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  2. 西安交通大學(xué)《JPS》:打破使用氧等離子體處理的單層石墨烯的直接甲醇燃料電池中的電導(dǎo)率-選擇性權(quán)衡
    2025-07-18 10:11:59 作者:本網(wǎng)發(fā)布 來源:材料分析與應(yīng)用 分享至:



    成果簡介


    直接甲醇燃料電池(DMFC)相比氫燃料電池具有更簡單的燃料系統(tǒng),且在便攜式和小型化電源領(lǐng)域展現(xiàn)出廣闊應(yīng)用前景。然而,商業(yè)化Nafion膜的甲醇滲透問題會在陰極產(chǎn)生混合電位,導(dǎo)致開路電壓(OCV)降低及整體性能下降。盡管將單層石墨烯引入Nafion膜可緩解甲醇滲透并提升OCV,但往往會犧牲質(zhì)子導(dǎo)電性本文,西安交通大學(xué)史樂教授團隊在《Journal of Power Sources》期刊發(fā)表名為“Breaking the conductivity-selectivity trade-off in direct methanol fuel cells using oxygen plasma-treated monolayer graphene”的論文,研究將氧等離子體處理的單層石墨烯嵌入Nafion膜中,可同時提升質(zhì)子導(dǎo)電性和選擇性。


    這種雙重提升使DMFC性能較商業(yè)Nafion膜提升92.74%,功率輸出分別為60℃時的134.56 mW cm−2和90℃時的254.84 mW cm−2。分子動力學(xué)模擬表明,通過等離子體處理引入的含氧功能基團形成了納米孔,增強了石墨烯與Nafion之間的界面親和力,從而改善了界面處的水分分布和質(zhì)子傳導(dǎo)。這種方法有效打破了導(dǎo)電性與選擇性之間的權(quán)衡關(guān)系,為提升DMFC性能提供了可行解決方案。



    圖文導(dǎo)讀


    圖1. Schematic of the synthesis of Nafion/nanoporous graphene/Nafion. a) CVD graphene on copper substrate (centimeter scale, actual size 3 × 3 cm2); b) plasma treatment on copper substrate; c) D520 spin-coating; d) N212 hot-press; e) copper etching in FeCl3; f) air-dried nanoporous graphene on N212; g) another D520 spin-coating on the graphene side; h) another N212 hot-press (actual size 3 × 3 cm2).


    圖2. Characterization of CVD graphene and the composite N/G/N membrane. a) SEM of graphene on SiO2/Si, rectangles indicate the areas for Raman characterization in b); b) Raman spectra of graphene on SiO2/Si substrate; c) SEM of graphene on N212; d) cross section SEM of N/G/N membrane; e) contact angle of N212; f) contact angle of N212 with graphene transferred; g) photograph of the composited N/G/N membrane; h) photograph of the composited MEA.


    圖3. Characterization of the perforated graphene. a) photograph of the plasma treating process (left: Ar 20W; right: O2 7W with homemade Faraday cage); b) Raman spectra of perforated graphene; c) Defect density analysis from the Raman spectra in b).


    圖4. Membrane performance of N212/nanoporous graphene/N212 composite membranes. a) proton conductivity, b) CH3OH permeation, c) selectivity of proton over CH3OH.


    圖5Polarization curve of N212/nanoporous graphene/N212 composite membranes in 60 °C DMFC.


    圖6Fuel cell performance comparison of N212/nanoporous graphene/N212 composite membranes.


    圖7. Voltage degradation of best-performed N/G O10 s/N and commercial N115 at 0.08 mA cm−2, 60 °C.


    圖8Water distribution analysis at the interfacial regions of Nafion/nanoporous graphene/Nafion composite membranes (grey dots indicate the position of graphene layer). a1, a2) bulk Nafion (λ = 20); b1, b2) Nafion/pristine graphene/Nafion; c1, c2) Nafion/H decorated nanoporous graphene/Nafion; d1, d2) Nafion/epoxy decorated nanoporous graphene/Nafion; e1, e2) Nafion/hydroxyl decorated nanoporous graphene/Nafion; f) Layer-to-layer distribution functions analysis between atoms in water molecule and graphene; g) Layer-to-layer distribution functions analysis between atoms in Nafion and graphene.



    小結(jié)


    一系列夾層結(jié)構(gòu)的Nafion/等離子體穿孔石墨烯/Nafion質(zhì)子交換膜被合成,以保持對甲醇穿透的顯著阻抗,同時克服由原始石墨烯的高質(zhì)子滲透屏障引起的性能限制。引入氧等離子體穿孔石墨烯后,質(zhì)子導(dǎo)電率較原始石墨烯膜提高了超過三倍。在燃料電池測試中,N/G O10 s/N膜在開路電壓(OCV)方面優(yōu)于商業(yè)N212膜,并實現(xiàn)了最大功率密度92.74%的提升。這一改進歸因于質(zhì)子導(dǎo)電性的提升,同時保留了石墨烯對甲醇的選擇性。等離子體穿孔不僅在原始石墨烯中引入選擇性納米孔,通過更大孔徑提升質(zhì)子導(dǎo)電性,還在納米孔邊緣添加功能基團,影響鄰近水分布情況。氧等離子體可引入羥基促進質(zhì)子滲透。然而,延長氧等離子體處理時間會導(dǎo)致羥基轉(zhuǎn)化為環(huán)氧基團,反而阻礙質(zhì)子滲透。這一現(xiàn)象導(dǎo)致石墨烯等離子體處理時間延長時性能下降。因此,適當(dāng)?shù)臅r間控制至關(guān)重要。根據(jù)我們的實驗結(jié)果,采用法拉第籠進行6秒氬等離子體處理和10秒氧等離子體處理可實現(xiàn)最佳燃料電池性能。這項工作為在DMFCs中應(yīng)用納米孔單層石墨烯作為新一代質(zhì)子交換膜鋪平了道路。

    文獻:

    https://doi.org/10.1016/j.jpowsour.2025.237800



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