熔融碳酸盐燃料电池LiCoO2涂覆阴极的微观结构和性能

采用溶胶-凝胶技术，制备了LiCoO2涂覆的熔融碳酸盐燃料电池NiO阴极．研究了LiC002涂覆阴极的微观组织和在Li2CO3-K2CO3熔融碳酸盐中的溶解特性，并对其电化学性能进行了测试．结果表明LiCoO2涂层有效地降低了NiO在Li2CO3-K2CO3熔盐电解质中的溶解度和溶解速率，对单电池的性能有所改善，并在一定程度上抑制了Ni在电解质基板中的沉淀．     

多孔镍和多孔氧化镍在熔融碳酸盐中原位形变行为的研究

熔融碳酸盐燃料在开始运行初期，承受一定负荷的多孔镍在率为多孔氧化镍阴极的过程中往往会受到较严重的形变破坏，对电池的使用性能和寿命造成不良影响。本文采用一套自行设计研制的LVDT侠移测试系统，对多孔镍和多孔氧化镍在恒载荷下的形变行为进行初步研究。结果表明，加载下的多孔镍在熔融碳酸盐中进行原位氧化、锂化时其形变最为严重；而经预先氧化锂化的多孔镍在相同实验条件下形变相对较小。多孔氧化镍在不同实验条件下的形变总体上均不明显。研究结果对防止MCFC阴极材料的形变破坏有重要指导意义。     

新型熔融碳酸盐燃料电池阴极的制备及其溶解性的研究

以LiNO_3和Co(NO_3)_2·6H_2O为原料,以柠檬酸为燃料,采用燃烧合成法制备了LiCoO_2包覆的多孔NiO阴极。X射线衍射技术(XRD)、X射线能量散射谱(EDAX)和电子显微镜(TEM和SEM)分析表明,NiO颗粒表面的包覆层是由尺寸小于100纳米的LiCoO_2微粒构成,并与NiO颗粒紧密烧结在一起,有效地减少了NiO与熔融碳酸盐的接触面积,降低了氧化镍的溶解度。     

MCFC用电解质基板的相稳定性

采用浸入法来模拟熔融碳酸盐燃料电池（MCFC）环境，研究了MCFC电解质基板材料LiAlO2在不同条件下相的稳定性。α-、β－LiAlO2在空气环境下是不稳定的；在含CO2气氛中却发现γ-和α－两相存在相互转变，说明混合体系在MCFC环境下能够保持初始相组成。     

熔融碳酸盐燃料电池系统研究

全部采用国内易购的材料，研制出有效面积为336cm^2的NiO阴极和Ni-Al合金阳极及面积为900cm^2的γ-LiAlO2电解质板和双极板；采用62％Li2CO3 38%K2CO3熔融盐作为电解质，组装出由30个电池组成的千瓦级熔融碳酸盐燃料电池堆；在800小时连续运行试验中，电堆性能稳定。以摩尔组分为99．7％的H2为燃料气，空气中的氧气为氧化剂进行测试，单电池平均工作电压大于0．72V，最大电流密度达165mA/cm^2，最大输出功率达1080瓦。     

MCFC型燃料电池的神经网络建模与基于FGA的模糊控制研究

为了提高燃料电池的发电性能,熔融碳酸盐燃料电池(MCFC)堆的运行温度应该控制在一个合适的范围内。本文首先利用RBF神经网络辨识复杂非线性系统的能力,基于实验的输入输出数据,建立起MCFC电堆的神经网络温度模型;然后设计了MCFC电堆工作温度的一个基于模糊遗传算法的在线模糊控制器,用模糊遗传算法同时优化模糊控制器的参数及规则。最后用神经网络的辨识模型代替实际的电堆进行控制仿真,仿真结果证明建模是有效的,所设计的模糊控制器具有较好的性能。     

燃料电池实现商业化应用的大门正在打开--2005年全球燃料电池应用调查报告

燃料电池是一个将化学能直接转化为电能的电化学系统。依据所用电解质的不同，燃料电池可分为碱性燃料电池（AFC）、质子交换膜燃料电池（PEMFC）、磷酸型燃料电池（PAFC）、熔融碳酸盐燃料电池（MCFC）和固体氧化物燃料电池（SOFC）五类。近年来，由于PEMFC中的直接甲醇燃料电池（Direct Methanol Fuel Cell，DMFC）具有激活速度快，使用的燃料为甲醇，具有储运方便且成本低等优势而倍受青睐，在全球国际大厂积极投入研发推波助澜下，技术进展迅速。     

熔融碳酸盐燃料电池研制

研制了 330cm2 × 3的MCFC电堆 ,平均每个电池的开路电压达到 1 10V左右 ,电堆电流密度达到 15 0mA/cm2 ,输出功率为 10 0W。在电解质基板以及电极内部添加增强纤维 ,有效地防止了运行时基板断裂。电池以多孔陶瓷板材料γ LiAlO2 作为电解质支持体 ,阳极、阴极采用多孔板Ni,孔隙率大于 5 0 %。     

日本第45届电池研讨会概要

日本第45届电池研讨会于2004年11月27日～29日在京都召开，发表论文330篇。其中锂2次电池160篇，占48％；燃料电池132篇，占40％；镍氢电池15篇；电容器12篇：铅电池8篇，其余3篇。在锂2次电池中，正极69篇：负极、电解液、固体电解质68篇；大型电池、评价、安全性23篇。在燃料电池中，PEFC(固体高分子燃料电池)83篇；DMFC(直接甲醇燃料电池)35篇；SOFE(固体氧化物燃料电池)10篇：MCFC(熔融碳酸盐燃料电池)4篇。     

熔融碳酸盐燃料电池阴极材料的水基流延制备

水/乙醇取代传统具有毒性的有机溶剂,采用水基流延工艺制备多孔NiO阴极,研究造孔剂尿素和活性炭的添加量对孔隙率的影响。通过对电极孔隙率测定以及扫描电镜(SEM)分析,结果表明水基流延法能够制备出质地均匀的NiO电极,当活性炭与Ni的质量比为0.075时,NiO电极孔隙率达到最大值66.6%;而当尿素与Ni的质量比为0.05时,NiO电极最大孔隙率则达到了60.1%。     

Behaviour of Ni, NiO and LixNi1−xO in molten alkali carbonates

Ni, NiO and Li_xNi_1-xO are the cathodic materials commonly used in molten carbonate fuel cells (MCFCs). Since the instability of the cathode is recognized as a major hindrance to MCFC development, in this report the behaviour of these nickel species in molten alkali carbonates is reviewed, analyzing step by step the processes of lithiation, dissolution and sinterization at cell operating temperatures.     

Overview of the effects of rare-earth elements used as additive materials in molten carbonate fuel cell systems

From the viewpoint of materials issues, there are some problems in molten carbonate fuel cell (MCFC) systems due to the corrosive and evaporative electrolytes and the high pressure caused by a stack in temperature of 650°C. The rare earth metals (RE) in as material additives primarily improve the creep resistance, corrosion resistance and high temperature resistance of materials. However, efforts to enhance the properties of MCFC materials using RE have not yielded the marked effects associated with their use in solid oxide fuel cells (SOFC). Therefore, we have conducted this review in order to describe and discuss the effects of RE as additive materials in the context of MCFC. This review also provides information regarding the development of MCFC materials using RE. The incorporation of low concentrations of RE into previously RE-free materials may improve the stability of these materials to some degree, and also effect an increase in the cell efficiency of MCFC. La₂O₃-added cathode materials have primarily been applied as alternative materials, for the reduction of the dissolution of conventional NiO cathodes. Ce and Dy have both been theorized to possibly enhance the stability of anode electrode materials. Ce and La can both be employed as additives which enhance the stability of reforming catalysts. The addition of La₂O₃ to electrolytes has been previously shown to reduce the degree of dissolution in cathodes. Ce-based ceramics are thought to be promising coating materials, and it is believed that they may help to prevent the corrosion of the separator. However, future research into materials which exhibit long-term stability and low electrical conductivity is clearly warranted, as the field is in its infancy.     

Electrochemical performance of Y2O3/NiO cathode in the molten Li0.62/K0.38 carbonates eutectics

The preparation and subsequent oxidation of Ni cathodes modified by impregnation with yttria were evaluated by surface and bulk analysis. The electrochemical behavior of Y₂O₃/NiO cathodes was also evaluated in a molten 62 mol% Li₂CO₃ + 38 mol% K₂CO₃ eutectic at 650 °C by electrochemical impedance spectroscopy (EIS) as a function of yttria content and immersion time under the standard cathode gas condition (CO₂:O₂ = 67:33%). The stability tests of Y₂O₃/NiO cathodes showed that the yttria additive could dramatically reduce the solubility of NiO in the eutectic molten Li/K carbonates due to the preferential dissolution of yttria. The loss of yttria was confirmed by chemical analysis and X-ray diffraction (XRD). The Y₂O₃/NiO cathodes showed higher catalytic activity for oxygen reduction and lower dissolution of NiO than the pure NiO cathode. The cathode material with 1.0 wt.% of yttria showed the optimum behavior.     

Stability of NiO cathode modified by ZnO additive for molten carbonate fuel cell

The preparation and subsequent oxidation of nickel cathodes modified by impregnation with zinc oxide (ZnO) were evaluated by surface and bulk analysis. The ZnO impregnated cathodes showed the similar porosity, pore size distribution and morphology as the reference nickel cathode. The stability tests of ZnO impregnated NiO cathodes in the eutectic molten Li/K carbonates showed that the ZnO additive could dramatically reduce the solubility of NiO in the melts under the standard cathode condition. The mechanism of ZnO additive on the solubility reduction of NiO cathode in the melts was also proposed in this paper. ZnO/NiO materials could be alternative cathode materials for molten carbonate fuel cells.     

An Ultrastable and High‐Performance Flexible Fiber‐Shaped Ni–Zn Battery based on a Ni–NiO Heterostructured Nanosheet Cathode

Currently, the main bottleneck for the widespread application of Ni–Zn batteries is their poor cycling stability as a result of the irreversibility of the Ni‐based cathode and dendrite formation of the Zn anode during the charging–discharging processes. Herein, a highly rechargeable, flexible, fiber‐shaped Ni–Zn battery with impressive electrochemical performance is rationally demonstrated by employing Ni–NiO heterostructured nanosheets as the cathode. Benefiting from the improved conductivity and enhanced electroactivity of the Ni–NiO heterojunction nanosheet cathode, the as‐fabricated fiber‐shaped Ni–NiO//Zn battery displays high capacity and admirable rate capability. More importantly, this Ni–NiO//Zn battery shows unprecedented cyclic durability both in aqueous (96.6% capacity retention after 10 000 cycles) and polymer (almost no capacity attenuation after 10 000 cycles at 22.2 A g^?1) electrolytes. Moreover, a peak energy density of 6.6 µWh cm^?2, together with a remarkable power density of 20.2 mW cm^?2, is achieved by the flexible quasi‐solid‐state fiber‐shaped Ni–NiO//Zn battery, outperforming most reported fiber‐shaped energy‐storage devices. Such a novel concept of a fiber‐shaped Ni–Zn battery with impressive stability will greatly enrich the flexible energy‐storage technologies for future portable/wearable electronic applications.     

Tuning Oxygen Redox Chemistry in Li‐Rich Mn‐Based Layered Oxide Cathodes by Modulating Cation Arrangement

Li‐rich Mn‐based oxides (LRMO) are promising cathode materials to build next‐generation lithium‐ion batteries with high energy density exceeding 400 W h kg^?1. However, due to a lack of in‐depth understanding of oxygen redox chemistry in LRMO, voltage decay is not resolved thoroughly. Here, it is demonstrated that the oxygen redox chemistry could be tuned by modulating cation arrangement. It declares that the materials with Li/Ni disorder and Li vacancies can inhibit the formation of O? O dimers. Because of the high chemical activity, O? O dimers could accelerate lattice oxygen release and NiO/spinel formation. The samples without forming O? O dimers show improved performance in suppressing oxygen overoxidation and mitigating cation dissolution. As a result, the optimized cathode exhibits a high capacity over 280 mA h g^?1 at 0.1 C and a high plateau voltage of 3.58 V with a very low voltage decay of 1.6% after 150 cycles at 1 C. This study opens an attractive path in designing Li‐rich electrodes with stabilized redox chemistry.