SOFC电解质薄膜YSZ制备技术

综述了固体氧化物燃料电池 (SOFC)电解质薄膜YSZ的制备方法 ,通过EPD、APS、VPS、EVD、Sol Gel和流延、轧膜、丝网印刷等方法都可以制备YSZ薄膜。从成膜质量上比较 ,APS、VPS、EVD等方法制得的YSZ薄膜气密性好 ;从生产成本上分析 ,由高到低依次是VPS、APS、EVD、Sol Gel和流延、轧膜、丝网印刷等陶瓷成膜方法。目前 ,制备YSZ电解质薄膜使用较多的是APS、EVD ,最适合大工业化生产、成本低廉的是陶瓷薄膜成型方法 ,市场前景广阔     

Carbon tolerance effects of Sr<Subscript>2</Subscript>NiMoO<Subscript>6-δ</Subscript> as an alternative anode in solid oxide fuel cell under methane fuel condition

Sr₂NiMoO_6-δ (SNMO) with a double perovskite structure has been investigated as an alternative anode material for solid oxide fuel cells. The SNMO anode was compatible with the GDC electrolyte at the SOFC operating conditions. The SNMO anode was not stable at high temperatures and reducing atmospheric conditions, where Ni exsoluted from the SNMO double perovskite structure to form Ni nanoparticles. Ni nanoparticles provided highly electrochemically active sites in both H₂ and CH₄. Ni nanoparticles also provided chemically active sites for the pyrolysis of methane under H₂O shortage, leading to carbon deposition on the anode. To improve the cell performance, the SNMO anode was modified by a GDC thin film coating on the anode pore wall surface to increase the number of reaction sites and also accelerate the electrochemical reaction kinetics of the anode. The anode polarization resistance in CH₄ was decreased by the GDC modification from 18.39 Ωcm² to 0.55 Ωcm² at 800 °C. The 60% of the cell performance was improved by the GDC modification on the SNMO anode. The GDC-modified SNMO anode cell was stable for 100 h when CH₄ fuel was used.     

湿化学法制备LT-SOFCs材料及其性能研究

采用湿化学法制备了低温固体氧化物燃料电池(LT-SOFCs)阳极材料NiO、阴极材料LSCF(La0.6Sr0.4Co0.2Fe0.8O3)和电解质材料GDC(Gd0.1Ce0.9O1.95)粉体。X射线衍射(XRD)结果表明三种粉体成相良好,没有杂相存在。采用湿化学法合成的粉体成功制备了GDC膜电解质阳极支撑型固体氧化物燃料电池,并对单电池的电化学性能和稳定性进行了分析和研究。单电池在加湿氢气(3%H2O)燃料中,600℃下最大输出功率密度达384 mW/cm2,并在550℃下经历了约12 h的稳定性测试,输出电压恒定,电池稳定性良好。     

二氟磷酸锂对MCMB负极性能的影响

采用恒流充放电、电化学阻抗谱(EIS)、SEM及X射线光电子能谱(XPS)等方法,研究无机锂盐二氟磷酸锂(LiPO2F2)对锂离子电池负极材料中间相碳微球(MCMB)性能的影响。当电解液中LiPO2F2的含量为1.0%时,MCMB/Li电池在1.50~0.01 V以0.2 C放电、1.0 C充电循环100次,容量保持率为96.9%,比未添加LiPO2F2电解液的电池提高了22.0%。主要原因是LiPO2F2的加入有利于电极表面形成更稳定、致密的固体电解质相界面(SEI)膜,降低电极界面阻抗。     

Ce_(0.8)M_(0.2)O_(2-δ)(M=Co,Fe,Mn)用于天然气中温SOFCs阳极的研究

采用溶胶-凝胶法合成了过渡金属掺杂的CeO2新型中温固体氧化物燃料电池(IT-SOFCs)阳极材料Ce0.8M0.2O2-δ(M=Co,Fe,Mn)(20 CDC、20 FDC、20 MDC).采用共压-共烧结法制备了以NiO-20 CDC、NiO-20 FDC、NiO-20 MDC复合阳极为支撑、以Ce0.8Gd0.2O2-δ(GDC)为电解质、以La0.8Sr0.2Co0.8Fe0.2O3-δ(LSCF)-GDC为复合阴极的单电池.利用XRD、SEM等方法对阳极材料进行了物相结构和微观形貌分析.在400～700℃范围内,以湿天然气(3%H2O)为燃料气、氧气为氧化气测试比较了三种电池的放电性能.结果表明:所制的20 CDC、20 FDC、20MDC粉体均为萤石型结构;在制备的电池中,(50%)NiO-20 CDC阳极材料具有良好的孔道结构,且具有最佳的电化学性能,在650℃时其最大电流密度为148.84 mA/cm2,最大比功率为30.91 mW/cm2.     

Ceria-Zirconia Composite Electrolyte for Solid Oxide Fuel Cells

Ceria-zirconia-ceria sandwich structured composite filmelectrolytes were designed in order to offer high ionic and low electronicconductivity electrolyte films. Calculation of oxygen potential profile inthe composite film electrolyte indicates that a very thin zirconia filmkills the electronic current of ceria without affecting the ionicconductivity. The composite films were successfully prepared by a co-fireprocess. The main problem was the fact that the ceria and zirconia greenfilms had different shrinkage behaviors. Successful co-firing was achievedby controlling the temperature program and amount of binder. De-laminationbetween yttria stabilized zirconia(YSZ) and gadolinia doped ceria(GDC)layers was overcome by the formation of a solid solution phase at theinterface of the two films. The resultant composite films, however, showedpoor electrical conductivity compared with theoretical values. The formationof a solid solution phase can have a negative effect on compositeelectrolytes. Also, the composite film is unsatisfactory in terms ofmechanical strength. This could be due to the lattice expansion in reducingatmospheres, thermal expansion coefficient mismatch, or the intrinsicweakness of the ceria texture.     

Electrical properties of Bi4Ti3O12 textured by screen printing

The focus of this work is to explore the electrical properties of bismuth titanate, Bi₄Ti₃O₁₂, textured through the process of screen printing. Textured BTO samples were produced using the templated grain growth technique and the electrical properties were measured both within and normal to the texture plane. The relative permittivity and polarization were determined as a function of electric field, temperature, and frequency. The electrical properties improved dramatically (P_r?=?25 ??C/cm², ??_r(??)?=?1800 at 1 MHz) compared to a randomly oriented sample (P_r?=?10 ??C/cm², ??_r(??)?=?850 at 1 MHz) when measured within the texture plane. A corresponding reduction of electrical properties normal to the texture plane was observed (P_r?=?2 ??C/cm², ??_r(??)?=?300 at 1 MHz). The electrical properties of bismuth titanate textured by screen printing compare favorably to other texture-inducing techniques such as tape casting and hot forging.     

全固态薄膜锂蓄电池研究进展

全固态薄膜锂蓄电池是目前国内外电池研究的新热点,其在未来微电子器件中具有广泛的应用前景.综述了全固态薄膜锂蓄电池国内外研究状况,介绍了全固态薄膜锂蓄电池的结构、工作原理及制备方法,并对全固态薄膜锂蓄电池的正负极膜及电解质膜研究情况作了详细的阐述.     

Tailoring the pore structure of cathode supports for improving the electrochemical performance of solid oxide fuel cells

Two types of lanthanum doped strontium manganite (LSM)-yttria-stabilized zirconia (YSZ) composite cathodes were prepared, one with the finger-like straight open pores by the phase inversion tape casting, and the other with the randomly distributed tortuous pores by the conventional tape casting. A gas permeation flux of 42.5?×?10⁵ Lm^?2 h^?1 was measured under a trans-membrane pressure of 0.6 bar for the former while only 10.6?×?10⁵ Lm^?2 h^?1 for the latter. Fuel cells supported on the as-prepared LSM-YSZ composite cathodes were fabricated, comprising a 15 μm thick YSZ electrolyte layer and a 20 μm thick NiO-YSZ anode. The electrochemical performance of the fuel cells was measured using H₂ as fuels and air as oxidants. The cell supported on the phase-inversion derived cathode showed a maximum power density of 362 mWcm^?2 at 850 °C, while only 149 mWcm^?2 for the cell supported on the cathode formed by the conventional method. The difference in the electrochemical performance between the two cells can be attributed to the pore structure of the cathode supports. It is concluded that the phase inversion tape casting provides a simple and effective approach for tailoring the pore structure of the cathode support and thus enhancing the electrochemical performance.     

化成电压对锂离子电池性能的影响

研究化成电压对钴酸锂(Li Co O2)正极、石墨负极的锂离子电池性能的影响。从电池容量、倍率、阻抗、存储和循环性能等方面,并从负极固体电解质相界面(SEI)膜形成机理的角度,分析电池性能的差异。化成充电截止电压设定为3.70 V,与3.80 V相比,电池的容量、倍率、阻抗和存储等性能都有所改善。不同化成截止电压生成的SEI膜厚度不同,3.80 V时生成的SEI膜外层疏松,有机锂盐层增厚,因有机层稳定性差导致电芯的存储性能变差。     

Fabrication and performance of a ScMnSZ/LaSrCuFe cell with GDC interlayer for solid oxide fuel cells

Strontium- and copper-doped lanthanum ferrite (LaSrCuFe) was used as new cathode material for solid oxide fuel cells (SOFCs) with scandia-stabilized zirconia electrolyte at intermediate temperatures. The performance of an anode-supported single cell prepared using a Ni/YSZ anode, ScMnSZ ((ZrO₂)_0.89(Sc₂O₃)_0.1(MnO₂)_0.01) electrolyte, and a LaSrCuFe cathode was evaluated. The effects on the cell performance of the GDC (GD_0.1Ce_0.9O_1.95) interlayer between the electrolyte and cathode were also investigated. The microstructure and chemical composition of the cell were analyzed using a scanning electron microscope (SEM) equipped with an energy dispersive X-ray analyzer (EDS). AC impedance spectroscopy was used to measure the polarization resistance of a single cell. The results highlight the promising combination of ScMnSZ electrolyte and LaSrCuFe cathode material in terms of chemical compatibility and electrical performance.     

Sinterability,Mechanical, Microstructural,and Electrical Properties of Gadolinium-Doped Ceria Electrolyte for Low-Temperature Solid Oxide Fuel Cells

In this study, we report key functional properties of gadolinium-doped ceria (Gd_0.1Ce_0.9O_1.95, GDC) sintered at low temperatures as well as single-cell electrochemical performance of a single-cell prepared there of. GDC solid solutions were sintered at various temperatures ranging 1100–1400^∘C and characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), density measurements, mechanical strength tests and electrical conductivity measurements. The dry-pressed GDC disc sample sintered at 1100^∘C was found to have 96% of the theoretical density and higher sintering temperatures led to higher densities. SEM micrographs of the fracture and plan surfaces of the sintered discs established the absence of any open pores. The sample sintered at 1100^∘C exhibited high electrical conductivity of 0.027 S/cm at 650^∘C. The mechanical strength of the sintered samples was determined to be in the range of 150–175 MPa. Greater than 96% of theoretical density, good mechanical strength, and high electrical conductivity of GDC disc samples sintered at 1100^∘C established the viability of low-temperature processing of GDC for its use as an SOFC electrolyte. Accordingly, a single-cell was prepared by co-sintering of GDC electrolyte and LSCF-GDC cathode at 1100^∘C and subsequent firing of CuO-GDC anode at 900^∘C. The electrochemical performance of the cell was evaluated in H₂ fuel at 650^∘C.     

Acceptor-doped ceria deposited on a porous Ni film as a possible micro-SOFC electrolyte

Micro-SOFCs, miniaturized solid oxide fuel cells (SOFCs) for low temperature operation, are being developed as a power source for portable electronics. Reducing the thickness of the electrolyte and the adoption of acceptor-doped ceria as an electrolyte material are important to minimize the Ohmic resistance at low temperature. Acceptor-doped ceria thin-films are often deposited on nano-porous metal substrates to reduce cracking of the thin electrolyte. However, due to the difficulty of depositing a pore-free electrolyte on a porous medium, the cells often show the low open circuit voltages (OCVs). In this study, we have deposited ～1 μm-thick Gd-doped ceria on a nano-porous nickel film to assess whether a thin-film, metal-supported GDC can be deposited as a pore-free layer and would thus be suitable as an electrolyte of micro-SOFCs. The Ni-supported GDC cell showed an OCV of ～0.92 V at 450 °C under a hydrogen/air gradient. The high OCV verifies that the thin-electrolyte layer, deposited on porous Ni using the pulsed laser deposition (PLD) method, is dense enough to prevent gas leakage as also observed in its microstructure.     

带有YSZ保护膜的Bi_2O_3基固体电解质燃料电池的制备及其性能分析

用带(ZrO_2)_(0.92)(Y_2O_3)_(0.08)(YSZ)保护膜的Bi_2O_3基固体电解质(Bi_20_3)_(0.75)(Y_2O_3)_(0.25)、(Bi_2O_3)_(0.75)-(Gd_2O_3)_(0.25)、(Bi_2O_3)_(0.08)_(0.25)和(MoO_3)_(0.25)做成燃料电池.在600～800℃,将其输出特性与用纯的(ZrO_2)_(0.92)(Y_2O_3)_(0.08)做电解质的燃料电池进行比较.Bi_2O_3基电解质燃料电池的输出功率高于YSZ电解质的,这是由于Bi_20_3基固体电解质具有较高的氧离子导电率;Bi_20_3基电解质燃料电池的开路电压比YSZ的低,是由于Bi_20_3基电解质中存在着一定的电子导电率.从材料的结构、机理上对所得结果进行了分析.     

碳酸亚乙烯酯添加剂对锂离子电池性能的影响

用循环伏安(CV)、恒电流充放电(GC)、扫描电镜(SEM)以及傅里叶红外光谱(FT-IR)方法研究了添加剂碳酸亚乙烯酯(VC)对锂离子电池负极界面膜性质及电池循环性能的影响。研究表明,在首次充电过程中VC参与了SEI膜的形成,形成的膜主要成分为Li2CO3以及VC的还原聚合物。充放电实验结果表明电解液中加入少量VC能显著提高电池的初始放电容量,电池的循环稳定性也有所提高。     

浇铸法制备的PEO基偏铝酸锂复合固态电解质

通过浇铸法制备含快离子导体金属盐LiAlO2(LAO)的聚氧化乙烯(PEO)基复合固态电解质,对LAO不同质量分数的复合固态电解质进行电化学性能测试。复合固态电解质的电化学窗口拓宽,离子电导率提高到8.39×10^-5 S/cm。以复合物固态电解质组装Li/LiFePO4全固态电池,当LAO质量分数为4%,在60℃以0.1 C于2.5~4.0 V充放电,电池的首次放电比容量为153.61 mAh/g,循环50次的容量保持率仍在90%以上。     

Direct-write fabrication of integrated planar solid oxide fuel cells

Integrated planar solid oxide fuel cell (IP-SOFC) with multilayered structure has been fabricated via direct-writing process named robo-dispensing. Partially stabilized zirconia (PSZ) substrate with sufficient mechanical strength and gas permeability was utilized as a support for SOFC. The 2-cells serially integrated planar SOFC in which each cell is composed of the line-shaped electrode and electrolyte was produced The SOFC component paste materials were dispensed through cylindrical nozzle of 0.21 mm in diameter onto a moving plate that was controlled by robo-dispensing machine. The thicknesses of anode, electrolyte and cathode were 30 μm, 15 μm and 20 μm, respectively. The fabricated IP-SOFC exhibited OCV of 1.82 V and maximum power density of 35 mW.     

锂离子电池热失控过程负极放热反应研究

采用热重分析-傅里叶变换红外光谱法(TGA-FTIR)、差示扫描量热法(DSC)和X射线衍射光谱法(XRD)对锂离子电池中石墨负极材料在热失控和热爆炸中的反应机理进行了系统的研究和探讨.研究表明,石墨表面在最初循环中形成的原始固体电解质(SEE)膜具有热不稳定性,在t＞70 ℃时开始分解.而失去了原始SEI膜保护,会导致石墨中嵌入锂和其表面电解液的接触,在高温时形成二次电解质膜.详细讨论了石墨中嵌入锂的数量和石墨颗粒的结构、形状及其层状结构边缘的比表面对二次电解质膜形成的影响.     

Screen-printed piezoceramic thick films for miniaturised devices

The development towards smaller devices with more functions integrated calls for new and improved manufacturing processes. The screen-printing process is quite well suited for miniaturised and integrated devices, since thick films can be produced in this manner without the need for further machining. On the other hand, the process of screen printing thick films involves potential problems of thermal matching and chemical compatibility at the processing temperatures between the functional film, the substrate and the electrodes. As an example of such a miniaturised device, a MEMS accelerometer based on PZT thick film will be presented. The design and process flow of this accelerometer has been optimised by means of finite element modelling (FEMLAB©). Consequently it has proved possible to eliminate post-processing steps after the screen printing of the PZT thick film.     

以氯化镍作正极材料的热电池研究

以高温处理氯化镍作为热电池的正极材料制备热电池;用溶解理论解释了电池单体材料溢流现象,解决了电池的安全性问题;摸索了与之匹配的制备高比能量热电池所需电解质与负极材料,确定电解质为全锂电解质,负极为LiB合金;用浓差极化解释了氯化镍电池的电压起伏成因。所制备的氯化镍电池的单体电压比以二硫化钴为正极的电池单体电压高25%。与全锂电解质和LiB合金匹配制备的样品电池,比能量达到84Wh/kg。