Cross-linked anion membrane, preparation method thereof and application

Abstract

The invention discloses a high-performance cross-linked anion membrane and a preparation method thereof. The anion membrane is prepared from polymer containing benzyl halide perssad by means of biguanide or multi-guanidine cross-linking. The membrane can be applied to fuel batteries or energy storage batteries containing acid electrolyte flow. The membrane is compact in structure, low in deformation and moisture content and fine in ion selectivity, and is fine in thermal stability and anti-oxidation stability due to more dispersive distribution of positive charges. In addition, diffusion of vanadium ions in a full-vanadium-flow energy storage battery can be effectively blocked by high alkalinity of the biguanide or multi-guanidine inter-linked anion membrane, simultaneously, swelling can be inhibited by the inter-linked property, diffusion of the vanadium ions further can be inhibited, coulombic efficiency of the battery is increased to reach 99% at least, and high stability, high conductivity and low swelling are realized.

Description

technical field

[0001] The invention relates to the field of battery membrane materials, in particular to a high-performance cross-linked anion membrane, a preparation method thereof and the application of the membrane in fuel cells and acid electrolyte flow energy storage batteries. Background technique

[0002] Anion exchange membranes are key materials for separation and purification, and chemical power sources, and have important applications in water treatment, alkaline fuel cells, and liquid flow energy storage batteries. The commonly used anion exchange membranes are mainly quaternary ammonium anion membranes. However, such anionic membranes have low electrical conductivity, poor thermal and chemical stability, and are far from meeting the practical and commercial requirements of batteries.

[0003] Therefore, people try to change the ion-conducting groups of the anion membrane to improve the conductivity and stability of the membrane. Li Zhongfang et al. invented a ...

Examples

Embodiment 1

[0085] Under nitrogen atmosphere, at 0°C, add 1 mass part of tetramethylurea dissolved in 8 mass parts of ether, after mixing evenly, drop 4 mass parts of oxalyl chloride into the system at a speed of 2 drops / s After the dropwise addition, stir for 30 minutes, slowly raise the temperature to 60° C., and reflux for 3 hours. The solvent was removed by evaporation. A pale yellow solid was obtained. That is tetramethyl Vilsmeyer salt.

[0086]Dissolve 1 mole fraction of the prepared tetramethyl Vilsmeyer salt in 10 mole fractions of acetonitrile, slowly add 1 mole fraction of dry methylamine, after the addition, slowly raise the temperature to 90°C and reflux for over 4 hours. Stop responding. Under vigorous stirring, add 5molL -1 NaOH aqueous solution until the solution is clear. Separate the organic phase and remove the solvent to prepare pentamethylguanidine.

[0087] 1 mole fraction of the prepared Vilsmeyer salt was dissolved in 10 mole fractions of acetonitrile, and a ...

Embodiment 2

[0096] Under nitrogen atmosphere, at 0°C, add 1 mass part of tetramethylurea dissolved in 8 mass parts of ether, after mixing evenly, drop 4 mass parts of oxalyl chloride into the system at a speed of 2 drops / s After the dropwise addition, stir for 30 minutes, slowly raise the temperature to 60° C., and reflux for 3 hours. The solvent was removed by evaporation. A pale yellow solid was obtained. That is tetramethyl Vilsmeyer salt.

[0097] Dissolve 1 mole fraction of the prepared tetramethyl Vilsmeyer salt in 10 mole fractions of acetonitrile, slowly add 1 mole fraction of dry methylamine, after the addition, slowly raise the temperature to 90°C and reflux for over 4 hours. Stop responding. Under vigorous stirring, add 5molL -1 NaOH aqueous solution until the solution is clear. Separate the organic phase and remove the solvent to prepare pentamethylguanidine.

[0098] 1 mole fraction of the prepared Vilsmeyer salt was dissolved in 10 mole fractions of acetonitrile, and a...

Embodiment 3

[0104] Under an argon atmosphere, at 5°C, add 1 mass part of N,N-diethylpropenyl urea dissolved in 10 mass parts of dichloromethane, mix well, and add dropwise at a speed of 3 drops / s 6 parts by mass of oxalyl chloride was added to the system, after the dropwise addition, stirred for 20 minutes, slowly heated to 50°C, and refluxed for 4 hours. The solvent was removed by evaporation. A pale yellow solid was obtained. That is N, N-diethylpropenyl Vilsmeyer salt.

[0105] Take the prepared 1 mole fraction of N,N-diethylpropenyl Vilsmeyer salt and dissolve it in acetonitrile, and slowly add a dry mixture of 0.5 mole fractions of 1,6-hexanediamine and 2 mole fractions of triethylamine . After the dropwise addition, the temperature was slowly raised to 100° C. for reflux reaction for 24 hours. Under vigorous stirring, add 10molL -1 KOH aqueous solution until the system is clear. Separate the organic phase, remove the solvent and triethylamine, and dry in vacuum to prepare N,N-...

technical field

[0001] The invention relates to the field of battery membrane materials, in particular to a high-performance cross-linked anion membrane, a preparation method thereof and the application of the membrane in fuel cells and acid electrolyte flow energy storage batteries. Background technique

[0002] Anion exchange membranes are key materials for separation and purification, and chemical power sources, and have important applications in water treatment, alkaline fuel cells, and liquid flow energy storage batteries. The commonly used anion exchange membranes are mainly quaternary ammonium anion membranes. However, such anionic membranes have low electrical conductivity, poor thermal and chemical stability, and are far from meeting the practical and commercial requirements of batteries.

[0003] Therefore, people try to change the ion-conducting groups of the anion membrane to improve the conductivity and stability of the membrane. Li Zhongfang et al. invented a ...

Examples

Embodiment 1

[0085] Under nitrogen atmosphere, at 0°C, add 1 mass part of tetramethylurea dissolved in 8 mass parts of ether, after mixing evenly, drop 4 mass parts of oxalyl chloride into the system at a speed of 2 drops / s After the dropwise addition, stir for 30 minutes, slowly raise the temperature to 60° C., and reflux for 3 hours. The solvent was removed by evaporation. A pale yellow solid was obtained. That is tetramethyl Vilsmeyer salt.

[0086]Dissolve 1 mole fraction of the prepared tetramethyl Vilsmeyer salt in 10 mole fractions of acetonitrile, slowly add 1 mole fraction of dry methylamine, after the addition, slowly raise the temperature to 90°C and reflux for over 4 hours. Stop responding. Under vigorous stirring, add 5molL -1 NaOH aqueous solution until the solution is clear. Separate the organic phase and remove the solvent to prepare pentamethylguanidine.

[0087] 1 mole fraction of the prepared Vilsmeyer salt was dissolved in 10 mole fractions of acetonitrile, and a ...

Embodiment 2

[0096] Under nitrogen atmosphere, at 0°C, add 1 mass part of tetramethylurea dissolved in 8 mass parts of ether, after mixing evenly, drop 4 mass parts of oxalyl chloride into the system at a speed of 2 drops / s After the dropwise addition, stir for 30 minutes, slowly raise the temperature to 60° C., and reflux for 3 hours. The solvent was removed by evaporation. A pale yellow solid was obtained. That is tetramethyl Vilsmeyer salt.

[0097] Dissolve 1 mole fraction of the prepared tetramethyl Vilsmeyer salt in 10 mole fractions of acetonitrile, slowly add 1 mole fraction of dry methylamine, after the addition, slowly raise the temperature to 90°C and reflux for over 4 hours. Stop responding. Under vigorous stirring, add 5molL -1 NaOH aqueous solution until the solution is clear. Separate the organic phase and remove the solvent to prepare pentamethylguanidine.

[0098] 1 mole fraction of the prepared Vilsmeyer salt was dissolved in 10 mole fractions of acetonitrile, and a...

Embodiment 3

[0104] Under an argon atmosphere, at 5°C, add 1 mass part of N,N-diethylpropenyl urea dissolved in 10 mass parts of dichloromethane, mix well, and add dropwise at a speed of 3 drops / s 6 parts by mass of oxalyl chloride was added to the system, after the dropwise addition, stirred for 20 minutes, slowly heated to 50°C, and refluxed for 4 hours. The solvent was removed by evaporation. A pale yellow solid was obtained. That is N, N-diethylpropenyl Vilsmeyer salt.

[0105] Take the prepared 1 mole fraction of N,N-diethylpropenyl Vilsmeyer salt and dissolve it in acetonitrile, and slowly add a dry mixture of 0.5 mole fractions of 1,6-hexanediamine and 2 mole fractions of triethylamine . After the dropwise addition, the temperature was slowly raised to 100° C. for reflux reaction for 24 hours. Under vigorous stirring, add 10molL -1 KOH aqueous solution until the system is clear. Separate the organic phase, remove the solvent and triethylamine, and dry in vacuum to prepare N,N-...

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