CN111755647A - Preparation method of lithium-air battery composite diaphragm - Google Patents
Preparation method of lithium-air battery composite diaphragm Download PDFInfo
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- CN111755647A CN111755647A CN201910236315.9A CN201910236315A CN111755647A CN 111755647 A CN111755647 A CN 111755647A CN 201910236315 A CN201910236315 A CN 201910236315A CN 111755647 A CN111755647 A CN 111755647A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
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- 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 discloses a preparation method of a lithium-air battery composite diaphragm, which comprises the following steps: (1) sequentially carrying out soaking, washing, drying, mechanical treatment, carbonization, activation, secondary washing and final drying on the areca residue to obtain porous carbon; (2) mixing porous carbon, a binder and an organic solvent to prepare a membrane casting solution, and coating the membrane casting solution on a pre-installed diaphragm to prepare a composite membrane; (3) and (3) preparing the lithium-air battery by using the composite membrane prepared in the step (2). The invention successfully prepares porous carbon with large specific surface area and large pore volume by using the waste betel nut residues, and uses the porous carbon in the modified coating of the lithium-air battery diaphragm, thereby preparing the lithium-air battery composite diaphragm with excellent performance and the lithium-air battery using the composite diaphragm.
Description
Technical Field
The invention relates to a preparation method of a composite diaphragm of a lithium-air battery, belonging to the technical field of lithium-air batteries.
Background
Metal-air batteries are expected to outperform the most advanced lithium ion batteries as potential power sources, and have recently attracted considerable attention due to their potential high energy density. Among them, lithium air batteries have low cost, no pollution, and high energy density (5200W h kg)-1) And good safety properties are considered to be promising electrochemical energy systems. However, as the main discharge product of most lithium-air batteries, Li2O2Difficult to dissolve in almost all known electrolytes and very poor conductivity. These characteristics imply severe electrochemical polarization and higher decomposition voltages, which cause many obstacles in the application of lithium air batteries. For exampleUndecomposed Li2O2May result in a rapid drop in battery capacity. Discharge product Li2O2The precipitation of the lithium-air battery leads to the blockage of an air loop, and the discharge can not be continued, so that the discharge specific capacity of the lithium-air battery is greatly reduced.
The conductivity of the separator is inversely proportional to the thickness, but the strength of the separator is directly proportional to the thickness. The existing commonly used double-layer composite diaphragm has higher strength and rich pore structures by sacrificing the conductivity, and the strength of the diaphragm cannot be improved by modifying an air cathode. The coating layer with the porous carbon is coated on the diaphragm, so that the strength of the diaphragm can be improved, the capability of accommodating and decomposing discharge products of the air cathode can be supplemented, and the lithium conducting capability of the diaphragm cannot be sacrificed.
Every year, a large amount of areca nuts are consumed in the areas of Hunan and Hainan, and accordingly, a large amount of areca nut residues are generated, which causes great damage to the environment. The betel nut is a biological material rich in carbon and nitrogen, and the nitrogen-doped porous carbon with large specific surface area and large pore volume can be obtained by carbonization and activation. The large specific surface area can provide more active sites, and is beneficial to the decomposition of discharge products. The large pore volume can contain more discharge products, and is beneficial to improving the discharge specific capacity of the lithium air battery.
Disclosure of Invention
The invention aims to provide a method for manufacturing a composite diaphragm of a lithium-air battery. The porous nitrogen-doped porous carbon with large specific surface area is prepared by taking areca residue as a carbon source and is coated on a pre-installed diaphragm as a functional coating.
The invention is realized by the following technical scheme:
the invention provides a method for manufacturing a lithium-air battery composite diaphragm, which comprises the following steps:
step one, taking areca residue, soaking the areca residue in deionized water for 1 to 3 days, then washing the areca residue with the deionized water for 2 to 5 times, and then drying the areca residue in an oven at the temperature of between 60 and 150 ℃ for 6 to 24 hours;
step two, mechanically treating the dried areca residue obtained in the step one to obtain easily carbonized areca residue;
step three, putting the easy-carbonized areca-nut residues obtained in the step two into a tubular electric furnace, introducing protective gas, heating to 800 ℃ at the heating rate of 1-10 ℃/min, and carrying out heat preservation and calcination for 1-4 h to obtain carbonized areca-nut residues;
step four, grinding the carbonized areca-nut residues obtained in the step three and an activating agent into powder in a mortar according to the mass ratio of 1:0.2-5, putting the powder into a tubular electric furnace, introducing protective gas, heating to 400-1000 ℃ at the heating rate of 1-10 ℃/min, and carrying out heat preservation and calcination for 2-6 h to obtain activated areca-nut residues;
step five, washing the activated areca residue obtained in the step four in an acid solution for 3-5 times, then continuing to wash in deionized water for 2-4 times, and then drying in an oven at 80-150 ℃ for 6-48 h to obtain porous carbon;
step six, mixing an organic solvent, a high molecular organic substance and the porous carbon obtained in the step five according to a mass ratio of 5-20: 1: 0.05-0.3, heating and stirring for 6-36 h in an oil bath pan at 50-140 ℃, and standing for 6-24 h in an oven at 50-100 ℃ to obtain a casting solution;
step seven, coating the casting solution obtained in the step six on a pre-installed diaphragm, soaking the pre-installed diaphragm coated with the casting solution in a mixed coagulating bath for 6-48 h, and then putting the pre-installed diaphragm into an oven at 50-120 ℃ for drying for 12-48 h to obtain the lithium-air battery composite diaphragm;
and step eight, sequentially packaging the cathode of the lithium-air battery, the composite diaphragm of the lithium-air battery obtained in the step seven, the electrolyte and the metal lithium sheet in an anhydrous and oxygen-free environment to obtain the lithium-air battery.
Preferably, the mechanical treatment in the second step is one or more of ball milling, shearing and extrusion.
Preferably, the easy-carbonized areca residue obtained in the step two is filiform, strip-shaped, granular or powdery.
Preferably, the protective gas in step three and step four is one of argon, nitrogen or helium.
As a preferred methodIn the fourth step, the activating agent is KOH, KCl or FeCl3、Fe2O3Or ZnCl2One kind of (1).
Preferably, the acid solution in the fifth step is one of sulfuric acid, hydrochloric acid or nitric acid.
Preferably, in the sixth step, the polymer organic substance is one or more of PVDF, PTFE, PEI, PVDF-HFP, and HDPE, and the organic solvent is one of DMF, DMAC, and NMP.
Preferably, the pre-installed diaphragm in the seventh step is one of a glass fiber membrane, a PP membrane, a PE membrane, a PEI membrane, a PVDF membrane, and a PVDF-HFP membrane, and the mixed coagulation bath is a blended solution obtained by blending an organic solvent and deionized water in a mass ratio of 0-4:1, wherein the organic solvent is the same as the organic solvent selected in the sixth step.
Preferably, the coating mode in the seventh step is one of spraying, brushing and blade coating, and the coating thickness is 10-40 μm.
Preferably, the cathode of the lithium-air battery in the step eight is prepared by coating a blend of a carbon material, a binder and NMP on foamed nickel or carbon paper, wherein the blending mass ratio of the carbon material, the binder and the NMP is 1: 0.1-0.3: 4-20, wherein the carbon material is one of Super P, acetylene black and Ketjen black, and the binder is PVDF or PTFE; the electrolyte consists of lithium salt and solvent, wherein the lithium salt is selected from LiClO4、LiTFSI、LiNO3、LiFSI、LiCF3SO3、LiPF6The solvent is one or more selected from dimethyl sulfoxide, ethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 1-ethyl-3-methyl tetrafluoroborate imidazole and N, N-dimethylformamide.
The innovation points of the invention are as follows:
the waste betel nut residues are used as a carbon source to prepare porous carbon with large specific surface area and large pore volume, and further the lithium-air battery composite diaphragm is modified to prepare the lithium-air battery with excellent performance.
Compared with the prior art, the invention has the following beneficial effects.
1. The porous carbon is prepared by taking the areca residue as a carbon source and is applied to the preparation of the lithium-air battery composite diaphragm. The betel nut dregs are common wastes in Hunan and Hainan areas, and cause serious damage to the environment. The use of betel nut dregs as a carbon source is an action of changing waste into valuable and is beneficial to environmental protection.
2. The porous carbon prepared from the areca residue is loose and porous, has large specific surface area, large pore volume and good electrochemical performance, is prepared into a coating to be coated on the diaphragm, can improve the strength of the diaphragm on the premise of not sacrificing the conductive performance of the diaphragm, and simultaneously supplements the capacity of the lithium-air battery cathode for containing and decomposing discharge products.
Detailed Description
The present invention will be described in further detail with reference to the following embodiments, which are illustrative only and not limiting, and the scope of the present invention is not limited thereby.
Drawings
Fig. 1 is a scanning electron microscope image of porous carbon prepared from betel nut residues and used for a lithium-air battery composite diaphragm coating.
Example 1: selecting 20 g of areca residue, firstly soaking in deionized water for 1 day, then washing in deionized water for 3 times, drying in an oven at 80 ℃ for 12 hours, then cutting the areca residue into filaments with the diameter of about 3 mm, putting the filaments into a tubular electric furnace in an argon environment, and starting to heat up. The temperature rise speed is 3 ℃/min, the temperature is raised to 400 ℃, and the carbonized material is taken out after heat preservation and calcination are carried out for 2 h. 10 g of carbonized material was ground to a powder by blending with 30 g of KOH. And (3) placing the ground blended powder into an argon environment tubular electric furnace, continuously heating up to 700 ℃ at the heating rate of 5 ℃/min, keeping the temperature, calcining for 3 h, and taking out the activated material. And (3) washing the activated material with hydrochloric acid and deionized water respectively for 3 times, and drying in an oven at 100 ℃ for 24 hours to obtain dry porous carbon powder.
0.4 g of porous carbon powder, 2 g of PVDF granules, are dissolved in 25 g of DMAC and heated with stirring in an oil bath at 80 ℃ for 12 h. Standing in a 70 ℃ oven for 12 h to obtain the required membrane casting solution, and coating the obtained membrane casting solution on a glass fiber membrane by a scraper, wherein the coating thickness is 10 mu m. The coated glass fiber membrane was soaked in a 25% by mass aqueous DMAC solution for 12 h and then dried in an oven at 80 ℃ for 24 h. The finally obtained separator was die-cut into circular sheets with a diameter of 19 mm for use.
0.8 g of Super P, 0.2 g of PVDF and 10 g of NMP are mixed and ground to obtain slurry, the slurry is coated on a foam nickel screen with the diameter of 14 mm by a painting brush to obtain a battery cathode, and the coating amount is 0.5 mg cm-2. And dissolving 0.5M LiTFSI in tetraethylene glycol dimethyl ether in a glove box in an argon environment to prepare a required electrolyte, and sequentially packaging the battery cathode, the obtained circular membrane, the electrolyte and a lithium sheet to obtain the lithium-air battery.
The carbon material prepared in this example had a specific surface area of 1381 m2g-1Pore volume of 0.63 cm3g-1. The tensile strength of the composite diaphragm of the lithium-air battery prepared in the embodiment is 20 MPa, the tensile strength of the common glass fiber membrane is only 5 MPa, and the lithium-air battery prepared in the embodiment and the lithium-air battery using the common glass fiber membrane are subjected to charge and discharge tests under the voltage range of 2-4.5V. When not limited, the dischargeable specific capacity of the lithium-air battery prepared in the embodiment is 14325 mA h g-1The specific discharge capacity of the lithium-air battery using the common glass fiber membrane is 9783 mA h g-1(ii) a Limiting the specific capacity to 500 mA hg-1In the meantime, the lithium-air battery prepared in the embodiment can be cycled for 49 cycles, the maximum overpotential in the cycling process is 1.6V, the lithium-air battery using the common glass fiber membrane can be cycled for 21 cycles, and the maximum overpotential in the cycling process is 2.3V.
Example 2: selecting 20 g of areca residue, firstly soaking in deionized water for 2 days, then washing in deionized water for 4 times, drying in a 70 ℃ oven for 18 hours, then cutting into thin strips with the diameter of about 3 mm, putting into a tubular electric furnace in a nitrogen environment, and starting to heat up. The temperature rise speed is 5 ℃/min, the temperature is raised to 500 ℃, and the carbonized material is taken out after heat preservation and calcination are carried out for 3 h. 10 g of the carbonized material was blended with 20 g of KCl and ground into powder. And (3) placing the ground blended powder into a nitrogen environment tubular electric furnace, continuously heating up to 900 ℃ at the heating rate of 5 ℃/min, keeping the temperature, calcining for 3 h, and taking out the activated material. And (3) washing the activated material with nitric acid and deionized water respectively for 3 times, and drying in an oven at 100 ℃ for 36 hours to obtain dry porous carbon powder.
0.5 g of porous carbon powder and 2.5 g of PVDF pellets were dissolved in 20 g of DMAC and heated in an oil bath at 80 ℃ with stirring for 12 hours. Standing in an oven at 80 ℃ for 12 h to obtain the required membrane casting solution, and blade-coating the obtained membrane casting solution on a PVDF-HFP membrane by using a scraper, wherein the blade-coating thickness is 20 mu m. The coated glass fiber membrane was soaked in a 50% by mass aqueous DMAC solution for 12 h and then dried in an oven at 80 ℃ for 24 h. The finally obtained separator was die-cut into circular sheets with a diameter of 19 mm for use.
0.8 g of Super P, 0.2 g of PVDF and 10 g of NMP are mixed and ground to obtain slurry, the slurry is coated on a foam nickel screen with the diameter of 14 mm by a painting brush to obtain a battery cathode, and the coating amount is 0.5 mg cm-2. In a glove box under argon atmosphere, 0.5M LiTFSI and 0.5M LiClO were mixed4Dissolving the electrolyte in dimethyl sulfoxide to prepare the required electrolyte, and sequentially packaging the battery cathode, the obtained circular diaphragm, the electrolyte and the lithium sheet to obtain the lithium-air battery.
The carbon material prepared in this example had a specific surface area of 1782 m2g-1Pore volume of 0.84 cm3g-1. The tensile strength of the composite diaphragm of the lithium-air battery prepared in the embodiment is 53 MPa, the tensile strength of the common PVDF-HFP diaphragm is 46 MPa, and the lithium-air battery prepared in the embodiment and the lithium-air battery using the common PVDF-HFP diaphragm are subjected to charge and discharge tests under the voltage range of 2-4.5V. Without being limited to capacity, the dischargeable specific capacity of the lithium-air battery prepared by the embodiment is 19378 mAh g-1And the specific dischargeable capacity of the lithium-air battery using the common PVDF-HFP diaphragm is 12519 mA h g-1(ii) a The specific capacity is limited to 500 mA h g-1Meanwhile, the lithium-air battery prepared in the present example can be cycled for 59 cycles, the maximum overpotential during cycling is 1.5V, and the lithium-air battery using the common PVDF-HFP separator can be cycled for 32 cycles, the maximum overpotential during cycling is 2.1V.
Example 3: selecting 20 g of areca residue, firstly soaking in deionized water for 1 day, then washing in deionized water for 4 times, drying in an oven at 100 ℃ for 24 hours, then cutting the areca residue into filaments with the diameter of about 3 mm, putting the filaments into a tubular electric furnace in a helium environment, and starting to heat up. The temperature rise speed is 5 ℃/min, the temperature is raised to 500 ℃, and the carbonized material is taken out after heat preservation and calcination are carried out for 2 h. 10 g of the carbonized material was mixed with 40 g of FeCl3Blending and grinding into powder. And (3) putting the ground blended powder into a helium environment tubular electric furnace, continuously heating up to 900 ℃ at the heating rate of 2 ℃/min, keeping the temperature, calcining for 5 h, and taking out the activated material. And (3) washing the activated material with sulfuric acid and deionized water respectively for 4 times, and drying in an oven at 100 ℃ for 48 hours to obtain dry porous carbon powder.
0.6 g of porous carbon powder, 3 g of PVDF granules, are dissolved in 30 g of DMAC and heated with stirring in an oil bath at 80 ℃ for 18 h. Standing in an oven at 80 ℃ for 12 h to obtain the required membrane casting solution, and coating the obtained membrane casting solution on a PP membrane by a scraper with the thickness of 15 mu m. The coated glass fiber membrane was soaked in 70% by mass aqueous DMAC solution for 18 h and then dried in an oven at 90 ℃ for 36 h. The finally obtained separator was die-cut into circular sheets with a diameter of 19 mm for use.
0.9 g of Super P, 0.1 g of PVDF and 20 g of NMP are mixed and ground to obtain slurry, the slurry is coated on a foam nickel screen with the diameter of 14 mm by a painting brush to obtain a battery cathode, and the coating amount is 1.0 mg cm-2. And (3) dissolving 0.1M LiTFSI in 1-ethyl-3-methyl tetrafluoroborate imidazole in a glove box in an argon environment to prepare a required electrolyte, and sequentially packaging the battery cathode, the obtained circular membrane, the electrolyte and a lithium sheet to obtain the lithium-air battery.
The carbon material prepared in this example had a specific surface area of 1865 m2g-1Pore volume of 0.77 cm3g-1. The tensile strength of the composite diaphragm of the lithium-air battery prepared in the embodiment is 158 MPa, the tensile strength of the common PP diaphragm is 156 MPa, and the lithium-air battery prepared in the embodiment and the lithium-air battery using the common PVDF-HFP diaphragm are applied under the voltage range of 2-4.5VCharge and discharge tests were performed. When not limited, the dischargeable specific capacity of the lithium-air battery prepared by the embodiment is 39353 mA h g-1The specific dischargeable capacity of the lithium-air battery using the common PP diaphragm is 22628 mA h g-1(ii) a Limiting the specific capacity to 500 mA hg-1In this case, the lithium-air battery prepared in this example can be cycled for 396 cycles with a maximum overpotential of 1.1V during cycling, and the lithium-air battery using a common PVDF-HFP separator can be cycled for 232 cycles with a maximum overpotential of 1.8V during cycling.
Claims (10)
1. A preparation method of a lithium-air battery composite diaphragm is characterized by comprising the following steps:
step one, taking areca residue, soaking the areca residue in deionized water for 1 to 3 days, then washing the areca residue with the deionized water for 2 to 5 times, and then drying the areca residue in an oven at the temperature of between 60 and 150 ℃ for 6 to 24 hours;
step two, mechanically treating the dried areca residue obtained in the step one to obtain easily carbonized areca residue;
step three, putting the easy-carbonized areca-nut residues obtained in the step two into a tubular electric furnace, introducing protective gas, heating to 800 ℃ at the heating rate of 1-10 ℃/min, and carrying out heat preservation and calcination for 1-4 h to obtain carbonized areca-nut residues;
step four, grinding the carbonized areca-nut residues obtained in the step three and an activating agent into powder in a mortar according to the mass ratio of 1:0.2-5, putting the powder into a tubular electric furnace, introducing protective gas, heating to 400-1000 ℃ at the heating rate of 1-10 ℃/min, and carrying out heat preservation and calcination for 2-6 h to obtain activated areca-nut residues;
step five, washing the activated areca residue obtained in the step four in an acid solution for 3-5 times, then continuing to wash in deionized water for 2-4 times, and then drying in an oven at 80-150 ℃ for 6-48 h to obtain porous carbon;
step six, mixing an organic solvent, a high molecular organic substance and the porous carbon obtained in the step five according to a mass ratio of 5-20: 1: 0.05-0.3, heating and stirring for 6-36 h in an oil bath pan at 50-140 ℃, and standing for 6-24 h in an oven at 50-100 ℃ to obtain a casting solution;
step seven, coating the casting solution obtained in the step six on a pre-installed diaphragm, soaking the pre-installed diaphragm coated with the casting solution in a mixed coagulating bath for 6-48 h, and then putting the pre-installed diaphragm into an oven at 50-120 ℃ for drying for 12-48 h to obtain the lithium-air battery composite diaphragm;
and step eight, sequentially packaging the cathode of the lithium-air battery, the composite diaphragm of the lithium-air battery obtained in the step seven, the electrolyte and the metal lithium sheet in an anhydrous and oxygen-free environment to obtain the lithium-air battery.
2. The method for preparing a lithium-air battery composite separator according to claim 1, wherein the mechanical treatment in the second step is one or more of ball milling, shearing or extrusion.
3. The method for preparing the lithium-air battery composite diaphragm as claimed in claim 1, wherein the easy-carbonized areca residue obtained in the second step is in a shape of thread, strip, granule or powder.
4. The method of claim 1, wherein the protective gas in step three and step four is one of argon, nitrogen or helium.
5. The method of claim 1, wherein the activator is KOH, KCl, FeCl3、Fe2O3Or ZnCl2One kind of (1).
6. The method according to claim 1, wherein the acid solution in the fifth step is one of sulfuric acid, hydrochloric acid and nitric acid.
7. The method according to claim 1, wherein in the sixth step, the polymer organic substance is one or more of PVDF, PTFE, PEI, PVDF-HFP and HDPE, and the organic solvent is one of DMF, DMAC and NMP.
8. The method according to claim 1, wherein the pre-installed membrane in the seventh step is one of a glass fiber membrane, a PP membrane, a PE membrane, a PEI membrane, a PVDF membrane, and a PVDF-HFP membrane, and the mixed coagulation bath is a blended solution of an organic solvent and deionized water in a mass ratio of 0-4:1, wherein the organic solvent is the same as the organic solvent selected in the sixth step.
9. The method of claim 1, wherein the coating in step seven is one of spraying, brushing and knife coating, and the coating thickness is 10-40 μm.
10. The method according to claim 1, wherein in the eighth step, the lithium-air battery cathode is prepared by coating a blend of a carbon material, a binder and NMP on foamed nickel or carbon paper, and the blending mass ratio of the carbon material, the binder and the NMP is 1: 0.1-0.3: 4-20, wherein the carbon material is one of Super P, acetylene black and Ketjen black, and the binder is PVDF or PTFE; the electrolyte consists of lithium salt and solvent, wherein the lithium salt is selected from LiClO4、LiTFSI、LiNO3、LiFSI、LiCF3SO3、LiPF6The solvent is one or more selected from dimethyl sulfoxide, ethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 1-ethyl-3-methyl tetrafluoroborate imidazole and N, N-dimethylformamide.
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Application publication date: 20201009 |