Microfabricated solid oxide fuel cells

Micro-fabricated solid oxide fuel cells (µSOFCs) are finding an increasing interest as potential power sources for portable devices such as MP3 players or laptops. The aim of this work was to fabricate a µSOFC demonstrator that works at 500°C and is fuelled by hydrogen. This thesis was divided into two parts. The first one was devoted to the development of an electrolyte and electrodes in form of sputtered thin films with electrical and mechanical properties suitable for the implementation in a real cell. YSZ and CGO electrolyte have been reactively sputtered from metallic targets. Both films are dense and have a columnar microstructure. The ionic conductivity of these films was of 0.5 S/m at 550°C for the CGO and of 5.5 x 10-3 S/m at 500°C for the yttria stabilized zirconia (YSZ) . Albeit the ceria doped gadolinia (CGO) was a better ionic conductor at low temperature, it was not possible to obtain an open circuit voltage (OCV) with a CGO electrolyte film. Most likely, the reduction of the Ce+4 ion into Ce+3 in a hydrogen atmosphere creates an electrical leakage. Better results were obtained with YSZ layers. Single, (111) textured columnar films showed OCV's of 200 mV. Best results were obtained with a double layer of two different microstructures. The first one exhibited a dense, columnar microstructure with (111) texture. The second layer was porous with nanocrystalline grains and preferential (200) orientation. The improved properties are ascribed to the absence of film crossing grain boundaries. Of special interest is the mechanical stress behaviour upon heating to the operation temperature. The stress was investigated as a function of temperature up to 700°C. An anomalous, hysteretic behaviour was found during the first heating cycle in YSZ as well as CGO thin films. This phenomenon could be modelled as an oxygen uptake to fill up excess oxygen vacancies created during the sputtering process. The model allowed to derive a diffusion activation energy of 0.6 eV for these excess vacancies in YSZ. Annealing in air at 700 °C permits to reduce stress and to stabilize the YSZ membrane. As electrode materials, sputter deposited, porous platinum, porous Ni-CGO composites and dense LaxSr1-xCoO3-y (LSCO) thin films were developed and characterized. The PEN (Positive electrode-Electrolyte-Negative electrode) layer processes were combined with Micro Electro Mechanical System (MEMS) process technology to fabricate µSOFC test devices. The PEN membranes were liberated by deep silicon dry etching. The cell diameter was varied between 0.5 and 5 mm, the electrolyte thickness between 500 and 700 nm. A nickel grid grown by electroplating was used to support the electrolyte layer and to serves as current collector for the anode. The cell with a 5 mm diameter shows a very good mechanical stability up to 600°C in SOFC operating conditions and for several heating cycles. The functionality of the fuel cell with two 20 nm thick porous platinum electrodes and a YSZ bil