全钒液流电池用酸碱对质子交换膜的制备及性能
发布时间：2019-04-16 20:59
【摘要】：全钒液流电池具有充放电效率高、使用寿命长、绿色安全和价格低廉等优点,成为储能系统的最佳选择。质子交换膜是全钒液流电池的核心组件之一,决定了钒电池的能量效率和使用寿命。目前钒电池质子交换膜为Nafion系列,但昂贵价格,高钒离子透过率,低的电流效率制约了钒电池的商业化。研究开发一种低成本、化学稳定性好、质子传导率高和钒离子渗透率低的质子交换膜是推进全钒液流电池应用的关键。磺化聚醚醚酮(sulfonated poly(ether ether ketone),SPEEK)质子交换膜具有低成本、高选择性、制备简单等优点。作为钒电池膜材料使用时,电池能量效率与其磺化度高低有密切关系。低磺化度SPEEK的质子传导性低,不适合用于钒电池;高磺化度SPEEK的溶胀度大,增加了钒离子透过率。本论文通过掺杂功能化氧化石墨烯(GO)改性高磺化度的SPEEK膜,探讨了复合膜结构与性能的关系。以对苯二胺(PPD)为修饰剂,制备了氨基化氧化石墨烯(PPD-GO),与SPEEK共混制备了 SPEEK/PPD-GO复合膜,对复合膜的结构和性能、钒电池性能进行了表征和测试。研究表明,PPD-GO与SPEEK基体界面处形成的酸碱离子对降低了复合膜的溶胀率和钒离子渗透率,保持了较高质子传导率。在30 mA·cm-2电流密度下,含1 wt%PPD-GO的SPEEK复合膜展现了良好的综合性能,单电池的库伦效率(96.9%vs 91%)和能量效率(82.8%vs 66.8%)均高于Nafion 117膜。经300次充放电循环测试,SPEEK/PPD-GO-1膜具有良好的耐酸性和化学稳定性。采用4,4-二氨基二苯醚(ODA)和苯胺(AN)对GO进行了化学修饰,制备了含氮量(3.04%)的氨基化石墨烯(ODA-AN-GO),与SPEEK共混制备了SPEEK/ODA-AN-GO复合膜。研究表明,复合膜中氨基含量的增加,复合膜的酸碱离子对作用增强,提高了复合膜的质子传导率。经300次单电池循环,电池的库伦效率和能量效率保持稳定,2 wf%ODA-AN-GO含量时SPEEK复合膜表现出良好的综合电池性能。
[Abstract]:The full-flow battery has the advantages of high charging and discharging efficiency, long service life, green safety, low price and the like, and becomes the best choice for the energy storage system. The proton exchange membrane is one of the core components of the full-flow battery, and the energy efficiency and the service life of the battery are determined. At present, the proton exchange membrane of the lithium ion battery is the Nafion series, but the high price, the high ion permeability and the low current efficiency restrict the commercialization of the solar cell. The research and development of a proton exchange membrane with low cost, good chemical stability, high proton conductivity and low ion permeability is the key to the application of the full-flow battery. The sulfonated polyetheretherketone (SPEEK) proton exchange membrane has the advantages of low cost, high selectivity, simple preparation and the like. As the battery membrane material is used, the energy efficiency of the battery is closely related to the degree of sulfonation. The low sulfonation degree of the SPEEK has low proton conductivity and is not suitable for use in the lithium ion battery; the swelling degree of the high sulfonation degree SPEEK is large, and the transmittance of the high sulfonation degree is increased. In this paper, the relationship between the structure and properties of the composite membrane is discussed by doping the functionalized graphene oxide (GO) modified SPEEK film with high degree of sulfonation. An amino-modified graphene (PPD-GO) was prepared by using p-phenylenediamine (PPD) as a modifier, and the SPEEK/ PPD-GO composite film was prepared by blending with SPEEK. The structure and properties of the composite film were characterized and tested. The results show that the acid-base ion formed at the interface of the PPD-GO and the SPEEK matrix reduces the swelling rate and the ionic permeability of the composite membrane, and maintains the higher proton conductivity. At the current density of 30 mA 路 cm-2, the SPEEK composite film with 1 wt% PPD-GO exhibited a good comprehensive performance, and the coulombic efficiency of the single cell (96.9% vs 91%) and the energy efficiency (82.8% vs 66.8%) were higher than that of the Nafion 117 film. After 300 charge and discharge cycles, the SPEEK/ PPD-GO-1 film has good acid resistance and chemical stability. In this paper,4,4-diaminodiphenyl ether (ODA) and aniline (AN) were used to chemically modify the GO. The aminolated graphene (ODA-AN-GO) with nitrogen content (3.04%) was prepared, and the SPEEK/ ODA-AN-GO composite film was prepared by blending with SPEEK. The results show that the content of amino groups in the composite membrane is increased, the acid-base ion of the composite membrane is enhanced, and the proton conductivity of the composite membrane is improved. After 300 single cell cycle, the cell's coulomb efficiency and energy efficiency were stable, and the SPEEK composite film exhibited good composite battery performance when the content of 2wf% ODA-AN-GO was stable.
【学位授予单位】：天津工业大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TM912
本文编号：2459099
[Abstract]:The full-flow battery has the advantages of high charging and discharging efficiency, long service life, green safety, low price and the like, and becomes the best choice for the energy storage system. The proton exchange membrane is one of the core components of the full-flow battery, and the energy efficiency and the service life of the battery are determined. At present, the proton exchange membrane of the lithium ion battery is the Nafion series, but the high price, the high ion permeability and the low current efficiency restrict the commercialization of the solar cell. The research and development of a proton exchange membrane with low cost, good chemical stability, high proton conductivity and low ion permeability is the key to the application of the full-flow battery. The sulfonated polyetheretherketone (SPEEK) proton exchange membrane has the advantages of low cost, high selectivity, simple preparation and the like. As the battery membrane material is used, the energy efficiency of the battery is closely related to the degree of sulfonation. The low sulfonation degree of the SPEEK has low proton conductivity and is not suitable for use in the lithium ion battery; the swelling degree of the high sulfonation degree SPEEK is large, and the transmittance of the high sulfonation degree is increased. In this paper, the relationship between the structure and properties of the composite membrane is discussed by doping the functionalized graphene oxide (GO) modified SPEEK film with high degree of sulfonation. An amino-modified graphene (PPD-GO) was prepared by using p-phenylenediamine (PPD) as a modifier, and the SPEEK/ PPD-GO composite film was prepared by blending with SPEEK. The structure and properties of the composite film were characterized and tested. The results show that the acid-base ion formed at the interface of the PPD-GO and the SPEEK matrix reduces the swelling rate and the ionic permeability of the composite membrane, and maintains the higher proton conductivity. At the current density of 30 mA 路 cm-2, the SPEEK composite film with 1 wt% PPD-GO exhibited a good comprehensive performance, and the coulombic efficiency of the single cell (96.9% vs 91%) and the energy efficiency (82.8% vs 66.8%) were higher than that of the Nafion 117 film. After 300 charge and discharge cycles, the SPEEK/ PPD-GO-1 film has good acid resistance and chemical stability. In this paper,4,4-diaminodiphenyl ether (ODA) and aniline (AN) were used to chemically modify the GO. The aminolated graphene (ODA-AN-GO) with nitrogen content (3.04%) was prepared, and the SPEEK/ ODA-AN-GO composite film was prepared by blending with SPEEK. The results show that the content of amino groups in the composite membrane is increased, the acid-base ion of the composite membrane is enhanced, and the proton conductivity of the composite membrane is improved. After 300 single cell cycle, the cell's coulomb efficiency and energy efficiency were stable, and the SPEEK composite film exhibited good composite battery performance when the content of 2wf% ODA-AN-GO was stable.
【学位授予单位】：天津工业大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TM912
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