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Điện hóa

Đinh Trần Trọng Hiếu, Lâm Hoàng Hảo, Trần Thanh Danh, Trần Hoàng Long, Nguyễn Tiến Cường(4), Trần Văn Mẫn(5), Trương Thị Hồng Loan, Trần Duy Tập(2)(1), Van Man TRAN(3)

Nghiên cứu cơ chế ghép mạch và sulfo hóa của màng dẫn proton sử dụng trong pin nhiên liệu hydro

Study on the mechanism of graft polymerization and sulfonation of proton exchange membranes for fuel cell

Khoa học & công nghệ Việt Nam

2022

6B

7 - 13

1859-4794

ETFE, Ghép mạch, Bức xạ, Màng dẫn proton, Pin nhiên liệu

ETFE, Fuel cell, Proton exchange membrane, Radiation induced-grafting

Poly(ethylene-co-tetrafluoroethylene) (ETFE) ghép poly(styrene sulfonic acid) màng điện giải polymer (ETFE-PEM) được tổng hợp ghép mạch khơi mào bởi bức xạ gamma từ nguồn 60Co thông qua 3 bước: (i) Chiếu xạ, (ii) Ghép polystyrene vào phim ETFE (PS-g-ETFE) và (iii) Sulfo hóa (ETFE-PEM). Cơ chế ghép mạch và sulfo hóa của ETFE-PEM với mức độ ghép 22% và sulfo hóa 93% được nghiên cứu bởi phổ cộng hưởng từ hạt nhân 13C rắn (solid 13C NMR), phổ hồng ngoại biến đổi Fourier (FT-IR) và kính hiển vi điện tử quét phát xạ trường (FE-SEM). Các kết quả cho thấy, styrene được ghép vào polymer nền ETFE bằng phản ứng phá vỡ liên kết π được gây ra bởi các gốc tự do và tạo thành chuỗi polystyrene trên bề mặt pha tinh thể. Các styrene vào sau vẫn tiếp tục khuếch tán vào sâu trong màng từ hai mặt do sự chênh lệch gradient nồng độ. Quá trình ghép mạch xảy ra trên cả vị trí C-H và C-F của mạch polymer ETFE nền, nhưng tại vị trí C-F nhiều hơn, trong khi đó các phản ứng sulfo hóa để tạo màng dẫn proton chỉ xảy ra tại vị trí para trên vòng thơm của polystyrene. Các phản ứng phụ, sản phẩm thứ cấp của quá trình ghép và sulfo hóa không được tìm thấy trên các phổ 13C NMR, FT-IR thu được, chứng tỏ các quá trình ghép, sulfo hóa đã được kiểm soát tốt.

Poly (styrenesulfonic acid)-grafted poly(ethylene-co-tetrafluoroethylene) polymer electrolyte membrane (ETFE-PEM) applied for fuel cells was prepared by radiation induced-grafting using gamma-ray f-rom 60Co source based on three steps (i) irradiation, (ii) polystyrene-grafted poly(ethylene-alt-tetrafluoroethylene) (PS-g-ETFE), and (iii) sulfonation (ETFE-PEM). Mechanism of grafting and sulfonation of ETFE-PEM with grafting degree of 22% and sulfonation degree of 93% was revealed by solid 13C nuclear magnetic resonance (solid 13C NMR), Fourier transform infrared spectroscopy (FT-IR), and field emission scanning electron microscopy (FE-SEM). The obtained results indicated that the styrene was grafted on the matrix of ETFE polymer by the π bond-breaking reaction which could be attributed to free radicals and formed the polystyrene chain at the surfaces of crystalline phases. The styrene migrated deep into the membrane due to the concentration gradient. The grafting reactions occurred at sites of C-H and C-F in the ETFE backbone but dominantly at the C-F sites while the sulfonation took place at the para position of polystyrene. The signatures related to side (secondary) reactions and by-products were not observed in the spectra indicating that the graft polymerization and sulfonation are well-controlled.

TTKHCNQG, CVv 8

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