Preparation and properties of sulfonated polysulfone/black phosphorus composite proton exchange membrane

doi:10.19491/j.issn.1001-9278.2023.11.003

Abstract

Abstract:

A series of sulfonated polysulfone （SPES） was prepared through controlling the reaction temperature and time with polyethersulfone as a raw material and chlorosulfonic acid as a sulfonating agent. Further， proton exchange membrane composites were fabricated through solution casting using 2D black phosphorus as a functional filler and SPES as a matrix. The structures of the as⁃prepared materials were characterized by Fourier transform infrared spectrometer， X⁃ray diffractometer， and scanning electron microscope， and their properties in terms of water absorption， proton exchange and alcohol resistance were studied. The results indicated that the sulfonation degree of SPES increased with increasing the reaction temperature， time， and sulfonation agent concentration. The addition of black phosphorus enhanced the comprehensive properties of the composite membranes， which included thermal stability， oxidation stability， proton exchange ability， and alcohol resistance. Under the same test conditions， the SPES substrate membrane exhibited a methanol permeability of 1.185×10^-6 cm²/s， whereas the SPES/BP composite membrane containing 5 % BP only present a methanol permeability of 2.88×10^-7 cm²/s.

Key words: sulfonated polysulfone, proton exchange membrane fuel cell, black phosphorus, methanol permeability

CLC Number:

TQ326.55

HE Boyuan, LEI Hexiang, CAO Ning, CHEN Xi, YAO Lifei, JIA Weiyi, LIAN Huiqin, WANG Xiaodong, CUI Xiuguo. Preparation and properties of sulfonated polysulfone/black phosphorus composite proton exchange membrane[J]. China Plastics, 2023, 37(11): 15-23.

Figures/Tables 14

References 26

1	Hickner M A， Ghassemi H， Kim Y S， et al. Alternative polymer systems for proton exchange membranes （PEMs）［J］. Chemischer Informationsdienst，2004，104（10）： 4 587⁃4 611.
2	贾双珠，李会勇，李长安. 质子交换膜燃料电池关键材料的研究现状与进展［J］. 化工新型材料， 2019， 47（2）： 6⁃10.
	JIA S Z， LI H Y， LI C A. Research status and development of key material for proton exchange membrane fuel cells［J］. New Chemical Material， 2019， 47（2）： 6⁃10.
3	汤小明，曹宁，蒋岳航. 聚砜类燃料电池质子交换膜研究进展［J］. 中国塑料， 2022， 36（8）： 146⁃158.
	TANG X M， CAO N， JIANG Y H. Research progress in polysulfone for proton⁃exchange membrane fuel cell［J］. China Plastics， 2022， 36（8）： 146⁃158.
4	Laberty⁃Robert C， Valle K， Pereira F， et al. Design and properties of functional hybrid organic⁃inorganic membranes for fuel cells［J］. Chemical Society Reviews， 2011， 40（2）： 1 961⁃1 005.
5	Wen S， Gong C， Tsen W⁃C， et al. Sulfonated poly（ether sulfone）/silica composite membranes for direct methanol fuel cells［J］. Journal of Applied Polymer Science， 2009： 1 491⁃1 498.
6	Lee W， Gil S C， Kim H， et al. Partially sulfonated poly（arylene ether sulfone）/organically modified metal oxide nanoparticle composite membranes for proton exchange membrane for direct methanol fuel cell［J］. Composites Science and Technology， 2016， 129： 101⁃107.
7	Wang S， Luo H， Li X， et al. Amino acid⁃functionalized metal organic framework with excellent proton conductivity for proton exchange membranes［J］. International Journal of Hydrogen Energy， 2021， 46（1）： 1 163⁃1 173.
8	Sriram K， Arthanareeswaran G， Ismail A F，et al. Effects of special nanoparticles on fuel cell properties of sulfonated polyethersulfone membrane［J］. International Journal of Polymeric Materials， 2016， 65（6）： 294⁃301.
9	Muthumeenal A， Saraswathi M， Rana D， et al. Fabrication and electrochemical properties of highly selective SPES/GO composite membranes for direct methanol fuel cells［J］. Journal of Environmental Chemical Engineering， 2017， 5（4）： 3 828⁃3 833.
10	Divya K， Rana D， Saraswathi M， et al. Investigation of the versatility of SPES membranes customized with sulfonated molybdenum disulfide nanosheets for DMFC applications［J］. International Journal of Hydrogen Energy， 2020， 45（31）： 15 507⁃15 520.
11	Divya K， Sundaram M， Saraswathi S A， et al. Custom⁃made sulfonated poly （ether sulfone） nanocomposite proton exchange membranes using exfoliated molybdenum disulfide nanosheets for DMFC applications［J］. Polymer， 2018， 147： 48⁃55.
12	Jiang R， Kunz H R， Fenton J M. Investigation of membrane property and fuel cell behavior with sulfonated poly（ether ether ketone） electrolyte： Temperature and relative humidity effects［J］. Journal of Power Sources， 2005， 150（10）： 120⁃128.
13	Ramya K， Vishnupriya B， Dhathathreyan K S. Methanol permeability studies on sulphonated polyphenylene oxide membrane for direct methanol fuel cell［J］. Journal of New Materials for Electrochemical Systems， 2001， 4（2）： 115⁃120.
14	项昭保，霍丹群，候长军. 聚醚砜的磺化改性［J］. 重庆大学学报：自然科学版， 2002， 25（10）： 117⁃120.
	XIANG Z B， HUO D Q， HOU C J. Sulfonation of polyethersulfone for modification［J］.Journal of Chongqing University， 2002， 25（10）： 117⁃120.
15	Sri A， Rana D， Vijayakumar P， et al. Tailored PVDF nanocomposite membranes using exfoliated MoS₂nanosheets for improved permeation and antifouling performance［J］. New Journal of Chemistry， 2017， 41（23）： 14 315⁃14 324.
16	Lei L， Zhang J， Wang Y. Sulfonated poly（ether ether ketone） membranes for direct methanol fuel cell［J］. Journal of Membrane Science， 2003， 226（1/2）： 159⁃167.
17	Cai H， Ke S， Zhong S， et al. Properties of composite membranes based on sulfonated poly（ether ether ketone）s （SPEEK）/phenoxy resin （PHR） for direct methanol fuel cells usages［J］. Journal of Membrane Science， 2007， 297（1/2）： 162⁃173.
18	Feng K， Tang B， Wu P. Selective growth of MoS₂ for proton exchange membranes with extremely high selectivity［J］. ACS Applied Materials & Interfaces， 2013， 5（24）： 13 042⁃13 049.
19	Beydaghi H， Javanbakht M， Kowsari E. Synthesis and characterization of poly（vinyl alcohol）/sulfonated graphene oxide nanocomposite membranes for use in proton exchange membrane fuel cells （PEMFCs）［J］. Industrial Engineering Chemistry Research， 2014， 53（43）： 16 621⁃16 632.
20	Klaysom C， Ladewig B P， Lu G， et al. Preparation and characterization of sulfonated polyethersulfone for cation⁃exchange membranes［J］. Journal of Membrane Science， 2011， 368（1/2）： 48⁃53.
21	Hooshyari K， Javanbakht M， Naji L， et al. Nanocomposite proton exchange membranes based on Nafion containing Fe₂TiO₅ nanoparticles in water and alcohol environments for PEMFC［J］. Journal of Membrane Science， 2014， 454： 74⁃81.
22	Li J， Zhang Y， Zhang S， et al. Sulfonated polyimide/s⁃MoS₂ composite membrane with high proton selectivity and good stability for vanadium redox flow battery［J］. Journal of Membrane Science， 2015， 490： 179⁃189.
23	Zhu X， Yang C， Xiao F， et al. Synthesis of nano⁃TiO₂⁃decorated MoS₂ nanosheets for lithium ion batteries［J］. New Journal of Chemistry， 2014， 39（1）： 683⁃688.
24	Mohanapriya S， Bhat S D， Sahu A K， et al. A new mixed⁃matrix membrane for DMFCs［J］. Energy Environmental Science， 2009， 2（11）： 1 210⁃1 216.
25	Bhat S D， Sahu A K， George C， et al. Mordenite⁃incorporated PVA⁃PSSA membranes as electrolytes for DMFCs［J］. Journal of Membrane Science， 2009， 340（1/2）： 73⁃83.
26	Sahu A K， Selvarani G， Bhat S D， et al. Effect of varying poly（styrene sulfonic acid） content in poly（vinyl alcohol）⁃poly（styrene sulfonic acid） blend membrane and its ramification in hydrogen–oxygen polymer electrolyte fuel cells［J］. Journal of Membrane Science， 2008， 319（1/2）： 298⁃303.

样品名称	PES、CSA配比/g·mL^-1	反应温度/℃	反应时间/h
SPES1	1/2.50	0	10
SPES2	1/2.50	10	10
SPES3	1/2.50	20	10
SPES4	1/2.50	30	10
SPES5	1/3.00	10	7
SPES6	1/3.00	10	8
SPES7	1/3.00	10	9
SPES8	1/3.00	10	10
SPES9	1/2.00	10	10
SPES10	1/2.25	10	10

样品名称	PES、CSA配比/g·mL^-1	反应温度/℃	反应时间/h
SPES1	1/2.50	0	10
SPES2	1/2.50	10	10
SPES3	1/2.50	20	10
SPES4	1/2.50	30	10
SPES5	1/3.00	10	7
SPES6	1/3.00	10	8
SPES7	1/3.00	10	9
SPES8	1/3.00	10	10
SPES9	1/2.00	10	10
SPES10	1/2.25	10	10

样品	PES、CSA配比/ g·mL^-1	反应温度/℃	反应时间/h	磺化度/ %	IEC/ mmol·g^-1
SPES1	1/2.50	0	10	10.50	0.44
SPES2	1/2.50	10	10	26.26	1.04
SPES3	1/2.50	20	10	23.90	0.95
SPES4	1/2.50	30	10	37.30	1.42

样品	PES、CSA配比/ g·mL^-1	反应温度/℃	反应时间/h	磺化度/ %	IEC/ mmol·g^-1
SPES1	1/2.50	0	10	10.50	0.44
SPES2	1/2.50	10	10	26.26	1.04
SPES3	1/2.50	20	10	23.90	0.95
SPES4	1/2.50	30	10	37.30	1.42

样品	PES、CSA配比/g·mL^-1	反应温度/℃	反应时间/h	磺化度/ %	IEC/ mmol·g^-1
SPES5	1/3.00	10	7	14.01	0.58
SPES6	1/3.00	10	8	20.73	0.83
SPES7	1/3.00	10	9	29.47	1.15
SPES8	1/3.00	10	10	41.22	1.55