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A carborane-like covalent organic framework material modified separator and lithium-sulfur battery

A technology of covalent organic framework and lithium-sulfur battery, which is applied in the direction of lithium storage battery, battery pack components, non-aqueous electrolyte storage battery, etc. It can solve the problems of low efficiency and achieve low density, simple coating process and good thermal stability Effect

Active Publication Date: 2022-04-01
NANJING TECH UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, due to the large pore size of some COFs and the indirect trapping of LiPSs due to the interaction of polar sites with Li ions, the efficiency is not as good as the direct trapping of LiPSs anions, so in order to obtain high capacity and excellent cycle stability, rational design and Synthesis of COFs with suitable porosity and polar bonds (Adv.Energy Mater.2016,6,1601250.; J.Mater.Chem.A,2016,4,7416.)

Method used

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  • A carborane-like covalent organic framework material modified separator and lithium-sulfur battery
  • A carborane-like covalent organic framework material modified separator and lithium-sulfur battery
  • A carborane-like covalent organic framework material modified separator and lithium-sulfur battery

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Effect test

Embodiment 1

[0041] 1. Preparation of a novel separator containing p-carborane covalent organic framework materials

[0042] 1) Under the protection of nitrogen, dissolve 500mg p-carborane in 9.0ml anhydrous tetrahydrofuran, and cool to 0°C, add dropwise 4.56ml n-butyllithium, stir at room temperature for 2 hours, cool to 0°C again, add 800 μl of phenyl azide, the mixture was stirred at room temperature for 12 hours and then pumped dry, ether and saturated ammonium chloride solution were added, the organic phase was collected, washed three times with saturated brine, and the ether was concentrated to obtain substance I with a yield of 86%.

[0043] figure 1 It is the hydrogen spectrum of substance I: 1H NMR (400MHz, CDCl3) δ: 7.32 (t, J=11.0Hz, 4H), 7.09 (m, 6H) (aromatic H). It is worth noting that the chemical shifts of C-H(2H) belonging to the raw material p-carborane are all at 2.75, and the hydrogen spectrum of the product has disappeared, which means that the two hydrogens of p-carb...

Embodiment 2

[0062] 1. Preparation of new membranes modified with m-carborane-containing covalent organic framework materials

[0063] 1) Weigh 15 mg of m-carborane diamine compound and 18 mg of 2,4,6-trihydroxy-1,3,5-benzenetricarbaldehyde, and conduct a hydrothermal reaction at 115°C for 70 hours to obtain a new type of m-carborane-containing COFs Material.

[0064] 2) Weigh the new m-carborane-containing COFs material, Ketjen black and polyvinylidene fluoride (PVDF) obtained by the hydrothermal reaction according to the weight ratio of 4:5:1, grind for 20 minutes, and place it in a closed beaker Add an appropriate amount of N-methylpyrrolidone (NMP) solvent dropwise, followed by strong magnetic stirring for 10 h to form a uniform slurry, which is evenly coated on a polypropylene diaphragm (Celgard 2400) with a scraper, modified The thickness of the layer was 23 μm, and it was dried naturally for 8 minutes, and then dried overnight at 70° C. in a vacuum oven. Finally, punch the dried d...

Embodiment 3

[0071] 1. Preparation of a novel separator containing p-carborane covalent organic framework materials

[0072] 1) Weigh 10 mg of p-carborane diamine compound, 15 mg of 5,10,15,20-tetrakis(4-benzaldehyde) porphyrin, and conduct a hydrothermal reaction at 125°C for 75 hours to obtain a new p-carborane-containing COFs material b.

[0073] 2) The new p-carborane-containing COFs material B, Ketjen black and 5% LA 133 obtained by hydrothermal reaction were weighed according to the weight ratio of 4:5::1, ground for 20 minutes, and placed in a closed beaker. Add an appropriate amount of mixed solvent of water and propanol dropwise, followed by strong magnetic stirring for 8 hours to form a uniform slurry, and use a scraper to evenly coat the slurry on a polypropylene diaphragm (Celgard2400), the thickness of the modified layer is 21 μm, and let it dry naturally for 6 minutes , and then dried overnight at 60°C in a vacuum oven. Finally, punch the dried diaphragm into a disc with a ...

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Abstract

The invention provides a modified diaphragm and a lithium-sulfur battery of a carborane-based covalent organic framework material. The modified diaphragm used in the lithium-sulfur battery is selected from a polymer diaphragm as the main body, and a modified layer is coated on one side of the polymer diaphragm. The modified layer is a new type of carborane COFs material. The carborane COFs material modification layer contains a carborane structure. Due to the special and highly electron-deficient structure of carborane, boron at the polar site in the structure forms a strong bond with polysulfide, and carborane The structure provides extremely abundant polar sites for the adsorption of polysulfides (LiPSs), combined with the inherent excellent physical and chemical properties of COFs, significantly inhibits the generation of the shuttle effect, thereby improving the charge-discharge specific capacity of lithium-sulfur batteries and cycle stability, which result in fast reaction kinetics and excellent electrochemical stability.

Description

technical field [0001] The invention belongs to the technical field of energy materials, and in particular relates to a novel diaphragm modified by a covalent organic framework material, a preparation method thereof, and a lithium-sulfur battery with the diaphragm. Background technique [0002] In recent years, with the continuous growth of my country's economy and population, the consumption and demand for energy have increased sharply, and the concern about environmental pollution caused by the use of traditional fossil energy has become increasingly serious. To urgently address this concern, an urgent strategy is to develop and adopt novel renewable energy technologies, and rechargeable batteries have sparked extensive exploration as reliable electrochemical energy storage devices. Among the many existing electrochemical energy storage devices, lithium-sulfur batteries (Li-S) are considered to be one of the most promising energy storage systems for next-generation high-en...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): H01M50/414H01M50/449H01M50/403H01M10/052
CPCH01M10/052H01M50/403H01M50/411H01M50/449Y02E60/10
Inventor 于海洲朱跃进杨静莹
Owner NANJING TECH UNIV
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