溶胶-燃烧法制备Ce_(0.8)Gd_(0.2)O_(1.9)及其性能

采用溶胶-燃烧法合成了Gd掺杂CeO2的Ce0.8Gd0.2O1.9(GDC)电解质粉末.研究了热处理温度对其相组成、颗粒大小、晶胞参数的影响.并对GDC烧结体的性能进行了研究.结果表明,溶胶一燃烧法可以成功制备出具有良好的烧结性的GDC电解质粉末,1500℃下得到的GDC烧结体的相对密度可以达到95%.电性能测试表明烧结体在中温范围内具有较高的氧离子电导率.     

Solid oxide fuel cell with corrugated thin film electrolyte

A low temperature micro solid oxide fuel cell with corrugated electrolyte membrane was developed and tested. To increase the electrochemically active surface area, yttria-stabilized zirconia membranes with thickness of 70 nm were deposited onto prepatterned silicon substrates. Fuel cell performance of the corrugated electrolyte membranes released from silicon substrate showed an increase of power density relative to membranes with planar electrolytes. Maximum power densities of the corrugated fuel cells of 677 mW/cm2 and 861 mW/cm2 were obtained at 400 and 450 degrees C, respectively.     

Co-precipitation synthesis and characterization of NiO-Ce0.8Sm0.2O1.9 nanocomposite powders: effect of precipitation agents

NiO-Ce0.8Sm0.2O1.9 (NiO-SDC) nanocomposite powders applied as promising anode material for low-temperature solid oxide fuel cells (SOFCs) were synthesized by hydroxide co-precipitation method using NH3 x H2O, NaOH and NH3 x H2O + NaOH as precipitation agents. The crystal phases, morphologies and sintering behavior of the synthesized NiO-SDC nanocomposite powders were investigated by means of X-ray diffraction (XRD), transmission electron microscopy (TEM) and sintering experiments. The effect of precipitation agents on the synthesis of the NiO-SDC nanocomposite powders was discussed. Results show that different precipitation agents influence greatly the synthesis and characteristics of the NiO-SDC nanocomposite powders. The NiO-SDC nanocomposite powders synthesized with NH3 x H2O deviate from the original composition due to the loss of Ni. The loss of Ni is avoided and nano-sized NiO-SDC composite powders are synthesized, when NaOH and NH3 x H2O + NaOH are used as precipitation agents. The NiO-SDC nanocomposite powders can be synthesized at relatively low temperature using NH3 x H2O + NaOH as precipitation agent, and the synthesized NiO-SDC nanocomposite powders show good sintering characteristics.     

Bismuth oxide-based solid electrolytes for fuel cells

During the last three decades, a large number of investigations has been reported pertaining to the science and technology of solid oxide fuel cells (SOFCs) based mainly on the yttria-stabilized zirconia (YSZ) electrolyte. Because of the problems associated with the high temperature of operation (~ 1000°C) of the YSZ-based cells, there has been a substantial effort to develop alternative electrolytes with ionic conductivity comparable to that of YSZ at relatively lower temperatures. This review presents a systematic evolution in the area of the development of new electrolytes based on bismuth sesquioxide for fuel cell applications at moderate temperatures.     

The electrolyte materials for SOFCs of low-intermediate temperature: review

The low-temperature trend of solid oxide fuel cells is necessary for its commercialisation, and the electrolyte materials with excellent properties at low and intermediate temperatures, which have become the focus of research. In this paper, the conduction mechanism, performance and research status of each kind of electrolyte are reviewed, and their advantages, disadvantages and applications are discussed. Finally, the development direction of low-intermediate temperature electrolyte materials and the problems to be solved are pointed out.     

Preparation of YSZ/YDC and YSZ/GDC composite electrolytes by the tape casting and sol-gel dip-drawing coating method for low-temperature SOFC

The composite electrolytes for low-temperature solid oxide fuel cells were fabricated via coating the YSZ sol on tape-casted substrates of yttria doped ceria (YDC) and gadolinia doped ceria (GDC). The doped ceria substrates with 98% of relative density were prepared by the tape-casting method followed by the sintering at 1,500°C for 2 hours. The YSZ polymeric sol for dip-drawing coating was synthesized by the partial hydrolysis of Zr-n-butoxide. The optimum dip-drawing coating rate for obtaining pinhole and crack free YSZ film was 2 cm/min using YSZ polymeric sol with 1.13 mol/ of concentration. After 10 times coating on ceria substrates with YSZ followed by the heat-treatment at 1,400°C for 2 hours, the fully densified YSZ film with 2.0 m of thickness without pores, cracks, or chemical reactions could be obtained. The results of single cell tests shows that YSZ layer coated doped ceria composite electrolyte prepared by the sol-gel dip-drawing method has an superior single cell performance to YSZ electrolyte without dissociation of ceria substrate.     

Enhancement of ionic conductivity of PEO based polymer electrolyte by the addition of nanosize ceramic powders

The ionic conductivity of polyethylene oxide (PEO) based solid polymer electrolytes (SPEs) has been improved by the addition of nanosize ceramic powders (TiO2 and AL2O3). The PEO based solid polymer electrolytes were prepared by the solution-casting method. Electrochemical measurement shows that the 10 wt% TiO2 PEO-LiClO4 polymer electrolyte has the best ionic conductivity (about 10(-4) S cm(-1) at 40-60 degrees C). The lithium transference number of the 10 wt% TiO2 PEO-LiClO4 polymer electrolyte was measured to be 0.47, which is much higher than that of bare PEO polymer electrolyte. Ac impedance testing shows that the interface resistance of ceramic-added PEO polymer electrolyte is stable. Linear sweep voltammetry measurement shows that the PEO polymer electrolytes are electrochemically stable in the voltage range of 2.0-5.0 V versus a Li/Li+ reference electrode.     

质子陶瓷膜燃料电池电解质材料的研究进展

质子陶瓷膜燃料电池作为固体氧化物燃料电池低温工作的一种有效途径而受到了广泛的关注.本文介绍了以高温质子导体为电解质的质子陶瓷膜燃料电池的进展,指出传统质子陶瓷膜燃料电池较差的化学稳定性是阻碍其发展的重要因素.重点评述了近期化学稳定性好的高温质子导体电解质材料的发展以及新的掺杂体系对于经典BaCeO3基质子导体在化学稳定性、电导率和烧结活性等方面的作用,分析了高温质子导体作为电解质材料在质子陶瓷膜燃料电池发展中存在的问题和发展的方向.     

Nacre-Inspired Composite Electrolytes for Load-Bearing Solid-State Lithium-Metal Batteries

Solid-state lithium-metal batteries with solid electrolytes are promising for next-generation energy-storage devices. However, it remains challenging to develop solid electrolytes that are both mechanically robust and strong against external mechanical load, due to the brittleness of ceramic electrolytes and the softness of polymer electrolytes. Herein, a nacre-inspired design of ceramic/polymer solid composite electrolytes with a “brick-and-mortar” microstructure is proposed. The nacre-like ceramic/polymer electrolyte (NCPE) simultaneously possesses a much higher fracture strain (1.1%) than pure ceramic electrolytes (0.13%) and a much larger ultimate flexural modulus (7.8 GPa) than pure polymer electrolytes (20 MPa). The electrochemical performance of NCPE is also much better than pure ceramic or polymer electrolytes, especially under mechanical load. A 5 × 5 cm² pouch cell with LAGP/poly(ether-acrylate) NCPE exhibits stable cycling with a capacity retention of 95.6% over 100 cycles at room temperature, even undergoes a large point load of 10 N. In contrast, cells based on pure ceramic and pure polymer electrolyte show poor cycle life. The NCPE provides a new design for solid composite electrolyte and opens up new possibilities for future solid-state lithium-metal batteries and structural energy storage.     

Present several items on ceria-based ceramic electrolytes: synthesis, additive effects, reactivity and electrochemical behaviour

Ceria-doped electrolytes have been extensively studied, because they are promising candidates for intermediate temperature solid oxide fuel cells (ITSOFC). In this work, several relevant aspects, such as powder synthesis, small additive effects, reactivity of electrode/electrolyte and interface microstructure were described. The combustion synthesis is a really suitable synthesis route to achieve, at low temperatures, finely, homogeneous and reactive powders for ceria based electrolytes. The presence of small amounts of titania is beneficial, since it produces a significant reduction of the grain boundary resistance. On the other hand, the reactivity of the ceria electrolyte against lanthanum-NiO perovskites at high temperatures (1475 °C), enhances both the LaNiO_3– decomposition and the diffusion of Ni and La ions as is noted in the reactivity analysis.     

Electrode materials: a challenge for the exploitation of protonic solid oxide fuel cells

Abstract

High temperature proton conductor (HTPC) oxides are attracting extensive attention as electrolyte materials alternative to oxygen-ion conductors for use in solid oxide fuel cells (SOFCs) operating at intermediate temperatures (400–700 °C). The need to lower the operating temperature is dictated by cost reduction for SOFC pervasive use. The major stake for the deployment of this technology is the availability of electrodes able to limit polarization losses at the reduced operation temperature. This review aims to comprehensively describe the state-of-the-art anode and cathode materials that have so far been tested with HTPC oxide electrolytes, offering guidelines and possible strategies to speed up the development of protonic SOFCs.     

La0.3Sr0.2Mn0.1Zn0.4 oxide-Sm0.2Ce0.8O1.9 (LSMZ-SDC) nanocomposite cathode for low temperature SOFCs

Nanocomposite based cathode materials compatible for low temperature solid oxide fuel cells (LTSOFCs) are being developed. In pursuit of compatible cathode, this research aims to synthesis and investigation nanocomposite La0.3Sr0.2Mn0.1Zn0.4 oxide-Sm0.2Ce0.8O1.9 (LSMZ-SDC) based system. The material was synthesized through wet chemical method and investigated for oxide-ceria composite based electrolyte LTSOFCs. Electrical property was studied by AC electrochemical impedance spectroscopy (EIS). The microstructure, thermal properties, and elemental analysis of the samples were characterized by TGA/DSC, XRD, SEM, respectively. The AC conductivity of cathode was obtained for 2.4 Scm(-1) at 550 degrees C in air. This cathode is compatible with ceria-based composite electrolytes and has improved the stability of the material in SOFC cathode environment.     

基于Pr0.6Sr0.4Co0.2Fe0.8O3-δ对称固体氧化物燃料电池的性能优化研究

采用柠檬酸-硝酸盐自蔓延燃烧法分别合成了Pr_0.6Sr_0.4Co_0.2Fe_0.8O_3-δ(PSCF)和Gd_0.2Ce_0.8O_2-δ(GDC)粉体, 高温固相法合成La_0.9Sr_0.1Ga_0.8Mg_0.2O_3-δ(LSGM)电解质粉体。以LSGM为电解质, PSCF同时作为阴极和阳极, GDC作为功能层材料, 构建了对称固体氧化物燃料电池PSCF│GDC│LSGM│GDC│PSCF。利用X射线衍射法研究材料的成相以及相互间的化学稳定性, 交流阻抗法记录界面极化行为, 用扫描电子显微镜观察电池的断面微结构, 用自组装的测试系统评价电池输出性能。结果表明, 合成的PSCF粉体呈立方钙钛矿结构, 具有良好的氧化-还原可逆性。使用GDC功能层明显改善了氢气环境下PSCF与LSGM材料间的化学相容性以及电池的输出性能, 800℃时, 电极│电解质界面极化电阻从6.892 Ω·cm²下降到0.314 Ω·cm²; 以加湿H₂(含体积分数3%的水蒸气)为燃料气, 空气为氧化气时, 单电池输出功率密度由269 mW/cm²增大至463 mW/cm²。研究结果显示, PSCF是对称固体氧化物燃料电池良好的候选电极材料, GDC功能层对改善电池长期稳定性能具有潜在的应用价值。     

Towards the next generation of solid oxide fuel cells operating below 600 °c with chemically stable proton-conducting electrolytes

The need for reducing the solid oxide fuel cell (SOFC) operating temperature below 600 °C is imposed by cost reduction, which is essential for widespread SOFC use, but might also disclose new applications. To this aim, high-temperature proton-conducting (HTPC) oxides have gained widespread interest as electrolyte materials alternative to oxygen-ion conductors. This Progress Report describes recent developments in electrolyte, anode, and cathode materials for protonic SOFCs, addressing the issue of chemical stability, processability, and good power performance below 600 °C. Different fabrication methods are reported for anode-supported SOFCs, obtained using state-of-the-art, chemically stable proton-conducting electrolyte films. Recent findings show significant improvements in the power density output of cells based on doped barium zirconate electrolytes, pointing out towards the feasibility of the next generation of protonic SOFCs, including a good potential for the development of miniaturized SOFCs as portable power supplies.     

Synthesis of yttria-doped bismuth oxide powder by carbonate coprecipitation for IT-SOFC electrolyte

Yttria-doped bismuth oxide (YBO) powders were synthesized by ammonium carbonate coprecipitation for the preparation of electrolytes of an intermediate temperature solid oxide fuel cell (IT-SOFC). The starting salts were yttrium and bismuth nitrate. The crystal structures and the morphological characteristics of the particles were analyzed by XRD and SEM, respectively. The ionic conductivity of the sintered pellet was measured by an electrochemical impedance analyzer. The size of the calcined YBO powders were in the range of 20-100 nm as measured by SEM images. The YBO pellets had a face-centered cubic structure, and their crystallite size was about 54-88 nm. The ionic conductivity of the YBO pellets sintered at 800 degrees C was observed to be 2.7 x 10(-1) Scm-(-1) at 700 degrees C. The ball-milling of the YBO powder before it was pelletized was found to have been unrequired probably because of a good sinterability of the YBO powders that was prepared via the ammonium carbonate coprecipitation method. The results showed that the ammonium carbonate coprecipitation process could be used as the cost-efficient method of producing YBO electrolytes for IT-SOFC.     

天然气中温SOFCs阳极材料钴掺杂氧化铈的制备与性能研究

采用溶胶凝胶法合成了新型中温固体氧化物燃料电池(IT-SOFCs)阳极材料Ce_1-xCo_xO_y（x＝0.10, 0.15, 0.20, 0.25, 0.30）(CDC),并采用共压共烧结法制备了以NiO-CDC复合阳极为支撑、以Ce_0.8Gd_0.2O_2-δ(GDC)为电解质、以La_0.8Sr_0.2Co_0.8Fe_0.2O_3-δ(LSCF)- GDC为复合阴极的单电池. 利用XRD和SEM等方法对阳极材料进行了晶相结构、微观形貌和化学相容性等分析. 在400~700℃范围内,以加湿天然气（3％H₂O）为燃料气,氧气为氧化气测试了电池的电化学性能. 结果表明：CDC阳极材料具有良好的孔道结构;八种不同阳极组成的单电池中50wt％NiO 50wt%Ce_0.8Co_0.2O_y（C20C80）阳极支撑的单电池具有最佳的电化学性能,在650℃时其最大电流密度为148.84mA/cm², 最大比功率为30.91mW/cm².     

The Influence of Interface Structures on the Conducting Properties of Zirconia (ZrO2)-Based Solid Electrolytes

Zirconia-based materials are the solid electrolytes used as the principal component of solid oxide fuel cells. The present generation of fuel cell designs incorporates self-supporting thin films (80–100 m) of the electrolyte on which various coatings of electrode are applied. The operating temperature of the cell is currently in the range 800–1000°C, and understanding the interface structures associated with these structurally complex components at these temperatures remains a constant challenge. Incremental changes in conductivity brought on by interface modifications can have a large influence on the viability of any particular system for commercial application. This review outlines the influence that a number of interface structures associated specifically with zirconia-based electrolytes have on the ionic conductivity. These include grain boundary structures, structures within grains, and the influence of additives. In addition, the effect of long-term anneals on the various interfaces is addressed. In each case, the combination of ionic conductivity measurements with detailed analytical electron microscopy has provided the clues as to how the various interface structures influence the physical properties of the solid electrolyte ceramic.     

Conductivity of the nanostructured ceramic material Zr<Subscript>0.88</Subscript>Sc<Subscript>0.1</Subscript>Ce<Subscript>0.01</Subscript>Y<Subscript>0.01</Subscript>O<Subscript>1.955</Subscript> prepared from mechanically activated powders

The structure of the Zr_0.88 Sc_0.1Ce_0.01Y_0.01O_1.955 solid solution, a candidate for the use as a solid electrolyte in fuel cells with a low temperature, has been investigated using x-ray powder diffraction and Raman spectroscopy. Single-phase ceramic materials have been produced from powders prepared by the mechanochemical synthesis from ZrO₂ nanoprecursors purified of the impurities introduced during grinding of commercial zirconia. The solid solution has a rhombohedral structure at room temperature owing to the partial ordering of oxygen vacancies. The electrical conductivity of the ceramic materials sintered at temperatures below 1570 K exhibits a hysteresis due to the delay of the martensitic transition from the cubic phase to the rhombohedral phase upon cooling of the sample. The nanostructured ceramic materials are characterized by a high mechanical strength and unusually close values of the activation energies for bulk and grain-boundary electrical conduction.     

基于热应力分析的固体氧化物燃料电池阳极功能层优化设计

为了降低固体氧化物燃料电池在制备和工作过程中产生的热应力, 提高电池的电化学性能, 在电池中引入功能梯度层可以有效减小电池各层之间材料参数的差异, 从而缓解各层之间的热失配应力。本研究将阳极功能层引入燃料电池中, 通过阳极功能层子层数目和非线性梯度成分指数n控制各子层材料属性的变化情况, 研究了燃料电池在800℃下的热应力分布。结果表明: 选取适当的指数n和阳极功能层的分层数目可以明显降低阳极层的最大拉应力和电解质层的最大压应力。     

Effect of submicron grains on ionic conductivity of nanocrystalline doped ceria

Doped ceria has been considered for high oxygen ion conductivity for solid oxide fuel cells. In the present study, 20 mole% samarium doped nano ceria powder was prepared by wet chemical synthesis and sintered at different temperatures to retain submicron grains (> 92-96% density). ionic conductivity of the sintered pellets was measured using impedance spectroscopy as a function of temperature (200-800 degrees C). The total maximum conductivity was 1.0 x 10(-2)S.cm(-1) (at 600 degrees C) for samples sintered at 1200 degrees C. The activation energy at higher test temperature decreases with the decrease in the sintering temperature (by 25%). The grain boundary, grain interior conductivity and activation energy of the electrolyte were correlated to the resulting microstructure. It has been demonstrated that use of doped nano ceria powder as precursor not only reduced the sintering temperature but also provided segregation free grain boundary for engineering higher conductivity dense electrolytes.