本研究藉由未飽合雙鍵環烯烴結構單體(NB-diOH)及帶有磺酸根的單體(DHNS)，並加上帶有氟原子的苯酮結構單體(DFBP)所聚合出帶有磺酸化聚醚醚酮酮的高分子聚合物，並進一步製成質子交換薄膜。當高分子薄膜帶有的磺酸根越多，所帶來的效應如：導電度、吸水量甚至離子交換容積也相對來的較高許多。除此之外，本實驗也藉由環烯烴結構中未飽和雙鍵進行交聯作用，降低在甲醇穿透率及吸水吸甲醇量的表現，對此電解質薄膜顯現出益處。在此研究可針對調控磺酸化程度(DHNS 含量)加上適當的交聯反應(di-vinyl benzene ；DVB 含量)可以呈現出高導電度及低膨潤的電解質薄膜。整個NB-系列的薄膜可以發現出具有好的導電度及低膨潤性的薄膜為NB-sPEEKK-80X，在薄膜厚度為85 μm 時，直接甲醇燃料電池測試中表現出：60℃時，效能為16.5 mW/cm2 及50℃時，效能則為14.5 mW/cm2。 另一方面，也在NB-sPEEKK 高分子中添加入sTNT(sulfonated Titanium dioxide nanotube)表面修飾磺酸根之奈米管狀結構，其具備良好的保水性質，並形成有機/無機複合薄膜，讓sTNT 無機物的混摻在NB-sPEEKK 主鏈上分散性有較佳的均勻度，再藉由無機物上的磺酸根及NB-sPEEKK 主鏈上磺酸根之間的作用力，使得水分子在有機/無機的介面產生更強的鍵結，來幫助質子在親水端的水通 道有更佳的傳遞路徑。初步看出，NB-sPEEKK80/10 sTNT 這塊薄膜有較佳的導電度及最佳分散性。 A novel proton conducting membrane where the poly (ether ether ketone ketone) copolymer containing unsaturated norbornene unit and pendant sulfonic acid were synthesized by aromatic substitution polymerization reaction using 4,4'-Difluorobenzophenone (DFBP), 6,7-dihydroxy -2-naphthalenesul -fonate (DHNS), and 1,4-dihydro-1,4-methanonaphthalene-5,8-diol (NB-diOH) monomers. The degree of sulfonation can be controlled by adjusting the DHNS and NB-ph-diOH mole ratio in feed stream. The proton conductivity, water uptake and ion exchange capacity (IEC) all increase with increasing the DHNS feed concentration. On the other hand, cross-linking through double bond in norbornene unit reduces both the methanol permeability and methanol solvent uptake. Proton conducting membrane with high proton conductivity and low methanol swelling can be achieved by optimizing the degree of sulfonation (DS) with the degree of cross-linking. The study shows that these two structure characteristics can be adjusted separately by controlling the DHNS feed concentrations (for optimized DS) and di-vinyl benzene (DVB) for suitable degree of cross-linking. The best membrane with high proton conductivity and low degree of swelling is NB-sPEEKK-80X. The DMFC single cell assembled using this membrane (85μm thickness) displayed fair density reaching 16.5mW/cm2 at 60℃ and 14.5 mW/cm2 at 50℃. In addition, we also added the structure sTNT(sulfonated Titanium dioxide nanotube) into NB-sPEEKK polymers that sTNT have a good retention water and sulfonic acid groups on the surface to form a nice uniform in dispersion of organic/inorganic composite membrane. And the water in the membrane have a interaction by the sulfonic acid group bonding between sTNT and NB-sPEEKK polymer, to help the proton have a good transportation in the water channel of hydrophilic region. Now initially the NB-sPEEKK80/10 sTNT membrane had a good conductivity and dispersion.
