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A preparation method of a high-performance polyolefin composite battery separator and a lithium sulfur battery

A polyolefin separator and composite battery technology, applied in secondary batteries, battery pack parts, circuits, etc., can solve the problem of difficulty in ensuring battery volume energy density and mass energy density, the overall performance of the separator is not ideal, and tert-butyl lithium is easy to use. It is suitable for large-scale industrial production, alleviates the puncture ability of lithium dendrites, and improves cycle stability.

Active Publication Date: 2019-01-18
湖南烁普新材料有限公司
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the above methods all require the use of binders, which makes it difficult to ensure the volumetric energy density and mass energy density of the battery.
In addition, the preparation conditions of black phosphorus and pre-lithiated molybdenum disulfide are harsh, requiring high temperature and high pressure conditions, and the tert-butyllithium used in the pre-lithiation process is flammable and explosive, and safety is difficult to guarantee
[0004] Although the above studies have shown that modifying a layer of polar nanomaterials with high binding energy between polysulfides and polysulfides on the surface of traditional polyolefin separators can effectively inhibit the "shuttle effect" during the cycle of lithium-sulfur batteries, the overall performance of the separator The performance is still not ideal, and the key to mass production of polyolefin separator is to reduce the price and simplify the operation

Method used

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  • A preparation method of a high-performance polyolefin composite battery separator and a lithium sulfur battery
  • A preparation method of a high-performance polyolefin composite battery separator and a lithium sulfur battery
  • A preparation method of a high-performance polyolefin composite battery separator and a lithium sulfur battery

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0034] The preparation process of this embodiment is as follows:

[0035] (1) Cutting: Cut the polyolefin separator into discs with a diameter of 19 mm;

[0036] (2) Oxidation: immerse 5 polyolefin diaphragms prepared in step (1) into 100 ml of 98% concentrated nitric acid, stir for 3 hours, pre-oxidize the surface of the diaphragm, and prepare a dense active on the surface of the diaphragm. site;

[0037] (3) Mixed solvent: mix ethanol and deionized water to form a mixed solvent, and the volume ratio of ethanol to deionized water is 1:1;

[0038] (4) Prepare transition metal salt solution: dissolve 0.5 g of Ce(SO4)2 in 100 ml of the mixed solvent prepared in step (3), stir for 10 minutes to completely dissolve;

[0039] (5) Composite: immerse the diaphragm treated in step (2) into the transition metal salt solution prepared in step (4), then add 30 ml of hydrogen sulfuric acid solution with a concentration of 0.1 mole / liter dropwise, and then put the solution at room temper...

Embodiment 2

[0042] The differences between this embodiment and Embodiment 1 are:

[0043] Stirring in step (2) for 3.5 hours to pre-oxidize the surface of the diaphragm;

[0044] In step (4), dissolve 1.2 grams of FeSO4 7H2O in 100 ml of the mixed solvent prepared in step (3), stir for 10 minutes to completely dissolve

[0045] In step (5), immerse the diaphragm treated in step (2) into the transition metal salt solution prepared in step (4), then add 20 ml of hydrogen sulfuric acid solution with a concentration of 0.1 mole / liter dropwise, and then put the solution in Stir at room temperature for 2.5 hours;

[0046] In step (6), a polypropylene separator modified with ferrous sulfide nanoparticles is obtained, and the separator is applied to a lithium-sulfur battery.

[0047] All the other are the same as embodiment one.

Embodiment 3

[0049] The differences between this embodiment and Embodiment 1 are:

[0050]In step (2), immerse 5 polyolefin diaphragms prepared in step (1) into 100 ml of a mixed solution mixed with hydrogen peroxide and potassium peroxodisulfate at a volume ratio of 1:1, stir for 3.5 hours, and conduct Pre-oxidation, wherein the hydrogen peroxide is an aqueous hydrogen peroxide solution with a mass percentage of hydrogen peroxide of 15%, and the concentration of the potassium peroxodisulfate solution is 0.025 mole / liter;

[0051] In step (4), 0.9 g of MnSO4·H2O was dissolved in 100 ml of the mixed solvent prepared in step (3), and stirred for 10 minutes to completely dissolve;

[0052] In step (5), immerse the diaphragm treated in step (2) into the transition metal salt solution prepared in step (4), then add 30 ml of hydrogen sulfuric acid solution with a concentration of 0.1 mole / liter dropwise, and then put the solution in Stir at room temperature for 2.5 hours;

[0053] In step (6),...

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Abstract

The invention discloses a preparation method of a high-performance polyolefin composite battery separator and a lithium-sulfur battery, and belongs to the technical field of a method or a device for converting chemical energy into electric energy. The preparation method comprises the following steps of: (1) cutting the polyolefin separator into a circular pieces; 2, immersing 5 pieces of polyolefin membrane into concentrated nitric acid or a mixed solution composed of hydrogen peroxide and potassium persulfate solution, and continuously performing stirring to carry out oxidation; 3) mixing ethanol and deionized wat according to a volume ratio of 1: 1 to obtain a mixed solvent; (4) adding the transition metal salt into the mixed solvent prepared in the step (3), and continuously performingstirring to fully dissolve the salt; (5) immersing the treated diaphragm in the step (2) into the transition metal salt solution prepared in the step (4), adding hydrosulfuric acid drop by dropping, and continuously stirring to graft the transition metal sulfide onto the active site of the diaphragm; (6) cleaning and drying to obtain modified polyolefin membrane in six steps. The surface polarityof the polyolefin separator and the rate performance of the battery can be greatly improved by this method.

Description

technical field [0001] The invention belongs to the technical field of methods or devices for directly converting chemical energy into electric energy, and specifically relates to a preparation method of a high-performance polyolefin composite battery diaphragm and a lithium-sulfur battery. Background technique [0002] The theoretical specific capacity of lithium-sulfur batteries can reach 1675mAh / g, and the energy density can reach 2600Wh / kg. Moreover, lithium-sulfur batteries have the advantages of low price, abundant sulfur reserves, and environmental friendliness, which have gradually attracted widespread attention. Separator is an integral part of lithium-sulfur batteries. Because polyolefin materials have the advantages of low price, good mechanical strength and chemical stability, and have high-temperature self-closing properties, they can ensure the stability of lithium-ion secondary batteries in daily use. Safety, the microporous diaphragm made of this raw material...

Claims

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Application Information

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IPC IPC(8): H01M2/14H01M2/16H01M10/0525H01M50/403H01M50/446H01M50/489
CPCH01M10/0525H01M50/403H01M50/411Y02E60/10
Inventor 王书珍
Owner 湖南烁普新材料有限公司
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