膜科学与技术

位置：首页 >> 期刊内容阅读

氧化黑磷纳米片/SPEEK复合质子交换膜制备及性能

作者：afzal，陈婉婷，逄博，姜晓滨，吴雪梅，贺高红

单位：大连理工大学化工学院，精细化工国家重点实验室，膜科学与技术研究中心，大连 116024

关键词：质子交换膜；磺化聚醚醚酮；氧化黑磷纳米片；复合膜

DOI号：

分类号： TM911.4；TQ425.236

出版年,卷(期):页码： 2022,42(1):18-23

摘要：

本文以红磷为前驱体，采用机械研磨法制备黑磷粉末，并通过液相剥离制备了氧化黑磷（ OBP）纳米片。进一步，将OBP纳米片与磺化聚醚醚酮（SPEEK）聚合物共混，制备掺杂量为0~2.5 wt.%的SPEEK/OBP复合质子交换膜。通过透射电镜表征了OBP形貌，并通过FTIR和XPS谱图确定OBP表面含有丰富的含氧官能团。这些含氧官能团可促进复合膜吸水，同时，可与SPEEK中磺酸基团形成氢键网络，促进质子传递。与纯SPEEK膜相比，SPEEK/OBP复合膜具有较高的离子交换容量、吸水率、溶胀率和质子传导率。当OBP纳米片添加量为2.0 wt.%时，SPEEK/OBP复合膜性能最优，其质子传导率在30℃时为0.026 S/cm，为纯SPEEK膜的1.71倍。

Oxidized black phosphorus (OBP) nanosheet was prepared by mechanical grinding of black phosphorus powder using red phosphorus as precursor and subsequent liquid-phase exfoliation process. OBP nanosheets were further incorporated into sulfonated poly (ether ether ketone) matrix to regulate ionic channels and enhance proton transport. The obtained composite proton exchange membranes (SPEEK/OBP) with 0~2.5 wt.% of OBP were prepared by a conventional solution casting method. As confirmed by FTIR and XPS spectra, OBP surface contains abundant oxygen-containing functional groups, which can promote water sorption of the composite membranes and form hydrogen bond network with sulfonic acid groups in SPEEK, facilitating proton transfer. Compared with the pristine SPEEK membrane, the SPEEK/OBP composite membrane exhibits higher ion exchange capacity (IEC), water uptake, swelling ratio and proton conductivity. With the optimal content of OBP nanosheets (2.0 wt.%), the SPEEK/OBP membrane achieves to the best performance, i.e., its proton conductivity was 0.026 S/cm at 30 ℃, which is 1.71 times as high as that of the pristine SPEEK membrane.

基金项目：

国家自然科学基金（22008021, 21776034, 创新群体22021005）。

作者简介：

Afzal（1995-），男，巴基斯坦，硕士生，主要从事质子交换膜的制备及性能研究

参考文献：

[1] Ran J, Wu L, He Y, et al. Ion exchange membranes: New developments and applications[J]. J Membr Sci, 2017, 522: 267-291.
[2] Dai W, Yu L, Li Z, et al. Sulfonated poly(ether ether ketone)/graphene composite membrane for vanadium redox flow battery[J]. Electrochim Acta, 2014, 132: 200-207.
[3] 王云晴, 苑倩倩, 吴雪梅, 等. SGO/SPEEK同轴电纺纤维质子交换膜的制备[J]. 膜科学与技术, 2019, 39(4): 1-7.
[4] Chen W, Chen M, Zhen D, et al. SO42–/SnO2 solid superacid granular stacked one-dimensional hollow nanofiber for a highly conductive proton-exchange membrane[J]. ACS Appl Mater Interfaces, 2020, 12: 40740-40748.
[5] Tong X, Zhang B, Fan Y, et al. Mechanism exploration of ion transport in nanocomposite cation exchange membranes[J]. ACS Appl Mater Interfaces, 2017, 9: 13491-13499.
[6] Li X, Yu Y, Meng Y, Novel quaternized poly(arylene ether sulfone)/Nano-ZrO(2) composite anion exchange membranes for alkaline fuel cells[J]. ACS Appl Mater Interfaces, 2013, 5: 1414-1422.
[7] 甄栋兴, 唐帅, 陈木森, 等. 硫酸化SnO2/SPPESK复合质子交换膜的制备及燃料电池性能[J]. 化工进展, 2019, 38(1): 529-537.
[8] Guo Z, Ding W, Liu X, et al. Two-dimensional black phosphorus: A new star in energy applications and the barrier to stability[J]. Appl Mater Today, 2019, 14: 51-58.
[9] Edmonds M T, Tadich A, Carvalho A, et al. Creating a stable oxide at the surface of black phosphorus[J]. ACS Appl Mater Interfaces, 2015, 7: 14557-14562.
[10] Zhang Z, Zhang P, Yang S, et al. Oxidation promoted osmotic energy conversion in black phosphorus membranes[J]. Proc Natl Acad Sci U S A, 2020, 117(25): 13959–13966.
[11] Park C M, Sohn H J, Black phosphorus and its composite for lithium rechargeable batteries[J]. Adv Mater, 2007, 19: 2465-2468.
[12] Yasaei P, Kumar B, Foroozan T, et al. A. Salehi-Khojin, High-quality black phosphorus atomic layers by liquid-phase exfoliation[J]. Adv Mater, 2015, 27: 1887-1892.
[13] Song S, Raja I, Lee Y, et al. Comparison of cytotoxicity of black phosphorus nanosheets in different types of fibroblasts[J]. Biomater Res, 2019, 23: 23.
[14] Nakhanivej P, Yu X, Park S, et al. Revealing molecular-level surface redox sites of controllably oxidized black phosphorus nanosheets[J]. Nature Mat, 2019, 18: 156-162.
[15] Destainville A, Champion E, Bernache-Assollant D, et al. Synthesis, characterization and thermal behavior of apatitic tricalcium phosphate[J]. Mater Chem Phys, 2003, 80: 269-277.
[16] Huang Y, Qiao J, He K, et al. Interaction of black phosphorus with oxygen and water[J]. Chem Mat, 2016, 28: 8330-8339.
[17] Li X, Nie G, Tao J, et al. Assessing the influence of side-chain and main-chain aromatic benzyltrimethyl ammonium on anion exchange membranes[J]. ACS Appl Mater Interfaces, 2014, 6: 7585-7595.
[18] Shin D W, Guiver M D, Lee Y M, Hydrocarbon-based polymer electrolyte membranes: Importance of morphology on ion transport and membrane stability[J]. Chem Rev, 2017, 117: 4759-4805.

服务与反馈：

【文章下载】【加入收藏】

《膜科学与技术》编辑部地址：北京市朝阳区北三环东路19号蓝星大厦邮政编码：100029 电话：010-64426130/64433466 传真：010-80485372邮箱：mkxyjs@163.com