Citation: Gang Wang, Jialin Li, Haibin Li, Haibo He, Liang Zhai, Xiang Li, Tingting Li, Chengji Zhao, Lixin Wu, Haolong Li. In situ crosslinking of polyoxometalate-polymer nanocomposites for robust high-temperature proton exchange membranes[J]. Chinese Chemical Letters, ;2023, 34(2): 107497. doi: 10.1016/j.cclet.2022.05.011 shu

In situ crosslinking of polyoxometalate-polymer nanocomposites for robust high-temperature proton exchange membranes

Gang Wang ^a ,
Jialin Li ^b ,
Haibin Li ^a ,
Haibo He ^a ,
Liang Zhai ^a ,
Xiang Li ^a ,
Tingting Li ^a ,
Chengji Zhao ^b ,
Lixin Wu ^a ,
Haolong Li ^{a, b, *,}

a.
State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130012, China
b.
Key Laboratory of High Performance Plastics, Ministry of Education, College of Chemistry, Jilin University, Changchun 130012, China

hl_li@jlu.edu.cn

Received Date: 14 April 2022
Revised Date: 30 April 2022
Accepted Date: 7 May 2022
Available Online: 11 May 2022

Figures(5)

The most practical high-temperature proton exchange membranes (PEMs) are phosphoric acid (PA)-doped polymer electrolytes. However, due to the plasticizing effect of PA, it is a challenge to address the trade-off between the proton conductivity and the mechanical performance of these materials. Here, we report an effective strategy to fabricate robust high-temperature PEMs based on the in situ electrostatic crosslinking of polyoxometalates and polymers. A comb copolymer poly(ether-ether-ketone)-grafted-poly(2-ethyl-2-oxazoline) (PGE) with transformable side chains was synthesized and complexed with H₃PW₁₂O₄₀ (PW) by electrostatic self-assembly, forming PGE/PW nanocomposite membranes with bicontinuous nanostructures. After a subsequent PA-treatment of these membranes, high-temperature PEMs of PGE/PW/PA ternary nanocomposites were obtained, in which the in situ electrostatic crosslinking effect between PW and PGE side chains was generated in the hydrophilic domains of the bicontinuous structures. The microphase separation structure and the electrostatic crosslinking feature endow the PGE/PW/PA membranes with excellent anhydrous proton conductive ability while retaining high mechanical performance. The membranes show a high proton conductivity of 42.5 mS/cm at 150 ℃ and a high tensile strength of 13 MPa. Our strategy can pave a new route based on electrostatic control to design nanostructured polymer electrolytes.
- Polyoxometalates,
- Comb copolymers,
- Self-assembly,
- In situ crosslinking,
- Proton exchange membranes
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