不锈钢网阴极微生物燃料电池的产电性能研究

构建了一个以曝气池污泥为阳极接种微生物、碳毡为阳极、无任何修饰的不锈钢网为阴极的双室微生物燃料电池. 通过输出电压、功率密度以及电化学阻抗等考察了阴极面积对电池产电性能的影响,并对电池的长期运行稳定性进行评价. 研究结果表明,不锈钢网作为微生物燃料电池的阴极性能稳定. 当不锈钢网面积为2 × 2 cm²时,最大输出电压达到0.411 V,功率密度为0.303 W•m^-2,内阻841 Ω,极化内阻80 Ω. 增大阴极面积至2 × 4 cm²,最大输出电压能达到0.499 V,内阻减小至793 Ω. 不锈钢网价格便宜,具有长期运行稳定性,适宜做MFCs的阴极.     

以椰壳生物质炭为燃料的直接炭固体氧化物燃料电池

通过热裂解制得椰壳炭,表征了其结构和组成,并将其用于电解质为钇稳定化氧化锆（YSZ）、电极材料为银和钆掺杂氧化铈（Ag-GDC）的固体氧化物燃料电池（SOFC）的燃料,对所构成的直接炭固体氧化物燃料电池（DC-SOFC）的性能进行了测试研究。结果表明,所制得的椰壳炭颗粒粒径在微米级别,具有介孔结构,而且椰壳炭中含有K、Ca等元素,可用作Boudouard反应催化剂。当使用椰壳炭作为DC-SOFC燃料时,在800 ℃下电池最大功率密度为255 mW/cm²;负载Fe催化剂后,最大功率密度提升为274 mW/cm²。以0.5 A/cm²的恒电流放电,0.5 g负载Fe椰壳炭燃料电池能够连续工作17.6 h,燃料利用率为39%,表明椰壳炭作为DC-SOFC燃料具有优异的性能和潜力。     

双极界面聚合物膜燃料电池Ⅱ:阴极催化层结构优化

以薄层亲水电极或者厚层憎水电极作为双极燃料电池(BPFC)阴极, 系统考察了薄层亲水阴极中季铵化聚砜(QAPSF)含量、厚层憎水电极中聚四氟乙烯(PTFE)含量对电池性能的影响. 结果表明, 采用薄层亲水阴极时, 催化层中QAPSF的最佳含量是20 wt%, 室温下BPFC的最大输出功率达到186.1 mW/cm². 采用厚层憎水电极时, 催化层中PTFE的合适含量是20 wt%, 40 ℃时BPFC的最大输出功率达到461.5 mW/cm². 由于碱性阴极对排水的需求较高, 厚层憎水电极相较于薄层亲水电极在BPFC中更有优势.     

全酶型乙醇/氧气生物燃料电池的构筑及性能研究

本文以乙醇脱氢酶（ADH）和胆红素氧化酶（BOD）为生物催化剂,以碳纳米管为电极材料,构筑了全酶型乙醇/氧气生物燃料电池. 将乙醇脱氢酶负载于单壁碳纳米管（SWCNT）上,采用亚甲基绿（MG）为NADH的电化学催化剂,实现乙醇的生物电化学催化氧化,制备了生物燃料电池ADH/MG/SWCNT/GC的电极（阳极）. 同时,将胆红素氧化酶固定于单壁碳纳米管上,通过其直接电子转移,实现了氧气的生物电化学催化还原,制得生物燃料电池的BOD/SWCNT/GC阴极. 据此构筑了全酶型的无膜生物燃料电池,在空气饱和40 mmol·L^-1乙醇磷酸缓冲溶液中该电池开路电压为0.53 V,最大输出功率密度为11 μW·cm^-2. 以商品化伏特酒作为燃料,该生物燃料电池最大输出功率为3.7 μW·cm^-2.     

葡萄糖乙酸钠不同基质微生物燃料电池电化学性能对比研究

本文通过接种生活污水处理厂的好氧污泥和厌氧污泥,撘建两个双室微生物燃料电池(MFC,Microbial fuel cell),分别以葡萄糖、乙酸钠作为基质,在0.0335 mol•L^-1基质浓度下研究不同基质微生物燃料电池的产电性能. 研究表明：葡萄糖体系的阳极半电池阻抗为222 Ω,乙酸钠体系为213.67 Ω,说明两种不同有机基质对电池内阻无明显影响. 葡萄糖、乙酸钠体系的交换电流密度i⁰分别为3.463 mA•m^-2、 5.987mA•m^-2;COD去除率分别为50.6%、55.8%;库仑效率分别为42.1%、46.2%. 葡萄糖为基质时最大输出功率密度为394.2 mW•m^-2,相应的最大电流密度为1800mA•m^-2;乙酸钠为基质时最大输出功率密度为311.9mW•m^-2,相应的最大电流密度为1527.5mA•m^-2. 葡萄糖代谢过程复杂并不单一,且代谢不彻底,乙酸钠分子简单更容易代谢,因此乙酸钠的库伦效率及COD去除率均高于葡萄糖,由以上数据可以得出葡萄糖为基质的燃料电池产电性能较好.     

离子型交联磺化聚酰亚胺质子交换膜的制备及高温燃料电池性能

以2,2′-双(4-磺基苯氧基)联苯二胺、 2-(4-氨基苯基)-5-氨基苯并咪唑和1,4,5,8-萘四甲酸二酐为单体, 通过逐步聚合和溶液成膜法制备了离子型交联磺化聚酰亚胺质子交换膜(SPI PEMs). SPI PEMs具有优异的机械性能和耐水解稳定性, 在高离子交换容量和高湿度下具有和NR212相当的质子传导性能. 电池工作温度为90 ℃时, 高加湿条件下, n(BSPOB)/n(DABI)为5/2的离子型交联SPI PEM(M1)的最大输出功率密度(W_max)为 0.93 W/cm², 高于NR212的0.86 W/cm². 当电池温度提高到110 ℃时, 所有PEMs的电池性能显著下降, M1的W_max为0.54 W/cm², 明显高于共价型交联的SPI PEM. 离子型交联的SPI PEM在110 ℃下300 h的开路电压(OCV)耐久性降低了约10%, 远高于NR212.     

真空注浆法制备YSZ电解质膜管及其在固体氧化物燃料电池中的应用

以吡啶为分散剂,采用真空注浆法制备出膜厚为0.2mm、长度为140mm的致密YSZ电解质膜管。研究了烧结温度对样品致密度和离子导电率的影响.用1650℃烧结2h制备的致密YSZ电解质膜管组装成固体氧化物燃料电池,以氢气和煤气为燃料,研究了电池在500～900℃的电化学性能.实验结果表明,用真空注浆法可制备出高质量和高密度的YSZ电解质膜管,在1600℃烧结后,其相对密度已达到理论密度的98.1%,接近理论密度.单电池的开路电压最大值为1.213V,最大输出功率为0.48W.以氢气为燃料的燃料电池性能明显高于以煤气为燃料的电池性能.     

生物膜电极在以苯酚为燃料的微生物燃料电池中的应用

以苯酚为燃料, 生物膜电极为负极, Ti/SnO₂-Sb₂O₅/PbO₂电极为正极, 构建了双室微生物燃料电池. 利用微电流驯化法和自然驯化法分别制备了生物膜电极, 研究了微生物的挂膜方法、 挂膜时间和负极基底材料种类对微生物燃料电池产电能力的影响. 结果表明, 微电流驯化法优于自然驯化法, 微电流驯化法制备的生物膜电极更利于电池的产电; 微生物的挂膜时间为8 d时, 电池的产电能力最高, 其最大输出功率密度达到39 mW/m²; 不同基底材料生物膜电极所组建的微生物燃料电池产电能力高低顺序为碳毡>石墨>钛网>泡沫钛.     

固体氧化物燃料电池Cu-LSCM-CeO2/LSCM-YSZ/Ni-ScSZ复合阳极制备及性能

采用流延法制得LSCM-YSZ阳极支撑层/Ni-ScSZ阳极活性层/ScSZ电解质层复合膜,在LSCM-YSZ支撑层上印刷一层Cu-LSCM-CeO₂阳极催化层,即Cu-LSCM-CeO₂/LSCM-YSZ/Ni-ScSZ功能梯度层阳极. 研究表明,Cu/LSCM/CeO₂质量配比为2:7:1功能梯度阳极（LSCM-YSZ2010）有较好的性能,单电池以氢气和乙醇为燃料（750 ^oC）最大功率密度分别为511和390 mW?cm^-2,单电池稳定性实验表明,LSCM-YSZ2010阳极单电池以乙醇为燃料750 ^oC长时间运行218 h,性能稳定. X-射线能量散射分析表明该阳极具有较好的抗碳沉积性能.     

一种新型的甲酸/铁离子燃料电池

以甲酸为燃料、 Fe³⁺为氧化剂组成了一种新型的甲酸/铁离子燃料电池, 阳极催化剂为多壁碳纳米管(MWCNT)或β-环糊精修饰的MWCNT(β-CD-MWCNT)负载的金属钯或钯锡纳米颗粒: PdSn/MWCNT, Pd/β-CD-MWCNT和PdSn/β-CD-MWCNT. 运用循环伏安(CV)和计时电流(CA)等技术研究了各催化剂在碱性条件下对甲酸氧化反应的电催化活性. 结果表明, 加入适量的金属锡能促进钯对甲酸的电催化氧化, 甲酸氧化电位提前, 电流密度增加; 环糊精的改性对催化剂电催化活性有一定提升. 将上述催化剂制成电池阳极片, 碳粉制成电极阴极片, 组成甲酸/铁离子燃料电池并测试其放电性能. 结果表明, 电池的开路电压在0.981.20 V之间; 以PdSn/β-CD-MWCNT为阳极时, 其最大放电电流密度达50 mA/cm², 最大功率密度达12.6 mW/cm², 远优于以Pd/C为阳极的电池性能.     

YSZ传导膜H_2S固体氧化物燃料电池

研究了Y2O3稳定的ZrO2(YSZ)氧离子传导膜H2S固体氧化物燃料电池性能。掺杂NiS、电解质、Ag粉和淀粉制备了双金属复合MoS2阳极催化剂,掺杂电解质、Ag粉和淀粉制备了复合NiO阴极催化剂,用扫描电镜对YSZ和膜电极组装(MEA)进行了表征,比较了不同电极催化剂的性能和极化过程,考察了不同温度对电池性能的影响。结果表明,双金属复合MoS2/NiS阳极催化剂在H2S环境下比Pt和单金属MoS2催化剂稳定,复合NiO阴极催化剂比Pt性能好,在电极催化剂中加入Ag可显著提高电极的导电性;与Pt电极相比,复合MoS2阳极和复合NiO阴极催化剂的过电位较小,阳极的极化比阴极侧小;温度升高,电池的电流密度与功率密度增加,电化学性能变好。在750℃、800℃、850℃和900℃及101.13 kPa时,结构为H2S、(复合MoS2阳极催化剂)/YSZ氧离子传导膜/(复合NiO阴极催化剂)、空气的燃料电池最大功率密度分别为30 mW/cm2、70 mW/cm2、155 mW/cm2及295 mW/cm2、最大电流密度分别为120 mA/cm2、240 mA/cm2、560 mA/cm2和890 mA/cm2。     

用于直接甲醇燃料电池的高活性PtCo-CNT@TiO_2复合纳米阳极催化剂

采用溶胶凝胶法制备CNT@TiO_2载体,利用电沉积法制备用于直接甲醇燃料电池的PtCo-CNT@TiO_2阳极催化剂。采用透射电子显微镜(TEM)、X射线衍射(XRD)和电化学工作站对其进行表征。结果表明,PtCo-CNT@TiO_2复合纳米材料有明显的结晶,且金属粒子围绕在TiO_2包覆的碳纳米管的周围,用于直接甲醇燃料电池阳极催化剂具有较高的活性与稳定性。该PtCo-CNT@TiO_2催化剂的电化学比表面积为164 m~2/g,65℃时甲醇的氧化峰电流达到45 mA/cm~2,计时电流曲线表明300 s后PtCo-CNT@TiO_2的氧化电流趋于24 mA/cm~2,在碱性条件下甲醇的氧化峰电流为39.7 mA/cm~2。     

基于纳米CdS对尿酸的光催化氧化和铜(Ⅱ)配合物对氧的电催化还原的燃料电池性能

以纳米硫化镉薄膜修饰的铟锡氧化物电极(CdS/ITO)作光阳极, 铜(Ⅱ)配合物[Cu(phen)(L-Trp)·(H₂O)]⁺(phen=1,10-菲啰啉, L-Trp=L-色氨酸)修饰单壁碳纳米管(SWCNTs)电极作阴极, 构建了光催化尿酸(UA)燃料电池, 并研究了其性能及热处理温度的影响. 结果表明, 在40 ℃以下获得的纳米CdS修饰电极在320~550 nm波长区间显现明显的吸收和光伏响应, 在可见光辐射下能光催化氧化UA; 较高温度的热处理(200~300 ℃)却降低了纳米CdS对UA的光催化氧化活性. [Cu(phen)(L-Trp)(H₂O)]⁺/SWCNTs电极在-0.131 V电位下呈现一对准可逆的氧化还原峰, 并能电催化还原O₂和H₂O₂. 此外, 基于UA在CdS/ITO电极上的光催化氧化及O₂在[Cu(phen)(L-Trp)(H₂O)]⁺/SWCNTs电极上的电催化还原, 组装了UA(0.2 mmol/L)燃料电池, 其在可见光照射(0.18 mW/cm²)下产生0.52 V开路电压, 13.08 μA/cm²短路光电流, 在0.41 V下呈现的最大功率密度为4.10 μW/cm².     

Preparation and Electrochemical Performance of Cobalt-free Cathode Material Ba0.5Sr0.5Fe0.9Nb0.1O3-δ for Intermediate-temperature Solid Oxide Fuel Cells

Perovskite oxide Ba0.5Sr0.5Fe0.9Nb0.1O3-δ（BSFN） as a cobalt-free cathode for intermediate-temperature solid oxide fuel cells（IT-SOFCs） on the Ce0.5Sm0.2O1.9（SDC） and La0.9Sr0.1Ga0.8Mg0.23O3-δ（LSGM） electrolytes was prepared and investigated. The single phase BSFN oxide with a cubic perovskite structure and relatively high elec- trical conductivities was obtained after sintering at 1250℃ for 10 h in air. The BSFN cathode exhibited excellent chemical stability on the SDC and LSGM electrolytes at temperatures below 950 ℃. The area specific resistance of the BSFN cathode on the SDC and LSGM electrolytes were 0.024 and 0.021 Ω·cm2 at 800℃, respectively. The maximum power densities of the single cell with BSFN cathode in 300 μm-thick SDC and LSGM electrolytes achieved 414 and 516 mW/cm2 at 800℃, respectively. These results show that the BSFN material is a promising co- bait-free cathode candidate to be used in IT-SOFCs. A combination of the BSFN cathode and LSGM electrolyte is preferred owing to its excellent electrochemical performance.     

可用作便携式电源的高性能直接碳固体氧化物燃料电池组

A direct carbon solid oxide fuel cell (DC-SOFC) stack was prepared with 3 tubular cells electrically connected in series. To increase carbon storage in the stack, the anode was fabricated outside the tubular cells so that carbon fuel can be loaded at the exterior of the stack, which is more spacious than the interior. The 3-cell-stack is operated directly with carbon as the fuel and oxygen in ambient air as the oxidant. With a total effective area of 10.2 cm² and a 5% (w) Fe-loaded activated carbon fuel of 17 g, the stack reveals a peak power of 4.1 W at 800℃. The stack discharged at a constant current of 1.0 A for 19 h, giving a charge capacity of 19 A·h and an energy capacity of 31.6 W·h, which are much higher than those of a similar stack with anode on the inside and carbon loaded at the interior. The high capacity of our DC-SOFC opens up potential applications in portable devices.     

Preparation and characterization of sulfated zirconia (SO4/ZrO2)/Nafion composite membranes for PEMFC operation at high temperature/low humidity

Fine particle superacidic sulfated zirconia (SO₄²⁻/ZrO₂, S-ZrO₂) was synthesized by ameliorated method, and composite membranes with different S-ZrO₂ contents were prepared by a recasting procedure from a suspension of S-ZrO₂ powder and Nafion solution. The physico-chemical properties of the membranes were studied by ion exchange capacity (IEC) and liquid water uptake measurements, scanning electron microscopy (SEM) and X-ray diffraction (XRD) analysis, thermogravimetry–mass spectrometry (TG–MS) and Fourier transform infrared (FT-IR) spectroscopy. The results showed that the IEC of composite membrane increased with the content of S-ZrO₂, S-ZrO₂ was compatible with the Nafion matrix, the incorporation of the S-ZrO₂ could increase the crystallinity and also improve the initial degradation temperature of the composite membrane. The performance of single cell was the best when the S-ZrO₂ content was 15 wt.%, and achieved 1.35 W/cm² at 80 °C and 0.99 W/cm² at 120 °C based on H₂/O₂ and at a pressure of 2 atm, the performance of the single cell with optimized S-ZrO₂ was far more than that of the Nafion at the same condition (e.g. 1.28 W/cm² at 80 °C, 0.75 W/cm² at 120 °C). The 15 wt.% S-ZrO₂/Nafion composite membrane showed lower fuel cell internal resistance than Nafion membranes at high temperature and low relative humidity (RH).     

CeO2/RP-PSCFM@CoFe阳极材料用于质子导体乙烷燃料电池共生乙烯和电能

The continuous consumption and excessive use of fossil fuels promote the exploration of new energy conversion technologies. Meanwhile, the increase in the supply of ethane encourages the development of industrial technology for the production of ethylene chemical raw materials. Compared with traditional fossil fuel energy conversion equipment, solid oxide ethane cogeneration fuel cells are an efficient energy processing device. Through selective oxidation of fuel gas on the anode, the endothermic process of ethane dehydrogenation is converted into an exothermic oxidation reaction, which has a greater driving force for reaction thermodynamics, and simultaneously produces clean electricity and value-added chemicals without CO₂ emissions. The anode material used for the proton conductor ethane fuel cells needs to operate stably and efficiently under hydrocarbon fuel. Consequently, excellent catalytic activity, low polarization resistance, and anti-coking stability are essential. In this work, CeO₂ was uniformly impregnated into the surface of the porous cubic perovskite Pr_0.4Sr_0.6Co_0.2Fe_0.7Mo_0.1O_3−δ anode by wet impregnation, and then calcined and reduced to obtain a CeO₂/RP-PSCFM@CoFe composite anode embedded with nanoparticles, which was successfully used in electrolyte-supported proton conductor fuel cells. CeO₂ has a high ionic conductivity and transport capacity, which accelerates the transfer rate of protons on the anode and improves the catalytic reaction and transport process. Moreover, uniformly dispersed CeO₂ can effectively increase the three-phase interface of the anode reaction and increase the range of reaction activity. The peak power densities before and after wet impregnation reached 172 and 253 mW·cm⁻², respectively, at 750 ℃. When switching to ethane as the fuel, the peak power densities reached 136 and 183 mW·cm⁻², respectively. The polarization resistance of the impregnated single cell was significantly reduced, and the catalytic activity improved. Moreover, there was no attenuation for 10 h in the long-term test. Inversely, the current density increased with the continuous reduction of the composite anode. Product analysis revealed that the yield of ethylene increased from 23.52% at 650 ℃ to 34.09% at 750 ℃, and the ethylene selectivity exceeded 94%. These results clearly show that the impregnated anode exhibited excellent catalytic activity and anti-coking ability in hydrocarbon fuels at high temperatures. Combining CoFe nanoparticles with CeO₂ enhanced the electronic conductance and ionic conductance of the electrode, improved the transmission of electric energy and the efficient conversion of chemicals, thus successfully producing the cogeneration of electric energy and ethylene.     

硬模板法制备固体氧化物燃料电池Ni_(0.5)Cu_(0.5)Ba_(0.05)O_x包覆管状SDC立体阳极

为在固体氧化物燃料电池中有效利用干甲烷为燃料,需制作多孔立体阳极。采用硬模板法和浸渍法制备Ni_(0.5)Cu_(0.5)Ba_(0.05)O_x包覆管状SDC阳极材料(Ni_(0.5)Cu_(0.5)Ba_(0.05)O_x/SDC),为作对比,用溶胶凝胶法制备粉末状Ni_(0.5)Cu_(0.5)Ba_(0.05)O_x,机械混合SDC粉末制备Ni_(0.5)Cu_(0.5)Ba_(0.05)O_x-SDC。将这两种阳极材料分别制作电解质支撑的单电池Ni_(0.5)Cu_(0.5)Ba_(0.05)O_x/SDC|YSZ|LSMYSZ与Ni_(0.5)Cu_(0.5)Ba_(0.05)O_x-SDC|YSZ|LSM-YSZ,并进行发电性能测试以及长期稳定性实验。结果表明,800℃下,干甲烷环境中,Ni_(0.5)Cu_(0.5)Ba_(0.05)O_x-SDC为阳极的单电池最大功率密度为324.99 m W/cm2,运行10 h后,电压下降5.60%;而以Ni_(0.5)Cu_(0.5)Ba_(0.05)O_x/SDC为阳极的单电池最大功率密度达到384.54 m W/cm2,运行100 h后,电压未严重衰减。实验后阳极的SEM照片表明,Ni_(0.5)Cu_(0.5)Ba_(0.05)O_x-SDC阳极内孔隙狭小,易被积炭堵塞;而Ni_(0.5)Cu_(0.5)Ba_(0.05)O_x/SDC阳极呈立体多孔结构,有利于燃料气体与反应后气体的扩散。催化剂颗粒均匀地包覆在SDC纤维管表面,有利于增加三相界面,提高电池的稳定性。     

三组Pt- Ru/C催化剂前驱体对其性能的影响

分别以三组不同的Pt和Ru化合物为前驱体, 采用热还原法制备了Pt-Ru/C催化剂, 比较不同前驱体对催化剂性能的影响；通过XRD和TEM技术对催化剂的晶体结构及微观形貌进行了分析. 结果表明以H₂PtCl₆+RuCl₃和自制(NH₄)₂PtCl₆+Ru(OH)₃为前驱体的催化剂Pt和Ru没有完全形成合金状态, 在Pt(111)和Pt(200)之间有Ru(101)存在；以Pt(NH₃)₂(NO₂)₂和自制含钌化合物为前驱体制备的催化剂未检测出Ru金属或其氧化物的衍射峰, Pt-Ru颗粒在载体上分散均匀, 粒径最小, 为3.7 nm. 利用玻碳电极测试了循环伏安、记时电流和阶跃电位曲线, 考核了上述催化剂对甲醇阳极催化氧化活性的影响；结果表明：以Pt(NH₃)₂(NO₂)₂和自制含钌化合物为前驱体制备的催化剂对甲醇的电催化氧化活性最高, 循环伏安曲线峰电流密度达11.5 mA•cm^-2.