逆电渗析热机新型工质开发及电化学特性研究

逆电渗析(reverse electrodialysis,RED)热机能够将低品位热能有效地转换为电能。作为热机的核心部件,RED电堆的性能直接影响热机的整体能量转换性能。为提升RED热机能量转换效率,通过开发一种由氯化锂、氯化铵与水混合形成的三元工质用于RED电堆,并与常规氯化钠水溶液对比探讨了进、出口溶液电导率和电化学性能。首先,测试了不同比例氯化锂与氯化铵混合水溶液作为RED电堆工质的电导率,并根据相关性能指标筛选出两种盐的最佳质量摩尔浓度比例为2∶8。然后,将此最佳比例下的溶液应用于RED。通过实验与NaCl水溶液对比研究了改变浓、稀溶液浓度对电堆进、出口溶液电导率和电堆内阻的影响。结果表明,适当增加进料浓、稀溶液浓度有利于降低RED电堆内阻,从而改善电堆性能。     

海水中的污染物对逆电渗析电堆性能的影响

海水淡化装置排出的浓缩卤水会造成盐差能的浪费,逆电渗析电堆可以有效回收这种盐差能,并直接转换为电能。但是以海水和浓缩卤水为工作溶液的电堆性能易受工作溶液中不溶性物质的影响。为揭示这种影响规律,对逆电渗析电堆进行了定期的污染物附着实验研究。首先定期测试逆电渗析电堆的输出性能,获得了电堆性能衰减的规律;进而采用扫描电镜和能谱分析仪对离子交换膜和隔垫上的污染物种类进行分析,探究各附着物引起电堆性能下降的原因。结果表明：运行初期（0～20 d）,电堆的开路电压、最大功率密度、能量转换效率,以及内阻变化速度快;运行后期（20～45 d）,浓缩卤水侧的压降增速较快。本研究可为逆电渗析电堆的清洗策略提供一定的理论支持。     

负载跟踪状态下的铝空气电池堆最优功率点优化方法

基于铝空气电池堆二阶等效电路,建立内阻特性和电气输出特性模型,研究操作条件对活化内阻、欧姆内阻、浓差内阻和电堆总内阻的影响作用和变化规律;以电堆输出满足任意负载需求为前提,以总内阻最小为优化目标,基于“最优功率点”概念,提出一种基于粒子群算法的操作条件优化方法,获得最优工作温度、电解液浓度和输出电压等,实现电堆输出性能优化;通过仿真研究和实验研究,验证模型、方法的有效性和可靠性。研究结果表明:在负载跟踪状态下,电堆工作在最优功率点处其堆内总内阻最小;操作条件对电堆输出性能的影响作用和变化规律,在交流阻抗特性和U-I输出特性中的表现具有一致性;该优化方法能够提高电堆输出性能,减少堆内能量损耗。     

高温质子交换膜燃料电池电堆稳定性分析与优化

高温质子交换膜燃料电池（HT-PEMFC）应用前景广阔,但是目前HT-PEMFC电堆寿命较短。为此,本文对一个百瓦级空冷HT-PEMFC电堆的稳定性进行了研究。恒电流测试结果发现电堆中间位置单电池电压的衰减速率是两端的5～10倍。XRD、TEM测试结果表明电堆不同位置单电池催化剂Pt粒径变化较小,而极板吸酸量滴定与欧姆极化损失分析结果表明中间位置单电池磷酸流失速率是两端的2～3倍,导致其内阻是两端的5～8倍,膜中磷酸的流失迁移至电极导致氧增益电压比两端增加41～102mV。综上,电堆中间位置单电池磷酸流失过快是导致电堆寿命缩短的主要原因,而电堆温度分布不均则是磷酸流失过快的主要原因。因此,若要提高电堆的寿命,关键要从电堆磷酸与热的管理方面进行优化。     

电流与浓差对逆电渗析电堆内质量传递的影响

以氯化钠溶液作为工质情况下,通过改变逆电渗析电堆输出电流和溶液浓差,对由5对Selemion型离子交换膜（IEMs）单元电池所构成的实验用RED电堆进行堆内质量传递规律的实验研究。研究结果发现,IEMs选择性系数（a）、溶剂透膜渗透速率（v_w）、溶质透膜迁移通量（J_NaCl）和同价离子透膜扩散率（D_NaCl）均受电堆电流密度和溶液浓差的影响。当溶液浓差增大时,a降低,而v_w、J_NaCl和D_NaCl均增大;当电流密度增大时,a和v_w降低,J_NaCl和D_NaCl增大。     

1.5 kW质子交换膜燃料电池堆动态工况响应特性

考察了自制1.5 kW质子交换膜燃料电池(PEMFC)电堆在动态工况下的性能。研究了PEMFC电堆电压、功率、反应参数随车载工况运行出现的响应情况。发现在大电流密度下,由于各单电池的差异,电堆电压和功率出现比较明显的波动现象。在选定两个工况周期中,电堆各单电池电压的差异系数C_V最大达到4.23%,最高单电池电压和最低单电池电压相差0.106 V。数据分析表明在该动态工况下,PEMFC电堆的动态响应特性受到反应物和电堆温度变化、空气局部流量过大或不足以及电堆内部阳极和阴极出现明显压降等因素的影响。该研究不仅为后续耐久性测试提供分析依据,还对PEMFC电堆实际车载运行参数与控制策略的优化具有指导意义。     

逆向电渗析法海水盐差能发电工艺研究

采用逆电渗析法技术对反渗透浓排水进行浓差发电,考察了浓溶液和稀溶液的浓度比、浓溶液与稀溶液流向、离子交换膜类型、反渗透浓海水和模拟海水等对逆电渗析发电装置功率密度的影响。结果表明:在其它条件相同情况下,随着溶液的浓度比增加,功率密度也随之增加;低面电阻高渗透选择性的离子交换膜具有高的功率密度;采用并流的方式所得到的功率密度比错流的高;反渗透浓海水中的多价离子对逆电渗析海水盐差能发电功率密度有一定的影响。     

PEMFC电堆动态工况响应性能试验

质子交换膜燃料电池（PEMFC）电堆动态响应特性对PEMFC电堆的耐久性和可靠性具有很大影响。本文试验考察了PEMFC电堆在动态工况下的输出性能、单电池电压均衡性变化和动态响应特性。结果表明,在整个动态运行工况下,电堆运行良好,进出口冷却液温差小于5℃。电流阶跃变化时电堆电压均衡性出现突增变化,同时随着电流的增大,稳态时电堆均衡性变差。在超负荷（200A）运行工况下,电堆各单电池之间输出差异变大,均衡性持续变差,电堆中间和前端单电池电压明显降低。此外,在整个动态响应过程中电流阶跃上升时的电压最大下冲值比电流阶跃下降时的电压最大上调量大,但输出电压能在10s内达到相对稳定的状态（电压波动率＜0.02）。通过该研究,以期为实际车载电堆运行和控制优化提供参考。     

空气流量对空冷燃料电池电堆性能的影响研究

空冷型氢燃料电池采用开放型阴极,具有自增湿、系统简单轻便等特点。为了揭示空气流量对输出性能的影响机制,对自组装的800 W空冷型燃料电池电堆进行了实验测试和数值分析,对比了不同空气风扇转速下电堆输出电压、净功率以及传质传热特性。结果表明：小电流条件下小空气流量可以保持电堆内较高的温度,减少活化损失,实现高净输出功率。然而,大电流条件下,小空气流量将导致电堆温度过高且分布不均匀。利用数值方法对组分和温度分布进行了可视化分析,结果表明低含水量引起的欧姆损失增加是限制输出功率的关键因素,通过提高风扇转速增加空气流量可以保证较好的冷却效果,从而提高含水量,减少欧姆损失。     

空气流量对空冷燃料电池电堆性能的影响研究

空冷型氢燃料电池采用开放型阴极,具有自增湿、系统简单轻便等特点。为了揭示空气流量对输出性能的影响机制,对自组装的800 W空冷型燃料电池电堆进行了实验测试和数值分析,对比了不同空气风扇转速下电堆输出电压、净功率以及传质传热特性。结果表明：小电流条件下小空气流量可以保持电堆内较高的温度,减少活化损失,实现高净输出功率。然而,大电流条件下,小空气流量将导致电堆温度过高且分布不均匀。利用数值方法对组分和温度分布进行了可视化分析,结果表明低含水量引起的欧姆损失增加是限制输出功率的关键因素,通过提高风扇转速增加空气流量可以保证较好的冷却效果,从而提高含水量,减少欧姆损失。     

Electric conductivity and electric convertibility of potassium acetate in water,ethanol, 2,2,2–trifluoroethanol, 2–propanol and their binary blends

Salinity gradient energy between the concentrated and diluted electrolyte solutions can be converted to electric energy by using reverse electrodialysis (RED) technology. Electrolyte solution is a vital factor that impacts the energy conversion efficiency. Potassium acetate (KAc) was chosen as solute, and water, ethanol, 2,2,2-trifluoroethanol (TFE), 2-propanol (IPA) and several of their binary mixtures were selected as solvents. Electric conductivity of these solutions were measured under varying conditions. KAc was easily ionized in water and possessed the maximum electric conductivity, following by KAc–H₂O–TFE and KAc–H₂O–ethanol, and then KAc in pure TFE, ethanol, and IPA respectively. For electric convertibility of these solutions working in a RED power generation system, it was found that the KAc–H₂O possessed the maximum power density, and the KAc–ethanol–H₂O possessed the larger open circuit voltage than aqueous KAc solution under the same working condition. Besides, it was observed that both the electric conductivity and electric convertibility were significantly influenced by the concentration and temperature of solution. With the increasing of concentration, electric conductivity of these solutions increased firstly and then reached to the peak, but later it decreased. Solution temperature took a positive impact role to the electric conductivity. Electric conductivity of these solutions can be estimated by using a modified amplitude version of Gaussian peak function.     

Evaluation of a Non‐sealed Solid Oxide Fuel Cell Stack with Cells Embedded in Plane Configuration

A non‐sealed solid oxide fuel cell stack with cells embedded in plane configuration was fabricated and operated successfully in a box‐like stainless‐steel chamber. For a two‐cell stack, it demonstrated an open circuit voltage (OCV) of 2.13 V and a maximum power output of 569 mW at the flow rate of 67 sccm CH₄ and 33 sccm O₂. A fuel utilization of 4.16% was obtained. The cell performance was dominated by two different mechanisms, the polarization of the cathode at low current and the concentration polarization of the anode at high current. Finally, a scaled‐up stack with six cells in series generated an OCV of 6.4 V and a maximum power output of 8.18 W.     

应用于大尺寸平板型固体燃料电池电堆的Al2O3-SiO2-CaO基密封材料软化特性及其验证

设计研制了Al₂O₃-SiO₂-CaO基密封材料,对其高温晶化与软化、热性能、界面黏结特性开展了原位观察,并进行了电堆实际应用验证。结果表明:在不高于1 100℃时该密封材料均为非晶态,850℃开始软化,900~1 000℃出现球化。热重分析表明密封材料在0~960℃的质量损失较小,约为0.06%;密封材料与连接板、电池界面黏结紧密,利于固体氧化物燃料电池(SOFC)电堆密封应用。采用研制的密封材料组装了2个5单元SOFC短堆,分别进行了热循环与稳定性研究。结果表明:2个5单元电堆的开路电压达到6.0 V,平均开路电压1.2 V,电堆1热循环前后在35 A(0.56 A/cm²)条件下输出功率为运行无衰减,电堆2在27 A(电流密度0.43 A/cm²)进行恒流放电,运行300 h较为稳定。     

反电渗析法海洋盐差电池的结构优化与能量分析

盐差能是存在于海水和淡水之间或者两种含盐浓度不同的海水之间的化学位差能,是以化学能形态存在的海洋能。反电渗析法是一种利用盐差能发电的方法,相比于其他方法,具有更高的能量密度。但是,目前对反电渗析法盐差电池的研究均限于小尺寸膜堆,放大实验发现功率密度显著降低,对过程的能量效率更少有分析。因此,对反电渗析法海洋盐差能利用过程进行数学模拟,对膜堆进行结构优化,研究在不同的结构参数下反电渗析盐差电池的功率密度和能量效率。结果表明,减小隔板厚度可以很大程度地提高反电渗析过程的功率密度和能量效率,增加RED装置的长度会获得较高的能量效率,但是平均功率密度有所降低。     

New Stack Design of Micro‐tubular SOFCs for Portable Power Sources

Micro‐tubular solid oxide fuel cells (SOFCs) have high thermal stability and higher volumetric power density, which are considered to be ideal features for portable power sources and auxiliary power units for automobile. Here, we report a new stack design using anode supported micro‐tubular SOFCs with 2 mm diameter using Gd doped CeO₂ (GDC) electrolyte, NiO‐GDC anode and (La, Sr)(Co, Fe)O₃ (LSCF)‐GDC cathode. The new stack consists of three bundles with five tubular cells, sealing layers and interconnects and fuel manifolds. The performance of the stack whose volume is 1 cm³ was shown to be 2.8 V OCV and maximum power output of 1.5 W at 500 °C, applying air only by natural convection. The results also showed strong dependence of the fuel flow rates on the stack performance, which was correlated to the gas diffusion limitation.     

Novel design of flow path spacers for reverse electrodialysis cell

Reverse electrodialysis (RED) is one of the technologies used to harness ‘Blue Energy’, which is generated from the controlled separation of ions between salt water and fresh water through cation and anion exchange membranes (CEM/AEM) stack with end electrodes. The spacers present in between CEM and AEM allows the flow of salt and fresh water significantly affecting the fouling and concentration polarization in the RED cell. The present work focuses on improvement in flow path design, which may be used in place of mesh spacers in order to reduce pressure drop and enhance shear stress on the surface of the membrane to reduce concentration polarization. A three-dimensional direct numerical simulation of the Navier–Stokes equation is conducted using Fluent 14.0 to analyze four different flow field designs, including serpentine, criss-cross, rhombus, diamond, and standard mesh spacers. The simulation predicted closely the experimental data on pressure drop for the mesh spacers available in the literature. The present study points out that the diamond type flow field design, which combines characteristics of mesh spacers and flow field plates, gives lesser pressure drop per unit length with the increase in velocity within the same range of shear stress generated in mesh spacers. In other words, net power density of RED would improve with the use of diamond type spacer flow field with the decrease in concentration polarization loss and pumping power density.     

低温等离子体用于柴油机尾气脱硝的实验

柴油机作为卡车、重型机械以及船舶的主动力装置仍被广泛采用,其尾气中氮氧化物的脱除技术也是目前的研究热点。本文搭建了模拟柴油机尾气的配气系统,采用介质阻挡放电产生低温等离子体（non-thermal plasma,NTP）的方法对模拟柴油机尾气进行了脱硝的实验研究。实验结果表明：针对本系统,电源效率和能量密度随着输入电压的增大而升高,当输入电压高于60V时,电源效率在90%以上;在O₂/N₂条件下,随着O₂浓度以及能量密度的增加,NO生成量逐渐增加,NO₂生成量先增加后降低最终趋于稳定;在NO/N₂条件下,低温等离子体对NO的脱除率接近100%;在NO/O₂/N₂条件下,随着NO浓度的增加,临界O₂浓度升高,O₂体积分数为1%时脱硝效率在90%以上,O₂体积分数高于14%时低温等离子体的脱硝率为负值,且随着能量密度的增加,生成的NO _x 浓度也更高,O₂浓度对低温等离子体的脱硝性能起决定性作用;在低能量密度时,加入NH₃会提高脱硝性能,高能量密度时NH₃会略微降低NTP的脱硝性能,当加入H₂O模拟真实柴油机尾气成分且喷氨时,获得的脱硝率最高为40.6%。     

A study on direct glucose and fructose alkaline fuel cell

Direct glucose fuel cell (DGFC) has huge potential as a power source in low power long term portable devices. Electro-oxidation of glucose and fructose on PtRu/C catalyst are studied using cyclic voltammetry in alkaline medium to study the reason for deactivation of glucose fuel cell. A simple direct glucose fuel cell with PtRu/C as anode and activated charcoal as cathode was constructed and operated to study the effect of different temperature and concentration of glucose and KOH. An open-circuit voltage (OCV) of 0.91 V is obtained using 0.3 M glucose in 1 M KOH solution. OCV increased with the increase in glucose concentration. The maximum peak power density of 1.38 mW cm⁻² is obtained using 0.2 M glucose in 1 M KOH at 30 °C and it decreases with further increase in glucose concentration and temperature. In order to determine the reason for decrease in performance of glucose fuel cell due to conversion of glucose to fructose, the fuel cell was operated using 0.2 M fructose in 1 M KOH. The peak power density delivered is 0.57 mW cm⁻². The DGFC is continuously operated for 260 h at constant load of 500 Ω produces final constant voltage of 0.21 V.     

带有蛇形流场的微生物燃料电池串联堆性能特性

以四个成功启动的带有蛇形流场的单电池构造了微生物燃料电池串联堆(MFCS-S),测试了MFCS-S性能,探讨了其性能提升的限制因素,研究了增加反极电池阴、阳极电解液流量,采取混联的方式运行,移除反极电池和反接反极电池对电堆性能的影响。实验结果表明:MFCS-S在输出电压为2.11 V时获得最大功率密度(2226 mW·m^-2);在一定电流条件下,性能较差的单电池发生电压反极,这是限制MFCS-S性能提高的主要原因;增加反极电池阴、阳极流量虽然不能较大幅度地改善单电池反极,但是却能大幅度提高电堆功率密度;采用混联方式运行不但可以有效避免电池反极,而且可以大幅度提高电堆功率密度;移除反极电池并不能有效地避免电池的反极,反接反极电池反而进一步加剧反极。