Research Progress of Side-Chain Sulfonated Polyarylene Ether Proton Exchange Membranes

doi:10.19894/j.issn.1000-0518.220114

Chinese Journal of Applied Chemistry ›› 2022, Vol. 39 ›› Issue (12): 1783-1802.DOI: 10.19894/j.issn.1000-0518.220114

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Research Progress of Side-Chain Sulfonated Polyarylene Ether Proton Exchange Membranes

Tong CAO¹^,², Jun PENG¹^,², Yan FENG³, Xiao-Bo LIU¹^,²(), Yu-Min HUANG¹^,²()

^1.School of Materials and Energy，University of Electronic Science and Technology of China，Chengdu 611731，China
^2.Sichuan Province Engineering Technology Research Center of Novel CN Polymeric Materials，Chengdu 611731，China
^3.Shenzhen Extender Co. ，Ltd，Shenzhen 518103，China

Received:2022-04-07 Accepted:2022-09-04 Published:2022-12-01 Online:2022-12-13
Contact: Xiao-Bo LIU,Yu-Min HUANG
About author:hym@uestc.edu.cn
liuxb@uestc.edu.cn
Supported by:
the National Natural Science Foundation of China(21805027);Sichuan Science and Technology Program(2019YJ0197)

Abstract

Abstract:

Fuel cell is a new type of energy conversion device using hydrogen， methanol， etc. as fuel， among which the proton exchange membrane fuel cell （PEMFC） has been widely used in mobile power， submarines and electric vehicles by virtue of its high energy power， fast start-up speed and long service life. Proton exchange membranes （PEM） have the greatest impact on the performance of PEMFC. Efficient PEMFC requires PEM with high proton conductivity， good thermal stability and mechanical properties， low fuel permeability and excellent physical and chemical stability. Most of the membranes currently used in the market are Nafion membranes with excellent proton conductivity， but they have disadvantages such as difficulty in preparation， expensive cost， and heavy dependence on humidity for proton conductivity， which limits their development to some extent. In order to make more options for proton exchange membranes， scientists have been focusing on using new materials to replace Nafion membranes. In recent years， scientists have simulated the Nafion structure by synthesizing various side chain polyaryl ether structures containing sulfonic acid groups， allowing the formation of microphase separation structures between hydrophilic sulfonic acid groups and hydrophobic groups， resulting in a series of proton exchange membranes with excellent overall performance. This paper focuses on the synthesis methods and properties of several common strategies， such as side chain alkyl sulfonated type， side chain sulfonated block type， side chain partially dense sulfonated type， side chain sulfonated cross-linked type and side chain sulfonated composite type. Finally， the advantages and development prospects of side chain sulfonated polyaryl ethers in the field of proton exchange membranes are reviewed.

Key words: Fuel cell, Proton exchange membrane, Side chain sulfonation, Proton conductivity

CLC Number:

O633

Tong CAO, Jun PENG, Yan FENG, Xiao-Bo LIU, Yu-Min HUANG. Research Progress of Side-Chain Sulfonated Polyarylene Ether Proton Exchange Membranes[J]. Chinese Journal of Applied Chemistry, 2022, 39(12): 1783-1802.

Figures/Tables 24

Fig.1 Operating principle of hydrogen-oxygen proton exchange membrane fuel cells［7］

Fig.2 Proton passage mechanism in ion channels of PEMs

Fig.3 Synthesis route of comb-shaped SPAE and SPAEN［42］

Fig.4 Morphology of SPAE-1，3 and SPAEN-1，3 ionomers studied by TEM. （A） SPAE-1， DS=0.74；（B） SPAE-3， DS=0.92；（C） SPAEN-1， DS=0.68；（D） SPAEN-3， DS=0.90［42］

Fig.5 Chemical structure of SPAEKS -PSA X［43］

Fig.6 The proton transport mechanism in SPAEKS-PSA X membranes［43］

Fig.7 Synthesis of MTSPAEK［44］

Fig.8 Synthesis of PPO-g-PSSA［45］

Fig.9 Chemical structure of SPAEK copolymer［50］

Fig.10 AFM phase image of the SPAEK membranes under 100% RH（700 nm×700 nm）：（a） SPAEK （X4.8Y8.8），（b）SPAEK（X7.5Y8.8） and （c） SPAEK （X9.1Y8.8）［50］

Fig.11 Chemical structure of multi-block poly（aryl ether ketone）［51］

Fig.12 Synthesis of highly branched sulfonated block poly（arylene ether sulfone）s［52］

Fig.13 Synthetic route of GSPHP［35］

Fig.14 Chemical structure of PEK-SPx［55］

Fig.15 The chemical structure of cross-linkable side chain sulfonated polyarylene ether sulfone copolymer （S-SPAES （x/y））［63］

Fig.16 Schematic chemical structure based on the cross-linked of ammonium salts of S-SPAES （x/y） and 3，3'-diaminobenzidine［63］

Fig.17 Synthesis of densely sulfonated poly（arylene ether sulfone）s［64］

Fig.18 Schematic diagram of self-crosslinked SPEEK74-O-Pax［65］

Fig.19 Synthesis of SPEEK74-O-Pax［65］

Fig.20 Synthesis process of NmAn-SCBTA［66］

Fig.21 Composite mechanism of side-chain sulfonated poly（aryl ether ketone） and MOF［71］

Fig.22 Schematic of the interaction between HBSPE and SGO and the ion channel in the HBSPE/SGO nanocomposite membranes［72］

Table 1 Comparison of the main properties of proton exchange membranes based on hydrogen fuel cell appearing in this paper

质子交换膜 Proton exchange membrane	质子电导率 Proton conductivity/ （mS·cm^-1）	离子交换容量 Ion-exchange capacity/ （mmol·g^-1）	吸水率 Water uptake/ %	燃料电池性能 Fuel cell performance/（mW·cm^-2）	温度 Temperature/ ℃	相对湿度 Relative humidity/%	参考文献 Ref.
GSPHP 25	102.6	1.47	60.28	620.0	80	90	［35］
PPO-g-0.08PPSA-13	45.5	3.24	/	/	95	90	［45］
SPAEK（X9.1Y8.8） PPEK-M20N10-SO₃H	154.1 150.0	2.01	70.00	323.9	60	100	［50］
SPAEK（X9.1Y8.8） PPEK-M20N10-SO₃H	154.1 150.0	1.41	25.60	768.0	70	80	［51］
SPAES-6f	420.0	1.60	59.50	/	80	100	［52］
SPDCP-1.5	248.2	1.52	33.80	/	90	100	［56］
CSP-1	215.0	1.72	27.80	1 660.0	70	65	［64］
SPEEK74-O-PA100	200.3	/	12.60	527.0	65	100	［65］
Nafion 211	102.8	0.90	32.13	630.0	80	90	［35］
Nafion 115	131.5	0.92	35.00	291.4	60	100	［50］
Nafion 212	142.0	0.91	15.40	744.0	70	80	［51］

Table 2 Comparison of the main properties of proton exchange membranes based on methanol fuel cell appearing in this paper

质子交换膜 Proton exchange membrane	质子电导率 Proton conductivity/ （mS·cm^-1）	离子交换容量 Ion-exchange capacity/ （mmol·g^-1）	吸水率 Water uptake/%	燃料电池性能 Fuel cell performance/ （mW·cm^-2）	温度 Temperature/ ℃	相对湿度 Relative humidity/ %	甲醇渗透率 Methanol permeability/ （cm²·s^-1）	参考文献 Ref.
SPAE-3	120.0	1.50	79.60	/	100	100	2.90×10^-7	［42］
SPAEKS-PSA15 MTSPAEK-2.10	101.0 181.0	0.78	15.72	30.50	80	100	9.44×10^-7	［43］
SPAEKS-PSA15 MTSPAEK-2.10	101.0 181.0	2.57	87.00	70.00	80	100	7.80×10^-7	［44］
PEK-SP20	100.0	1.78	34.10	45.50	80	100	3.60×10^-7	［55］
S-SPAES（1/2）	180.0	2.01	46.20	314.5	60	100	7.12×10^-7	［63］
N7A3-SCBTA	89.0	1.81	20.00	/	90	100	0.79×10^-7	［66］
MNS@SNF-PAEK-3%	192.0	1.85	73.34	125.70	80	100	5.28×10^-7	［71］
HBSPE/SGO 0.50	355.0	1.74	39.00	82.36	80	100	7.87×10^-7	［72］
Nafion117	30.2	0.80	19.60	21.30	80	100	1.22×10^-6	［73］

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Research Progress of Side-Chain Sulfonated Polyarylene Ether Proton Exchange Membranes

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