Lithium single ionic conductive microporous electrolyte membrane and preparation method thereof

An electrolyte membrane and single-ion technology, applied in the manufacture of electrolyte batteries, non-aqueous electrolytes, solid electrolytes, etc., can solve problems such as low ion conductivity, loss of migration ability, reduced lithium-ion battery capacity, cycle performance, and energy efficiency , to achieve the effect of simple preparation method

Active Publication Date: 2014-12-03
江苏明魁高分子材料技术有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

This is because in the lithium-ion battery, on the one hand, the migration of anions will lead to the consumption of battery energy; on the other hand, because the migration speed of anions is faster than that of lithium ions, it will lead to concentration gradients and extreme concentration differences of electrolyte salts during charging and discharging. degradation, thereby reducing the capacity, cycle performance and energy efficiency of lithium-ion batteries
In the existing single-ion polymer electrolyte, the anion of the lithium salt is bonded to the polymer and loses the ability to migrate, so the lithium ion migration number can be close to 1, but the existing reported single-ion polymer electrolyte All materials have the problems of low ionic conductivity and poor mechanical properties. For example, the room temperature conductivity of reported lithium single-ion polymer electrolyte materials is generally 1×10 -4 Below S / cm, much lower than 1×10 -3 Actual requirement of S / cm

Method used

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  • Lithium single ionic conductive microporous electrolyte membrane and preparation method thereof
  • Lithium single ionic conductive microporous electrolyte membrane and preparation method thereof
  • Lithium single ionic conductive microporous electrolyte membrane and preparation method thereof

Examples

Experimental program
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Effect test

Embodiment 1

[0042] The polyphenylene ether polymer whose side group is lithium fluorosulfonate group has the following chemical structure:

[0043]

[0044] The preparation process of the polymer: add hydroquinone (10g), 4,4'-diphenol (17g), potassium carbonate (65g), anhydrous dimethyl Acetamide (450mL), toluene (180mL). The mixture was heated to reflux for 3 hours and the toluene / water azeotrope was removed with a trap. Sodium 2-(2',3',5',6'-tetrafluorophenoxy)tetrafluoroethanesulfonate (68 g) was then added to the flask and the reaction was maintained at 160°C for 12 hours. After the reaction was cooled to room temperature, the reaction mixture was precipitated in water, and the precipitate was collected by filtration and washed well with water. The obtained polymer was converted from the sodium salt form to the lithium salt by immersion in a 10 mol / L lithium triflate aqueous solution at 60° C. for 15 hours. After filtering and fully washing with water, the obtained polyphenylene...

Embodiment 2

[0051] The polyphenylene ether polymer whose side group is lithium fluorosulfonate group has the following chemical structure:

[0052]

[0053] The preparation process of the polymer: add hydroquinone (10 g), potassium carbonate (33 g), anhydrous dimethylacetamide (280 mL) and toluene (120 mL) into a three-necked flask protected by an argon atmosphere. The mixture was heated to reflux for 3 hours and the toluene / water azeotrope was removed with a trap. Sodium 2-(2',3',5',6'-tetrafluorophenoxy)tetrafluoroethanesulfonate (38 g) was then added to the flask and the reaction was maintained at 160°C for 12 hours. After the reaction was cooled to room temperature, the reaction mixture was precipitated in water, and the precipitate was collected by filtration and washed well with water. The obtained polymer was impregnated with 10 mol / L LiSO at 60 °C 3 CF 3 It was converted from the sodium salt form to the lithium salt in aqueous solution for 15 hours. After filtering and full...

Embodiment 3

[0057] Take by weighing 60 grams of Nafion fluorine-containing sulfonic acid resin, 40 grams of polyethylene glycol (average molecular weight 1000); Nafion fluorine-containing sulfonic acid resin is placed in the LiOH saturated aqueous solution of 5mol / L and its fluorine-containing sulfonic acid conversion is carried out by ion exchange After forming fluorine-containing lithium sulfonate, it was dissolved in 1500 grams of N,N-dimethylformamide with polyethylene glycol; the prepared solution was spread on a clean glass plate by solution casting method, and allowed to The solvent evaporates to form a film; the glass plate and the film are immersed in a room temperature alcohol-water mixed solution (30% volume of methanol) for 60 minutes to separate the film from the glass plate, and the film is soaked in new 60°C deionized water for 560 minutes, and then again Soak in new deionized water at room temperature for 220 minutes, extract the polyethylene glycol in the membrane to obtai...

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Abstract

The invention discloses a lithium single ionic conductive microporous electrolyte membrane. The lithium single ionic conductive microporous electrolyte membrane is prepared from the following raw material components: a macromolecular material containing sulfonic acid or an amide sulphonate group, a water-soluble polymer and a macromolecular additive, wherein the macromolecular material containing sulfonic acid or the amide sulphonate group, the water-soluble polymer and the macromolecular additive respectively account for 25-95%, 5-75% and 0-40% of the weight of the total raw material components in percentage by weight. The lithium single ionic conductive microporous electrolyte membrane is simple in preparation method and can be electroconductive in a carbonate ester solvent without adding lithium salt; lithium ion content, hole ratio and hole size are adjusted by virtue of a reasonable formula, lithium ion transference number is close to 1, electrical conductivity at room temperature is excellent and stable, and the electrical conductivities at room temperature in different carbonate ester solvents can be more than 1*10<-3>S / cm; operating temperature ranges from -40 DEG C to 80 DEG C, and the electrical conductivity of the lithium single ionic conductive microporous electrolyte membrane at the temperature of minus 20 DEG C is still close to 1*10<-3>S / cm.

Description

technical field [0001] The invention relates to a lithium single-ion conductive microporous electrolyte membrane and a preparation method thereof. Background technique [0002] Lithium-ion batteries have become the most popular source of power due to their advantages such as high-density energy, long cycle life, no memory effect, strong safety and reliability, and fast charging and discharging. Lithium-ion batteries using polymer electrolyte membranes have the characteristics of small size and changeable shape, so they are widely used in portable electronic products, such as laptop computers, cameras, mobile communication equipment, etc. Large-capacity polymer lithium-ion batteries are also used in electric vehicles, and are expected to become one of the main sources of power for electric vehicles in the 21st century, and will be used in artificial satellites, aerospace and energy storage. [0003] The working principle of lithium-ion batteries is that lithium ions in the b...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): H01M10/0565C08J9/36C08J9/26
CPCH01M10/0565H01M10/058H01M2300/0065Y02E60/10
Inventor 蒋继明徐奎王庆
Owner 江苏明魁高分子材料技术有限公司
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