Preparation method of super-hydrophobic super-oleophylic lithium air battery composite diaphragm

Abstract

The invention discloses a preparation method of a super-hydrophobic super-oleophylic lithium air battery composite diaphragm. The preparation method comprises the following steps: preparing an alkyl chain modified linear dicarboxylic acid ligand by taking methyl hydroxyiodobenzoate as a raw material; the preparation method comprises the following steps: by taking N, N-dimethylformamide as a solvent and trifluoroacetic acid as a regulator, reacting metal ion clusters and ligands thereof at high temperature to synthesize super-hydrophobic and super-oleophylic MOFs (Metal Organic Frameworks) particles; and preparing the synthesized MOFs particles, a binder, a solvent and an additive into slurry, and coating a base membrane with the slurry to obtain the super-hydrophobic and super-oleophylic lithium air battery composite diaphragm. Compared with a glass fiber membrane commonly used in current research, the composite membrane prepared by the process disclosed by the invention not only can effectively prevent moisture in air from diffusing to a lithium metal negative electrode, but also can reduce the formation of negative electrode lithium dendrites, and meanwhile, the composite membrane also has good wettability to an electrolyte.

Description

technical field

[0001] The invention belongs to the field of lithium-air battery materials, and in particular relates to a preparation method of a superhydrophobic and superoleophilic lithium-air battery composite diaphragm. Background technique

[0002] Lithium-air batteries have a theoretical energy density much higher than that of lithium-ion batteries, and they have the highest energy density among existing battery systems. If the weight of oxygen involved in the reaction is not calculated, the energy density of the lithium-air battery is as high as 11430Wh Kg -1 , very close to fossil fuels. As it is expected to become a new source of driving energy for electric vehicles, researchers are gradually increasing investment in research and development of lithium-air batteries. Among lithium-air battery separators, glass fiber membranes are currently widely used in research. Researchers have also used different polymer materials, ceramic fillers, and functional additives to...

Examples

Embodiment 1

[0026] Example 1: Add 2.0 g of methyl 2-hydroxy-4-iodobenzoate to 3 mL of acetic anhydride, then add 85 μL of concentrated sulfuric acid to obtain a mixed solution, and magnetically stir the mixed solution at 80° C. for 12 h; after cooling to room temperature , add 15mL deionized water to the mixed solution, and then use 20mL CHCl 3 Extracted 3 times; the obtained 3 extracts were mixed, and then passed through a short silica gel column to remove part of the inorganic salt impurities, and the obtained liquid was sequentially washed with saturated NaHCO 3 solution washing, with MgSO 4 Product A was obtained as a white solid after drying, filtration and removal of solvent under vacuum;

[0027] in N 2 Under atmosphere, mix 1.60g product A, 3.00g active copper, 4mL N,N-dimethylformamide, then heat the mixed solution to 155°C for 10h; filter the reacted mixed solution while hot, and then collect The filtrate was poured into 40 mL of deionized water and stirred vigorously, the fo...

Embodiment 2

[0033] Example 2: Add 2.0 g of methyl 3-hydroxy-4-iodobenzoate to 2.8 mL of butenedioic anhydride, then add 80 μL of concentrated sulfuric acid to obtain a mixed solution, and magnetically stir the mixed solution at 80° C. for 12 h; leave to cool After reaching room temperature, 12 mL of deionized water was added to the mixed solution, followed by 20 mL of CH 2 ClCH 2 Cl extraction 3 times; the 3 extracts obtained were mixed, and then passed through a short silica gel column to remove part of the inorganic salt impurities, and the obtained liquid was successively passed through saturated NaHCO 3 solution washing, with Na 2 SO 4 Product A was obtained as a white solid after drying, filtration and removal of solvent under vacuum;

[0034] in N 2 Under the atmosphere, mix 1.70g of product A, 3.00g of active nickel, and 4mL of N,N-dimethylformamide, and then heat the mixed solution to 160°C for 12h; filter the reacted mixed solution while it is hot, and then collect The filtr...

Embodiment 3

[0040] Example 3: Add 2.2 g of methyl 4-hydroxy-3-iodobenzoate to 2.8 mL of phthalic anhydride, then add 80 μL of concentrated sulfuric acid to obtain a mixed solution, and magnetically stir the mixed solution at 85° C. for 15 h; After cooling to room temperature, 13 mL of deionized water was added to the mixed solution, and then 20 mL of C 2 HCl 5 Extracted 3 times; the obtained 3 extracts were mixed, and then passed through a short silica gel column to remove part of the inorganic salt impurities, and the obtained liquid was sequentially washed with saturated NaHCO 3 solution washing, with Na 2 SO 4 and CaSO 4 Product A was obtained as a white solid after drying, filtration and removal of solvent under vacuum;

[0041] in N 2 Under the atmosphere, mix 1.80g of product A, 3.00g of active titanium, and 4mL of N,N-dimethylacetamide, and then heat the mixed solution to 150°C for 10h; filter the reacted mixed solution while it is hot, and then collect The filtrate was poured ...

technical field

[0001] The invention belongs to the field of lithium-air battery materials, and in particular relates to a preparation method of a superhydrophobic and superoleophilic lithium-air battery composite diaphragm. Background technique

[0002] Lithium-air batteries have a theoretical energy density much higher than that of lithium-ion batteries, and they have the highest energy density among existing battery systems. If the weight of oxygen involved in the reaction is not calculated, the energy density of the lithium-air battery is as high as 11430Wh Kg -1 , very close to fossil fuels. As it is expected to become a new source of driving energy for electric vehicles, researchers are gradually increasing investment in research and development of lithium-air batteries. Among lithium-air battery separators, glass fiber membranes are currently widely used in research. Researchers have also used different polymer materials, ceramic fillers, and functional additives to...

Examples

Embodiment 1

[0026] Example 1: Add 2.0 g of methyl 2-hydroxy-4-iodobenzoate to 3 mL of acetic anhydride, then add 85 μL of concentrated sulfuric acid to obtain a mixed solution, and magnetically stir the mixed solution at 80° C. for 12 h; after cooling to room temperature , add 15mL deionized water to the mixed solution, and then use 20mL CHCl 3 Extracted 3 times; the obtained 3 extracts were mixed, and then passed through a short silica gel column to remove part of the inorganic salt impurities, and the obtained liquid was sequentially washed with saturated NaHCO 3 solution washing, with MgSO 4 Product A was obtained as a white solid after drying, filtration and removal of solvent under vacuum;

[0027] in N 2 Under atmosphere, mix 1.60g product A, 3.00g active copper, 4mL N,N-dimethylformamide, then heat the mixed solution to 155°C for 10h; filter the reacted mixed solution while hot, and then collect The filtrate was poured into 40 mL of deionized water and stirred vigorously, the fo...

Embodiment 2

[0033] Example 2: Add 2.0 g of methyl 3-hydroxy-4-iodobenzoate to 2.8 mL of butenedioic anhydride, then add 80 μL of concentrated sulfuric acid to obtain a mixed solution, and magnetically stir the mixed solution at 80° C. for 12 h; leave to cool After reaching room temperature, 12 mL of deionized water was added to the mixed solution, followed by 20 mL of CH 2 ClCH 2 Cl extraction 3 times; the 3 extracts obtained were mixed, and then passed through a short silica gel column to remove part of the inorganic salt impurities, and the obtained liquid was successively passed through saturated NaHCO 3 solution washing, with Na 2 SO 4 Product A was obtained as a white solid after drying, filtration and removal of solvent under vacuum;

[0034] in N 2 Under the atmosphere, mix 1.70g of product A, 3.00g of active nickel, and 4mL of N,N-dimethylformamide, and then heat the mixed solution to 160°C for 12h; filter the reacted mixed solution while it is hot, and then collect The filtr...

Embodiment 3

[0040] Example 3: Add 2.2 g of methyl 4-hydroxy-3-iodobenzoate to 2.8 mL of phthalic anhydride, then add 80 μL of concentrated sulfuric acid to obtain a mixed solution, and magnetically stir the mixed solution at 85° C. for 15 h; After cooling to room temperature, 13 mL of deionized water was added to the mixed solution, and then 20 mL of C 2 HCl 5 Extracted 3 times; the obtained 3 extracts were mixed, and then passed through a short silica gel column to remove part of the inorganic salt impurities, and the obtained liquid was sequentially washed with saturated NaHCO 3 solution washing, with Na 2 SO 4 and CaSO 4 Product A was obtained as a white solid after drying, filtration and removal of solvent under vacuum;

[0041] in N 2 Under the atmosphere, mix 1.80g of product A, 3.00g of active titanium, and 4mL of N,N-dimethylacetamide, and then heat the mixed solution to 150°C for 10h; filter the reacted mixed solution while it is hot, and then collect The filtrate was poured ...

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