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Branched structure type lithium bis(fluorosulfonyl) imide polymer(R-(PFSILi)n) and synthesis method and application thereof

A technology of polyfluorosulfonimide and branched structure, which is applied in electrochemical generators, electrical components, solid electrolytes, etc., and can solve problems such as toxicity, affecting the safety of battery systems, and being volatile

Active Publication Date: 2016-05-25
NINGBO INST OF MATERIALS TECH & ENG CHINESE ACADEMY OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

These organic electrolytes have many potential safety hazards such as poisonous, volatile and flammable, which seriously affect the safety of the battery system.

Method used

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  • Branched structure type lithium bis(fluorosulfonyl) imide polymer(R-(PFSILi)n) and synthesis method and application thereof
  • Branched structure type lithium bis(fluorosulfonyl) imide polymer(R-(PFSILi)n) and synthesis method and application thereof
  • Branched structure type lithium bis(fluorosulfonyl) imide polymer(R-(PFSILi)n) and synthesis method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0044] Step 1: In an inert atmosphere, the fluorine-containing monomer ClSO 2 CF 2 CF 2 OCF 2 CF 2 SO 2 NH 2 (M n =395.5, 7.1g, 18mmol) was dissolved in acetonitrile (100mL), and CsF (M n =152,12.2g,80mmol), phloroglucinol (M n =126, 0.76g, 6mmol) heated to 50°C and stirred for 4d, the reaction solution was filtered, and the filtrate was rotary evaporated to obtain the branched structure R-(PFSICs) in the form of cesium salt n Polymer, its molecular structural formula is shown in formula (r).

[0045]

[0046] In formula (r), m, n, and p are all integers greater than zero, preferably 20,000 to 50,000.

[0047] Step 2: The branched structure R-(PFSICs) of the cesium salt form obtained in step 1 n (6g) Polymer was dissolved in acetonitrile (16mL), LiClO 4 (1.9g, 18mmol) was dissolved in acetonitrile (2mL), added dropwise to the acetonitrile solution containing the polymer, stirred at 0°C for 24h, and filtered to obtain the lithium salt form polymer R-(PFSILi) n , ...

Embodiment 2

[0051] Step 1: In an inert atmosphere, the fluorine-containing monomer ClSO 2 CF 2 CF 2 OCF 2 CF 2 SO 2 NH 2 (M n =395.5, 8g, 20mmol) was dissolved in acetonitrile (100mL), and KF (M n =58,2.4g, 40mmol), phloroglucinol (M n =126, 0.76g, 6mmol) heated to 60°C and stirred for 5d, the reaction solution was filtered, and the filtrate was rotary evaporated to obtain the branched structure R-(PFSIK) in the form of potassium salt n Polymer, its molecular structure formula is shown in formula (s).

[0052]

[0053] In formula (s), m, n, and p are all integers greater than zero, preferably 20,000-50,000.

[0054] Step 2: the branched structure R-(PFSIK) obtained in step 1 in the potassium salt form n (6g) Polymer was dissolved in tetrahydrofuran (20mL), LiClO 4 (2.13g, 20mmol) was dissolved in tetrahydrofuran (10mL), added dropwise to the tetrahydrofuran solution containing the polymer, stirred at 20°C for 20h, and filtered to obtain the lithium salt form polymer R-(PFSIL...

Embodiment 3

[0058] Step 1: In an inert atmosphere, the fluorine-containing monomer ClSO 2 CF 2 CF 2 OCF 2 CF 2 SO 2 NH 2 (M n =395.5, 4g, 10mmol) was dissolved in acetonitrile (80mL), and Cs was added to this solution 2 CO 3 (M n =326,13g,40mmol), pentaerythriol (M n =120, 0.36g, 3mmol) heated to 100°C and stirred for 1d, the reaction solution was filtered, and the filtrate was rotary evaporated to obtain the branched structure R-(PFSICs) in the form of cesium salt n Polymer, its molecular structural formula is shown in (t) formula.

[0059]

[0060] In formula (t), m, n, and p are all integers greater than zero, preferably 20,000-50,000.

[0061] Step 2: The branched structure R-(PFSICs) of the cesium salt form obtained in step 1 n (7g) polymer was dissolved in acetonitrile (16mL), LiBF 4 (1g, 10mmol) was dissolved in acetonitrile (2mL), added dropwise to the acetonitrile solution containing the polymer, stirred at 30°C for 20h, and then filtered to obtain the polymer in ...

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Abstract

The invention discloses a branched structure type lithium bis(fluorosulfonyl) imide polymer(R-(PFSILi)n) and a synthesis method and application thereof. The polymer is a polyanionic lithium salt polymer with a starlike or treelike structure and the molecular structure of the polymer is as shown in the formula (I). The structuring method of the structure comprises the following steps: selecting different polyphenols or polyols as a substrate; carrying out condensation reaction on a fluorinated monomer and the substrate under the action of an acid-binding agent; and then carrying out lithium ion exchange through a lithium salt to obtain a target molecule. Compared with a one-dimensional direct-chain fluoroalkyl sulfimide structure type polymer, the branched structure type polymer disclosed by the invention has better conductivity and excellent compatibility with anode and cathode materials with high electrochemical activity, also has high lithium ion transference number (t<+> is greater than 0.9) and high electrochemical window (>6V), and further has excellent charge and discharge performance and service life.

Description

technical field [0001] The invention belongs to the technical field of macromolecular materials, and relates to a branched structure type polyfluorosulfonimide anion lithium salt and its synthesis method and application. Background technique [0002] Lithium-ion batteries have the advantages of high specific energy, large storage capacity, no memory effect, long cycle life, and small size. They are research hotspots in new power supply technologies. At present, the lithium-ion battery system mainly uses liquid electrolytes, such as EC (ethylene carbonate), DEC (diethyl carbonate), PC (propylene carbonate), DMC (dimethyl carbonate) and their mixtures. These organic electrolytes have many potential safety hazards such as toxicity, volatile and flammability, which seriously affect the safety of the battery system. Polymer electrolyte can act as electrolyte and battery separator at the same time, so there is no free-flowing electrolyte solution, thus fundamentally eliminating m...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): H01M10/0565H01M10/0525
CPCH01M10/0525H01M10/0565H01M2300/0082Y02E60/10
Inventor 温乐乐薛立新李丹秦德君
Owner NINGBO INST OF MATERIALS TECH & ENG CHINESE ACADEMY OF SCI
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