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Novel conjugated fluorine-containing sulfimide single ion conductor polymer and preparation and application methods thereof

A technology of sulfonimide single and conjugated structure, which is applied in structural parts, electrical components, electrochemical generators, etc.

Active Publication Date: 2019-03-12
宁波嘉玛材料科技有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] There is no report of a conjugated sulfonimide group containing two adjacent imide groups (i.e. -SO 2 -N (-) -SO 2 -N (-) -SO 2 -) polymer single ion conductor

Method used

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  • Novel conjugated fluorine-containing sulfimide single ion conductor polymer and preparation and application methods thereof
  • Novel conjugated fluorine-containing sulfimide single ion conductor polymer and preparation and application methods thereof
  • Novel conjugated fluorine-containing sulfimide single ion conductor polymer and preparation and application methods thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0049] Will ICF 2 SO 2 Dissolve Cl in a mixed solution of acetonitrile and water (acetonitrile:water=3:1), add sodium dithionite, react at 25°C for 6h, extract with acetonitrile and dry to obtain sodium perfluorobissulfinate NaSO 2 CF 2 SO 2 Na. NaSO 2 CF 2 SO 2 Na is dissolved in a certain amount of water to form a solution with a concentration of 1g / ml. Introduce chlorine gas, react at 0°C for 2 hours, and obtain perfluorobissulfonyl chloride ClSO with both chlorosulfonyl groups 2 CF 2 SO 2 Cl. The resulting perfluorobissulfonyl chloride ClSO 2 CF 2 SO 2 Cl monomer and sulfonamide SO 2 (NH 2 ) 2 Dissolve in dry ether and add Na 2 CO 3 , placed under the condition of 25° C. for 24 hours to obtain a novel conjugated structure fluorine-containing sulfonimide single ion conductor polymer. Its structure is shown in formula (Ⅶ):

[0050]

Embodiment 2

[0052] I(CF 2 ) 25 F was dissolved in a mixed solution of chloroform and water (chloroform:water=3:2), added lithium dithionite, reacted at 70°C for 24h, separated and dried to obtain lithium perfluorobissulfinate LiSO 2 (CF 2 ) 25 SO 2 Li. Will LiSO 2 (CF 2 ) 25 SO 2 Li is dissolved in a certain amount of water to form a solution with a concentration of 15 g / ml. Introduce chlorine gas, react at 20°C for 10 hours, and obtain perfluorobissulfonyl chloride ClSO with both chlorosulfonyl groups 2 (CF 2 ) 25 SO 2 Cl. The resulting perfluorobissulfonyl chloride ClSO 2 (CF 2 ) 25 SO 2 Cl monomer and sulfonamide SO 2 (NH 2 ) 2 Dissolve in dry chloroform, add KF, and react at 80°C for 10 days to obtain a novel conjugated structure fluorine-containing sulfonimide single ion conductor polymer. Its structure is shown in formula (Ⅷ):

[0053]

Embodiment 3

[0055] Will CF 3 CF 2 OCF 2 CF 2 SO 2 Dissolve Br in a mixed solution of dichloromethane and water (chloroform:water=1:1), add potassium dithionite, react at 50°C for 12h, separate and dry to obtain potassium perfluorobissulfinate KSO 2 CF 2 CF 2 OCF 2 CF 2 SO 2 K. will KSO 2 CF 2 CF 2 OCF 2 CF 2 SO 2 Dissolve K in a certain amount of water, prepare a solution with a concentration of 10g / ml, pass through chlorine gas, and react at 4°C for 4 hours to obtain perfluorobissulfonyl chloride ClSO with both chlorosulfonyl groups 2 CF 2 CF 2 OCF 2 CF 2 SO 2 Cl. The resulting perfluorobissulfonyl chloride ClSO 2 CF 2 CF 2 OCF 2 CF 2 SO 2 Cl monomer and sulfonamide SO 2 (NH 2 ) 2 Dissolve in dry acetonitrile, add CsF, and react at 50°C for 3 days to obtain a perfluorosulfonimide polyanion cesium salt polymer with a binary structure. Dissolve the obtained binary structure perfluorosulfonimide polyanion cesium salt polymer in acetonitrile, add lithium perchl...

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Abstract

The invention discloses a novel conjugated fluorine-containing sulfimide single ion conductor polymer and preparation and application methods thereof. The general formula of the novel conjugated fluorine-containing sulfimide single ion conductor polymer is shown as formula I. the preparation method of the novel conjugated fluorine-containing sulfimide single ion conductor polymer comprises dehalogenating and sulfonating perfluorochemicals and derivative monomers of the perfluorochemicals into perfluorochemical bisulfimides and derivatives of the perfluorochemical bisulfimides; then reacting the perfluorochemical bisulfimides and the derivatives with chlorine to graft chlorosulfonyl groups onto both ends of the perfluorochemical bisulfimides and the derivatives and then with sulfamides forpolycondensation under the action of acid-binding agent to obtain a perfuoropolymer containing a conjugated sulfimide structure. The prepared novel conjugated fluorine-containing sulfimide single ionconductor polymer is high in chemical stability and thermal stability, and with the unique conjugated sulfimide structure, achieves high ionic conductivity and high application values when applied tobattery materials such as lithium ion battery binders and solid and liquid eletrolytes. The preparation method of the novel conjugated fluorine-containing sulfimide single ion conductor polymer is fewin synthesizing processes, simple, low in cost and applicable to industrialized production.

Description

technical field [0001] The invention belongs to the technical field of polymer materials, and relates to the preparation of a novel conjugated structure fluorine-containing sulfonimide single-ion conductor polymer, and its application in battery materials such as polymer solid electrolytes, electrolytes, and binders. application. Background technique [0002] Fluorinated sulfonylimides are a class of stronger Bronsted acids. The negative charge on the N atom will be highly delocalized under the induction of the sulfonyl group and the fluoroalkyl group, and the fluoroalkyl group has a large volume, which makes this type of anion have a large steric hindrance and weak coordination ability with the positive ion, so Fluoroalkylsulfonylimides become super-strong protic acids, and their corresponding salts become strong Lewis acids. Due to their high ionic conductivity, superacid groups such as sulfonimides are often introduced into polymer systems as functional groups to prepar...

Claims

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Application Information

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IPC IPC(8): C08G75/30H01M4/62H01M10/0525H01M10/0565
CPCC08G75/30H01M4/622H01M10/0525H01M10/0565Y02E60/10
Inventor 李丹陆地
Owner 宁波嘉玛材料科技有限公司
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