the high-conductivity carbon nano tube film into a concentrated nitric acid solution with the volume fraction of 60% -65%, heating at 80-140 ℃ for 1-4 h, immersing the hydrophilically treated carbon nano tube film into an aqueous solution containing 0.5-2.0 g/mL guanidine hydrochloride and 1-10 mg/mL polyethylene glycol 4000 for 2.5-3.5 h at 75-85 ℃, taking out the film, spreading the film in a crucible, fully drying, and transferring the film into a tubular furnace; argon is used as an inert gas source, inert gas is firstly introduced at a flow rate of 100-400 sccm for 10-40 min to remove air, then the gas flow rate is adjusted to 50-200 sccm, the temperature is raised to 500-600 ℃ at a heating rate of 1-20 ℃/min, the thermal polymerization reaction is carried out for 2-6h, and after the reaction is finished, the graphite-phase carbon nitride and carbon nano tube composite film is obtained after cooling to room temperature at a cooling rate of 1-20 ℃/min and is used as a photocatalysis anode;
(2) Preparation of gel electrolyte
In a glove box with oxygen and water content lower than 1 ppm, dissolving lithium salt in an organic solvent or ionic liquid, wherein the concentration of the lithium salt is 0.1-2.0M, adding a proper amount of lithium scraps or molecular sieves, and drying to obtain a solution A; polyvinylidene fluoride-hexafluoropropylene and azamethylpyrrolidone were mixed at 1:4-1:5, mixing the materials according to the mass ratio to prepare a solution B; 2-hydroxy-2-methyl-1-phenyl-1-propanone was reacted with ethoxylated trimethylol propane triacrylate at 1: mixing the materials (295-305) in a mass ratio to prepare a solution C; solution A, solution B, solution C were mixed (3.8-4.2): (4.8-5.2): (2.8-3.2) mixing and fully stirring to obtain a viscous electrolyte precursor solution; dripping 0.2-0.5. 0.5 mL precursor solution on a glass fiber or polypropylene diaphragm, and uniformly radiating 10-40 s by ultraviolet light with the wavelength of 365 nm after the precursor solution is fully and uniformly leveled to prepare a gel electrolyte;
(3) Assembly of lithium carbon dioxide battery
In a glove box, the anode current collector, the photocatalysis anode obtained in the step (1), the gel electrolyte obtained in the step (2), the lithium sheet cathode, the gasket and the elastic sheet are sequentially placed in a stainless steel button cell mold with a net-shaped anode shell from bottom to top, pressure is applied on a cell tablet press for fixation, and then a layer of protective layer is packaged outside the anode shell, so that the light-assisted lithium carbon dioxide cell is obtained.
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