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An all-solid-state lithium-sulfur battery

A lithium-sulfur battery, all-solid-state technology, applied in the direction of batteries, battery electrodes, secondary batteries, etc., can solve the problems of shuttle effect, large interface contact resistance, and reduce Coulombic efficiency, etc., to achieve large-scale production and interface contact The effect of small impedance and improved Coulombic efficiency

Active Publication Date: 2019-07-05
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

1. Polysulfides, the discharge intermediate products of the sulfur positive electrode, dissolve in the electrolyte, which on the one hand causes the shuttle effect and reduces the Coulombic efficiency; on the other hand, the polysulfides diffuse through the diaphragm to the negative electrode, corroding metal lithium
2. In batteries using organic electrolytes, due to the uneven deposition of lithium ions, dendrites are easily formed on the metal lithium negative electrode. On the one hand, dead lithium affects the cycle performance of the battery; on the other hand, the dendrites penetrate the separator and cause a short circuit of the battery
3. The boiling point of the organic electrolyte is low. In the case of abuse, such as overcharging, over-discharging, and acupuncture batteries with external force, it will cause dangerous accidents such as combustion and explosion of the battery
[0004] The reported lithium-sulfur batteries or lithium-sulfur flow batteries all have one or more of the following defects: organic-inorganic composite solid electrolytes have low room temperature ionic conductivity; It is difficult to prepare; the interface contact resistance with the positive and negative electrodes is large; the inorganic solid electrolyte is brittle and fragile, and it is not easy to form; the preparation steps are cumbersome and not suitable for large-scale production
[0006] All-solid-state lithium-sulfur batteries using lithiated sulfonic acid polymer solid electrolytes have not been reported

Method used

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Examples

Experimental program
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Embodiment 1

[0042] Soak the perfluorosulfonic acid-polytetrafluoroethylene membrane in 1M LiOH aqueous solution at 80°C for 12 hours, then wash it with solvent for 3 to 10 times to remove the LiOH on the membrane surface, and then dry it at 100°C for 2 hours. Vacuum drying at 60°C for 48 hours to obtain a lithiated perfluorosulfonic acid-polytetrafluoroethylene membrane. Using NMP as solvent, a lithiated perfluorosulfonic acid-polytetrafluoroethylene polymer emulsion with a mass fraction of 5% was prepared at 80°C. Sulfurized polyacrylonitrile, acetylene black, and lithiated perfluorosulfonic acid-polytetrafluoroethylene polymer are weighed at a mass ratio of 6:2:2 as the positive electrode active material, mixed and ground with NMP as a solvent, and then coated on an aluminum foil and dried overnight in a vacuum oven at 55°C to obtain a sulfur cathode. The lithiated perfluorosulfonic acid-polytetrafluoroethylene membrane and the sulfur positive electrode were hot-pressed at 120 °C and 0...

Embodiment 2

[0044] Soak the polytrifluorostyrene sulfonic acid membrane in 2M LiOH in DMSO solution at 100°C for 12 hours, then wash it with a solvent for 3 to 10 times to remove LiOH on the membrane surface, and then dry it at 100°C for 6 hours. Then vacuum-dry at 100°C for 48 hours to obtain a lithiated polytrifluorostyrene sulfonic acid membrane. Using DMF as a solvent, a lithiated polytrifluorostyrene sulfonic acid polymer emulsion with a mass fraction of 10% was prepared at 60°C. Weigh the positive electrode active materials iron sulfide, Super-P, and lithiated polytrifluorostyrene sulfonic acid polymer at a mass ratio of 5:1:4, mix and grind them evenly with DMF as a solvent, and coat them on carbon-coated aluminum foil , dried overnight in a vacuum oven at 55°C to obtain a sulfur cathode. The lithiated polytrifluorostyrene sulfonic acid membrane and the sulfur positive electrode were hot-pressed at 110 °C and 1 MPa pressure for 3 min to obtain an integrated positive electrode and ...

Embodiment 3

[0046] The polydifluorostyrene sulfonic acid membrane was soaked in a mixed solution of 1M LiOH ethanol and water (volume ratio 1:1) at 80°C for 12 hours, then washed with solvent for 3 to 10 times to remove LiOH on the membrane surface, and then placed on Blast drying at 80°C for 6 hours, and then vacuum drying at 40°C for 48 hours to obtain a lithiated polydifluorostyrene sulfonic acid membrane. Using DMAc as a solvent, a lithiated poly(difluorostyrene sulfonic acid) polymer emulsion with a mass fraction of 4% was prepared at 90°C. The positive electrode active material sublimated sulfur selenium solid solution, ketjen black, and lithiated polydifluorostyrene sulfonic acid polymer were weighed at a mass ratio of 4:3:3, mixed and ground with DMAc as a solvent, and then coated on copper foil and dried overnight in a vacuum oven at 55°C. The lithiated polydifluorostyrene sulfonic acid membrane and the sulfur positive electrode were hot-pressed at 100°C and 2 MPa pressure for 3...

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Abstract

The invention discloses an all-solid-state lithium-sulfur battery, comprising a sulfur positive electrode, a lithium or lithium alloy negative electrode, and a lithiated sulfonic acid polymer solid electrolyte diaphragm; the solid electrolyte diaphragm is located between the sulfur positive electrode and the lithium or lithium alloy negative electrode; the sulfur positive electrode Including sulfur-containing active material, conductive agent and lithiated sulfonic acid polymer; sulfur positive electrode, lithiated sulfonic acid polymer solid electrolyte, lithium or lithium alloy negative electrode are sequentially stacked and assembled to form a battery. The room temperature ionic conductivity of the lithiated sulfonic acid polymer solid electrolyte is >10 ‑5 S / cm, no complex lithium salt is required, the preparation method is simple, and the room temperature ionic conductivity of the lithiated sulfonic acid polymer solid electrolyte is better than that of general inorganic-organic composite solid electrolytes. The polymer emulsion is used to prepare the sulfur positive electrode sheet, and an efficient "sulfur / carbon / solid electrolyte" interface is built inside the electrode to improve the activity of the sulfur electrode and obtain a battery with excellent performance; and the existing electrode sheet coating process and equipment, which is conducive to large-scale production.

Description

technical field [0001] The invention relates to a lithiated sulfonic acid polymer solid electrolyte, a preparation method thereof, and an all-solid lithium-sulfur battery. Background technique [0002] Lithium-sulfur batteries have become the next generation of secondary battery systems due to their high energy density and low cost. However, most of the lithium-sulfur batteries reported at present use organic electrolytes with low boiling points, and there are still some technical problems that need to be solved urgently. 1. Polysulfide, the discharge intermediate product of the sulfur positive electrode, dissolves in the electrolyte, which on the one hand causes the shuttle effect and reduces the Coulombic efficiency; on the other hand, the polysulfide diffuses through the separator to the negative electrode and corrodes metal lithium. 2. In a battery using an organic electrolyte, due to the uneven deposition of lithium ions, dendrites are easily formed on the metal lithiu...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): H01M10/0565H01M2/16H01M4/62H01M4/13H01M4/136H01M4/137H01M50/403H01M50/411H01M50/497
CPCH01M4/13H01M4/136H01M4/137H01M4/62H01M10/0565H01M2220/20H01M2220/30H01M50/411Y02E60/10
Inventor 陈剑高静陶韬刘颖佳
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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