空气阴极微生物燃料电池阴极结构及催化剂的研究-环境科学与工程专业毕业论文.docx

哈尔滨工业大学工学博士学位论文 哈尔滨工业大学工学博士学位论文 Ab Abstract - - PAGE IV - - - III - 极的稳定性明显优于 Pt/C 阴极，掺氮碳粉阴极 ACMFC 的最大功率密度几乎不 变，而 Pt/C 阴极 ACMFC 的最大功率密度下降达 13%，且有进一步下降的趋势。 通过优化阴极结构来提高 ACMFC 的产电能力，优化主要针对：催化层的 梯度、制备扩散层时的降温方式、碳基层碳粉的灰分和粒径的选择等。结果表 明，在不改变催化剂总用量和粘结剂总用量的前提下，将原来的单层催化层改 为催化剂和粘结剂用量梯度减少（从阴极液到空气方向）的多层催化层后， ACMFC 的功率密度有所提高。在扩散层的制备过程中，快速降温比慢速降温 更容易形成有利于氧气扩散的孔隙，使氧气顺利到达催化层参与氧还原反应。 碳基层的碳粉粒径存在一个最优值，约为 1300nm，此时氧气传质较好。碳粉 的灰分越小所制备的碳基层性能越好。 在合成低成本催化剂和阴极结构优化的基础上，考察了硫化物对掺氮碳粉 催化活性的影响，并与 Pt/C 催化剂进行了对比。当电解液中含有硫化物时，Pt/C 的氧还原催化活性明显降低。ACMFC 在 Na2S 浓度为 0.2g·L 时的最大功率密度 比中性电解液时减少了约 21.3%。而掺氮碳粉的催化活性基本不受硫化物的影 响，相同 Na2S 浓度下其 ACMFC 的最大功率密度比 Pt/C 高 11.4%。当 ACMFC 阴极受硫化物影响时，使用掺氮碳粉代替 Pt/C 作为阴极催化剂不仅能大幅降低 成本，且能获得更大的电能输出。 关键词：微生物燃料电池（MFC）；氧还原反应；催化剂；阴极材料；阴极结构 Abstract Taking advantage of bacterium consuming the organics in the wastewater, microbial fuel cell (MFC) directly converts the bioenergy to electricity and it is becoming a new research direction in the field of environmenetal engineering. Among many different types of MFC, air-cathode microbial fuel cell (ACMFC) provides relatively high theoretical cell voltage because it uses the oxygen in the air as the cathodic catalyst for oxygen reduction reaction (ORR). However, the expensive platinum (Pt), which serves as the indispensable ORR catalyst in cathodes, dramatically increases the cost of ACMFCs. The relative research on ACMFCs is still limited to the laboratory scale. Many low-cost substitutes for Pt have been developed and the cost of ACMFCs is indeed reduced, however, at the cost of degrading the electricity generation capacity. Reducing the cost of ACMFC while keeping its high electricity generation capacity is becoming an urgent problem to be solved in the field of research on ACMFC. Focusing the goal of reducing cost and improving cathodic performanc e of ACMFCs, cathodic materials and structure was studied, with the detailed contents as below: Catalytic activities of Pd/C and Ru/C for ORR were investigated by testing power densities of a sing