阅读说明：本技术 一种钒电池用聚醚醚酮基质子交换膜 (Polyether-ether-ketone matrix proton exchange membrane for vanadium battery ) 是由 陈德胜 于 2019-10-15 设计创作，主要内容包括：本发明涉及全钒液流电池技术领域,且公开了一种钒电池用聚醚醚酮基质子交换膜,包括以下重量份数配比的原料：8份的磺化聚醚醚酮(SPEEK)、0.42～1.41份的磺化高密度聚乙烯(SHDPE)、0.03～0.07份的纳米二氧化钛(TiO<Sub>2</Sub>)颗粒；上述质子交换膜的制备方法包括以下步骤：以N,N-二甲基甲酰胺(DMF)为溶剂,取上述的SPEEK、SHDPE、TiO<Sub>2</Sub>配制成质量分数为15％的均相溶液,使用100um厚度的刮膜棒进行刮膜,首先将膜在室温下真空干燥2h,然后在60℃烘箱中放置12h,之后在100℃真空干燥2h,最后冷却至室温将膜在去离子水中浸泡下揭膜,即制备得到质子交换膜。本发明解决了目前全钒液流电池使用的质子交换膜,存在钒离子透过率高且价格昂贵的技术问题。(The invention relates to the technical field of all-vanadium redox flow batteries, and discloses a polyether-ether-ketone matrix proton exchange membrane for a vanadium battery, which comprises the following raw materials in parts by weight: 8 parts of sulfonated polyether ether ketone (SPEEK), 0.42-1.41 parts of Sulfonated High Density Polyethylene (SHDPE) and 0.03-0.07 part of nano titanium dioxide (TiO) 2 ) Particles; the preparation method of the proton exchange membrane comprises the following steps: taking N, N-Dimethylformamide (DMF) as solvent, and taking the SPEEK, SHDPE and TiO 2 Preparing a homogeneous solution with the mass fraction of 15%, scraping the membrane by using a membrane scraping rod with the thickness of 100um, firstly drying the membrane in vacuum at room temperature for 2h, then placing the membrane in a drying oven at 60 ℃ for 12h, then drying the membrane in vacuum at 100 ℃ for 2h, finally cooling to room temperature, soaking the membrane in deionized water, and removing the membrane to obtain the proton exchange membrane. The invention solves the technical problems of high vanadium ion transmittance and high price of the proton exchange membrane used by the existing all-vanadium redox flow batteryTo give a title.)

1. The polyether-ether-ketone matrix proton exchange membrane for the vanadium battery is characterized by comprising the following raw materials in parts by weight: 8 parts of sulfonated polyether ether ketone (SPEEK), 0.42-1.41 parts of Sulfonated High Density Polyethylene (SHDPE) and 0.03-0.07 part of nano titanium dioxide (TiO)₂) Particles;

the preparation method of the proton exchange membrane comprises the following steps: taking N, N-Dimethylformamide (DMF) as solvent, and taking the SPEEK, SHDPE and TiO₂Is prepared into a substanceAnd (3) scraping the homogeneous solution with the quantity fraction of 15% by using a film scraping rod with the thickness of 100um, firstly drying the film at room temperature for 2h in vacuum, then placing the film in a drying oven at 60 ℃ for 12h, then drying the film at 100 ℃ in vacuum for 2h, finally cooling to room temperature, soaking the film in deionized water, and removing the film to obtain the proton exchange membrane.

2. The proton exchange membrane according to claim 1 wherein said nano titanium dioxide (TiO)₂) The average particle diameter of the particles is less than or equal to 10 nm.

3. The proton exchange membrane according to claim 2, wherein the proton exchange membrane comprises the following raw materials in parts by weight: 8g of sulfonated polyether ether ketone (SPEEK), 0.88g of Sulfonated High Density Polyethylene (SHDPE) and 0.03g of nano titanium dioxide (TiO)₂) And (3) granules.

4. The proton exchange membrane according to claim 3, wherein the proton exchange membrane comprises the following raw materials in parts by weight: 8g of sulfonated polyether ether ketone (SPEEK), 0.42g of Sulfonated High Density Polyethylene (SHDPE) and 0.05g of nano titanium dioxide (TiO)₂) And (3) granules.

Technical Field

The invention relates to the technical field of all-vanadium redox flow batteries, in particular to a polyether-ether-ketone matrix proton exchange membrane for a vanadium battery.

Background

The all-vanadium redox flow battery (VRB) is the best choice for an energy storage system due to high charging and discharging efficiency, long service life, green safety and low price. The Proton Exchange Membrane (PEM), one of the core components of a VRB system, directly affects the energy efficiency and service life of the cell. Few commercial membranes currently meet the requirements of an ideal PEM, and the expensive price and high vanadium ion permeability of Nafion membranes (perfluorosulfonic acid ion exchange membranes) limit their wider commercial application. Therefore, the research on a PEM which is relatively low in price and is suitable for vanadium batteries is the focus of the research on the vanadium batteries at present.

Disclosure of Invention

Technical problem to be solved

Aiming at the defects of the prior art, the invention provides a polyether ether ketone based proton exchange membrane for a vanadium redox flow battery, which aims to solve the technical problems of high vanadium ion transmittance and high price of the proton exchange membrane used in the existing all-vanadium redox flow battery.

(II) technical scheme

In order to achieve the purpose, the invention provides the following technical scheme:

a polyether-ether-ketone matrix proton exchange membrane for a vanadium battery comprises the following raw materials in parts by weight: 8 parts of sulfonated polyether ether ketone (SPEEK), 0.42-1.41 parts of Sulfonated High Density Polyethylene (SHDPE) and 0.03-0.07 part of nano titanium dioxide (TiO)₂) Particles;

the preparation method of the proton exchange membrane comprises the following steps: taking N, N-Dimethylformamide (DMF) as solvent, and taking the SPEEK, SHDPE and TiO₂Preparing a homogeneous solution with the mass fraction of 15%, scraping the membrane by using a membrane scraping rod with the thickness of 100um, firstly drying the membrane in vacuum at room temperature for 2h, then placing the membrane in a drying oven at 60 ℃ for 12h, then drying the membrane in vacuum at 100 ℃ for 2h, finally cooling to room temperature, soaking the membrane in deionized water, and removing the membrane to obtain the proton exchange membrane.

Further, the nano titanium dioxide (TiO)₂) The average particle diameter of the particles is less than or equal to 10 nm.

Further, the proton exchange membrane comprises the following raw materials in parts by weight: 8g of sulfonated polyether ether ketone (SPEEK), 0.88g of Sulfonated High Density Polyethylene (SHDPE) and 0.03g of nano titanium dioxide (TiO)₂) And (3) granules.

Further, the proton exchange membrane comprises the following raw materials in parts by weight: 8g of sulfonated polyether ether ketone (SPEEK), 0.42g of Sulfonated High Density Polyethylene (SHDPE) and 0.05g of nano titanium dioxide (TiO)₂) And (3) granules.

(III) advantageous technical effects

Compared with the prior art, the invention has the following beneficial technical effects:

the invention adopts sulfonated polyether ether ketone (PEEK), sulfonated High Density Polyethylene (HDPE) and titanium dioxide (TiO) with the average grain diameter less than or equal to 10nm₂) The particles are mixed with solution to obtain the proton cross-linked polymerFilm change, tested: the proton conductivity of the proton exchange membrane is 14.9-15.7 mS/cm, and the vanadium ion transmittance is (2.4-2.8) × 10^-7cm²/min；

Compared with the proton exchange membrane prepared in the comparative example, the proton conductivity is 10.2mS/cm, the vanadium ion transmittance is 6.9 multiplied by 10^-7cm²Compared with the method in/min, the method has the technical effects of obviously improving the proton conductivity and obviously reducing the vanadium ion transmittance; the price of the raw materials used in the invention is far lower than that of the raw materials used in the Nafion membrane;

therefore, the technical problems of high vanadium ion transmittance and high price of the proton exchange membrane used by the existing all-vanadium redox flow battery are solved.

Detailed Description

Sulfonation of Polyetheretherketone (PEEK):

slowly adding 30g of PEEK into a three-neck flask filled with 500mL of 98% concentrated sulfuric acid solution, violently stirring by using mechanical stirring, firstly reacting for 24 hours at room temperature under nitrogen atmosphere, then heating to 50 ℃ for reacting for a certain time, slowly pouring into an ice-water mixture, and continuously stirring to form fibrous white precipitate;

stirring the white fiber precipitate for 1h, standing for 12h, washing with deionized water for multiple times until the pH of the solution is close to 7, filtering to obtain a fibrous sulfonated polyether ether ketone polymer, and finally vacuum-drying at 60 ℃ for 24h and 100 ℃ for 2h to obtain yellow fibrous SPEEK;

wherein the polyether ether ketone (PEEK) has a density of 1.32g/cm³The glass transition temperature Tg is 143 ℃, the tensile strength is 94MPa, the elongation at break is 40-120%, and the bending strength is 140 MPa;

sulfonation of High Density Polyethylene (HDPE):

100mL three-necked flask, and evacuating to replace N₂Three times in N₂Adding 24mL of dichloromethane and 4.8mL of acetic anhydride under the atmosphere, stirring, cooling in an ice bath to 0 ℃, dropwise adding 1.8mL of concentrated sulfuric acid, stirring, continuing to react until the color of the reaction solution is uniform, and finishing the reaction to prepare acetyl sulfate;

adding 6g of High Density Polyethylene (HDPE) and 60mL of dichloromethane into a 100mL three-neck flask, heating to 50 ℃ until the polyethylene is completely dissolved, continuing heating to 60 ℃, then slowly dropwise adding the prepared acetyl sulfate, after dropwise adding, preserving heat for reaction for 2 hours, after the reaction is finished, pouring the reaction liquid into boiling water to precipitate the product, filtering, sequentially washing with acetone and water until the washing liquid is neutral, putting the product into an oven, and drying at 70 ℃ to obtain dried SHDPE;

high Density Polyethylene (HDPE) with a density of 0.941-0.965 g/cm³The melting temperature is 126-136 ℃, the tensile strength is 22-45 MPa, the elongation at break is 200-900%, and the bending strength is 25-40 MPa;