纺织学报 ›› 2024, Vol. 45 ›› Issue (09): 26-32.doi: 10.13475/j.fzxb.20230600801

• 纤维材料 • 上一篇    下一篇

聚乙烯亚胺/聚丙烯腈复合纤维薄膜的制备及其功能化应用

王浩然1, 于影2(), 左雨欣3, 顾志清2, 卢海龙1, 陈洪立1, 柯俊1   

  1. 1.浙江理工大学 机械工程学院, 浙江 杭州 310018
    2.嘉兴学院 信息科学与工程学院, 浙江 嘉兴 314001
    3.嘉兴南湖学院, 浙江 嘉兴 314001
  • 收稿日期:2023-06-05 修回日期:2024-03-22 出版日期:2024-09-15 发布日期:2024-09-15
  • 通讯作者: 于影(1988—),女,副教授,博士。研究方向为功能化纤维材料制备与柔性电子器件。E-mail: yingyu@zjxu.edu.cn。
  • 作者简介:王浩然(1999—),男,硕士生。主要研究方向为功能纤维。
  • 基金资助:
    国家自然科学基金项目(52305059);浙江省自然科学基金项目(LGG21E050021);嘉兴市应用性基础研究专项资助项目(2020AY10015);嘉兴市应用性基础研究专项资助项目(2020AD10015);嘉兴市应用性基础研究专项资助项目(2021AY30020)

Preparation and functional application of polyethyleneimine/polyacrylonitrile composite fiber membrane

WANG Haoran1, YU Ying2(), ZUO Yuxin3, GU Zhiqing2, LU Hailong1, CHEN Hongli1, KE Jun1   

  1. 1. School of Mechanical Engineering, Zhejiang Sci-Tech University, Hangzhou, Zhejiang 310018, China
    2. College of Information Science and Engineering, Jiaxing University, Jiaxing, Zhejiang 314001, China
    3. Jiaxing Nanhu University, Jiaxing, Zhejiang 314001, China
  • Received:2023-06-05 Revised:2024-03-22 Published:2024-09-15 Online:2024-09-15

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摘要：

针对金属-空气电池阴极易腐蚀的问题,将聚乙烯亚胺(PEI)和聚丙烯腈(PAN)共混,基于静电纺丝方法制备PEI/PAN复合纤维薄膜,抑制CO2对空气阴极的侵蚀。借助计算机模拟方法计算PEI/PAN复合纤维薄膜的最佳成分配比,采用扫描电子显微镜、傅里叶变换红外吸收光谱仪、同步热分析仪等对PEI/PAN复合纤维薄膜的物理特性、CO2吸附性能进行表征和分析。以铝-空气电池为例,通过电池测试系统分析了PEI/PAN复合纤维薄膜对电池电化学性能的影响情况。结果表明:基于静电纺丝技术可成功将PEI嵌入PAN纤维中,所制备的PEI/PAN复合纤维薄膜纤维直径均一且表面光滑;当PEI/PAN复合纤维薄膜中的PEI质量分数为50%时,在100 kPa条件下其CO2吸附量可达1.86 mmol/g;在金属-空气电池阴极添加PEI/PAN复合纤维薄膜,相较于传统铝-空气电池,其比容量提升19.5%,放电时间延长20.4%。

关键词: 复合纤维薄膜, CO2吸附, 聚乙烯亚胺, 聚丙烯腈, 空气阴极腐蚀, 金属-空气电池, 静电纺丝

Abstract:

Objective The CO2 corrosion of metal-air batteries is extremely serious, which greatly limits the service life of the metal-air batteries. Existing researches generally add CO2 absorbers or O2 selective membranes to the cathodes, which indeed inhibit the CO2 corrosion to a certain extent, but have a negative impact on the electrochemical performance of the batteries. Therefore, there is an urgent need to explore a new method to inhibit cathode corrosion in metal-air batteries, which would not sacrifice the electrochemical performance of the battery and can effectively inhibit CO2 corrosion.

Method Polyethyleneimine/polyacrylonitrile (PEI/PAN) precursor solutions with different PEI contents were prepared, and PEI/PAN composite fiber membranes were fabricated by electrospinning. The microstructure of the composite fiber membrane was characterized by scanning electron microscope and infrared spectrometer. The influences of different PEI contents on the CO2 adsorption performance of PEI/PAN composite fiber membranes were studied combining computer simulation and CO2 adsorption-desorption experiments. An aluminum-air battery with a PEI/PAN composite fiber membrane was prepared to verify the optimization effect of the composite fiber membrane on the discharge performance of the battery.

Results PEI was successfully embedded into PAN fibers through electrospinning, and the surface was smooth and the layered fiber structure was evenly distributed. The computer simulation results showed that the PEI/PAN composite fiber membrane of system II (50% PEI) illustrated excellent adsorption performance, and the CO2 adsorption-desorption experiment further confirmed the simulation results. When the pressure was 100 kPa, the adsorption capacity of PEI/PAN composite fiber membrane was 1.86 mmol/g. The experimental and simulation results agreed well to each other. Taking aluminum-air batteries as an example, aluminum-air batteries with PEI/PAN composite fiber membranes were assembled. Electrochemical test results showed that compared with conventional aluminum-air batteries, the cathode corrosion of aluminum-air batteries with PEI/PAN composite fiber membrane was significantly inhibited. The discharge time of the aluminum battery with PEI/PAN composite fiber membrane was 548 min, while the conventional aluminum-air battery was only 455 min. The discharge time of the battery with the composite fiber film was prolonged by 20.4%, and the specific capacity was increased by 19.5%, proving that the PEI/PAN composite fiber film could effectively inhibit the corrosion of the positive electrode and improve the electrochemical performance of the battery.

Conclusion The PEI/PAN composite fiber membrane prepared has excellent adsorption properties, and its application in metal-air batteries can effectively inhibit the corrosion of CO2 on the air cathode. Adding PEI/PAN composite fiber membrane to the cathode of aluminum-air battery can significantly increase the specific capacity and prolong the discharge time of the battery.

Key words: composite fiber membrane, CO2 adsorption, polyethyleneimine, polyacrylonitrile, air cathode corrosion, metal-air battery, electrostatic spinning

中图分类号: 

  • TQ152

图1

分子动力学模拟模型"

表1

不同PEI/PAN成分配比的模拟参数"

体系 PEI PAN
分子数 质量分数/% 分子数 质量分数/%
Ⅰ 575 33 970 67
Ⅱ 885 50 740 50
Ⅲ 1 050 60 565 40

图2

静电纺丝制备过程原理图及PEI/PAN复合纤维薄膜"

图3

铝空气电池组装及放电实验平台示意图"

图4

PEI/PAN复合纤维薄膜扫描电镜照片及红外光谱图"

图5

PEI/PAN复合纤维薄膜CO2吸附情况的模拟结果"

表2

不同压强条件PEI/PAN复合纤维薄膜的CO2吸附量模拟结果"

压强/
kPa		 吸附量/(mmol·g-1)
体系Ⅰ 体系Ⅱ 体系Ⅲ
40 1.34 1.65 1.01
65 1.55 1.95 1.05
100 1.82 2.05 1.26

表3

不同压强条件下PEI/PAN复合纤维薄膜的CO2吸附量实验测试结果"

压强/
kPa		 吸附量/(mmol·g-1)
体系Ⅰ 体系Ⅱ 体系Ⅲ
40 1.18 1.66 0.88
65 1.29 1.73 1.00
100 1.54 1.86 1.12

表4

Avrami力学模型计算参数"

体系 压强/
kPa		 qm/
(mmol·g-1)		 ka/
min-1		 n
Ⅰ 40 1.34 0.016 1.121
65 1.55 0.016 1.121
100 1.82 0.016 1.121
Ⅱ 40 1.65 0.018 1.131
65 1.95 0.018 1.131
100 2.05 0.018 1.131
Ⅲ 40 1.01 0.034 1.117
65 1.05 0.034 1.117
100 1.26 0.034 1.117

图6

复合纤维薄膜在不同压强下的CO2吸附量"

图7

CO2吸附循环曲线"

图8

铝-空气电池放电性能"

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