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Ion-selective gel-state electrolyte, preparation method and lithium-sulfur battery

A technology for ion-selective, lithium-sulfur batteries, applied in the field of preparation methods and lithium-sulfur batteries, ion-selective gel electrolytes, can solve the problems of reducing the solubility of polysulfide ions, low Coulombic efficiency, weakening shuttle behavior, etc., to achieve improved Effects of low Coulombic efficiency, promotion of transport, and inhibition of shuttle effect

Active Publication Date: 2022-03-04
NANJING UNIV OF INFORMATION SCI & TECH
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] The object of the present invention is to provide an ion-selective gel-state electrolyte, a preparation method and a lithium-sulfur battery. The gel-state polymer electrolyte membrane does not contain free electrolyte, which can reduce the solubility of polysulfide ions, which is conducive to weakening its shuttle behavior ; The polymer matrix contains benzene ring π bonds with high electron cloud density, sulfonic acid groups, phosphoric acid groups and other highly electronegative functional groups, which make the electrolyte membrane ion-selective. On the one hand, it can promote the transmission of electropositive lithium ions, and at the same time inhibit The migration behavior of polysulfide anions in the membrane, thereby inhibiting its shuttle effect, improving the capacity fading and low Coulombic efficiency of lithium-sulfur batteries; the scheme is simple and controllable, and has strong operability. The ionic conductivity is 10 -3 S cm -1 It is more than an order of magnitude, close to the conductivity of traditional liquid electrolytes, and the lithium ion migration number is close to 1, indicating that the electrolyte membrane has lithium ion selectivity

Method used

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  • Ion-selective gel-state electrolyte, preparation method and lithium-sulfur battery

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Embodiment 1

[0037] Mix polyetheretherketone and concentrated sulfuric acid at a mass ratio of 1:40, and react at 55°C for 6h. Add a cross-linking agent with a mass ratio of 1% and sodium trimetaphosphate to continue the reaction for 10 minutes. After the reaction is completed, pour the mixed solution into an ice-water bath to precipitate, filter and wash until the filtrate is neutral, and dry it in a vacuum oven at 50°C. After 24h, cross-linked sulfonated polyetheretherketone was obtained. Weigh cross-linked sulfonated polyetheretherketone dissolved in NMP+H 2 In a mixed solution of O (volume ratio 1:1), the mass concentration of cross-linked sulfonated polyetheretherketone was 4%, and the obtained homogeneous solution was coated on a glass plate to obtain a wet film, and stood at room temperature for 3 hours to defoam. Transfer to a vacuum oven and dry at 50°C for 24 hours to form a film. The dry polymer film was cut into a disc with a diameter of 16 mm, immersed in a lithium-sulfur el...

Embodiment 2

[0039] Mix polyetheretherketone and concentrated sulfuric acid at a mass ratio of 1:50, and react at 65°C for 4h. Add a cross-linking agent with a mass ratio of 30% and sodium trimetaphosphate to continue the reaction for 60 minutes. After the reaction is completed, pour the mixed solution into an ice-water bath to precipitate, filter and wash until the filtrate is neutral, and dry it in a vacuum oven at 90°C. 12h to obtain cross-linked sulfonated polyetheretherketone. Weigh cross-linked sulfonated polyetheretherketone dissolved in DMF+H 2 In a mixed solution of O (volume ratio 1:4), the mass concentration of the cross-linked sulfonated polyetheretherketone was 10%, and the obtained homogeneous solution was coated on a glass plate to obtain a wet film, and stood at room temperature for 6 hours to defoam. Transfer to a vacuum oven and dry at 90°C for 12 hours to form a film. The dry film was characterized by SEM, the surface of the film was relatively smooth, and uniform netw...

Embodiment 3

[0041] Mix polyetheretherketone and concentrated sulfuric acid at a mass ratio of 1:40, and react at 55°C for 6h. Add a cross-linking agent with a mass ratio of 5% and sodium trimetaphosphate to continue the reaction for 30 minutes. After the reaction is completed, pour the mixed solution into an ice-water bath to precipitate, filter and wash until the filtrate is neutral, and dry it in a vacuum oven at 80°C. After 24h, cross-linked sulfonated polyetheretherketone was obtained. Weigh cross-linked sulfonated polyetheretherketone dissolved in NMP+H 2 In a mixed solution of O (volume ratio 1:2), the resulting homogeneous solution was coated on a glass plate to obtain a wet film, left at room temperature for 4 hours to defoam, then transferred to a vacuum drying oven at 80°C for 24 hours to form a film. The dry polymer film was cut into a disc with a diameter of 16 mm, immersed in a lithium-sulfur electrolyte (1M LiTFSI DOL / DME (V / V=1:1)+1% LiNO 3 ), to obtain a polymer electrol...

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Abstract

The invention discloses an ion-selective gel-state electrolyte, a preparation method and a lithium-sulfur battery. The electrolyte comprises a polymer matrix and a liquid electrolyte contained in the polymer matrix, the polymer matrix is generated by carrying out sulfonation and cross-linking reaction on polyether-ether-ketone; the preparation method comprises the following steps: preparing a sulfonated polyetheretherketone solution system, and adding a cross-linking agent for cross-linking reaction to obtain a cross-linked sulfonated polyetheretherketone mixed solution; cooling and precipitating in an ice-water bath, and then filtering and washing to obtain the cross-linked sulfonated polyether-ether-ketone; dissolving in a mixed solution of an organic solvent and water to obtain a polymer precursor solution; coating on a glass plate to obtain a wet film, standing and defoaming, and then performing vacuum drying to obtain a cross-linked sulfonated polymer matrix; and cutting, immersing into a lithium-sulfur electrolyte, and removing excessive electrolyte on the surface to obtain the ion selective gel state electrolyte membrane. The gel-state polymer electrolyte membrane does not contain free electrolyte, the solubility of polysulfide ions can be reduced, and the shuttle behavior of the polysulfide ions can be weakened.

Description

technical field [0001] The invention relates to the field of lithium-sulfur batteries, in particular to an ion-selective gel-state electrolyte, a preparation method and a lithium-sulfur battery. Background technique [0002] A lithium-sulfur secondary battery (referred to as a lithium-sulfur battery) with lithium metal as the negative electrode and elemental sulfur as the positive electrode active material, and LiCoO 2 , LiMn 2 o 4 、LiFePO 4 Compared with lithium-ion batteries with positive electrode materials such as ternary materials and ternary materials, they have significant advantages in specific capacity, energy density and power density. The theoretical specific capacity of elemental sulfur is 1675mAh g -1 , with a theoretical specific capacity of 3861mAh g -1 The theoretical specific energy can reach 2600Wh kg after the metal lithium is assembled into a battery -1 , In addition, elemental sulfur also has the advantages of abundant resources, low cost, and envir...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): H01M10/052H01M10/0565
CPCH01M10/0565H01M10/052Y02E60/10
Inventor 李龙燕代启航涂天成贾益阳胡冰洁
Owner NANJING UNIV OF INFORMATION SCI & TECH
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