Tape suitable for use in fuel cells, electrode suitable for use in a fuel cell, method for sintering an electrode of this type and a fuel cell provided with an electrode of this type

Abstract: The invention relates to a tape suitable for use in fuel cells, to an electrode suitable for use in a fuel cell, to a method for sintering an electrode of this type and to a fuel cell which contains an electrode of this type. The invention provides a tape with improved properties, which is characterised in that said tape contains LiCoO₂. A tape of this type can be produced in a manner known per se using LiCoO₂ and a binder. Expediently, a plasticiser and/or dispersant and/or anti-foam is used together with the binder, as is known per se for the preparation of tapes. Platelets can be produced from such a tape, which platelets can then be sintered, optionally after stack-ing. Sintering is expediently carried out in an atmosphere consisting of 60 to 80% air and 40 to 20% carbon dioxide, in particular 68 to 72% air and 28 to 32% carbon dioxide. A suitable temperature programme is chosen for sintering. Good results are obtained by heating to 250°C at a heating rate of 100°C per hour, then heating to 450°C at a heating rate of 50°C per hour, then heating at a heating rate of 100°C per hour to the desired sintering temperature of 800 to 1000°C and finally, after sintering, cooling to room temperature at a rate of 100°C per hour. Of course, the invention also relates to fuel cells which are provided with a material according to the invention.

Description: The invention relates to a tape suitable for use in fuel cells, to an electrode suitable for use in a fuel cell, to a method for sintering an electrode of this type and to a fuel cell which contains an electrode of this type. Fuel cells are generally known and are becoming increasingly important in connection with economic energy conversion. From EP-A-0 101 422 a low temperature alkaline cell is known in which lithium is used as dotant. An other promising type of fuel cell is the molten carbonate fuel cell which functions at elevated temperature and places high demands on electrodes. The aim is inter alia to obtain cathodes which have a low overpotential and which also have long-term stability against the effects of the electrodes used in such a cell. The use of a cathode of lithium-containing nickel oxide (NiO) is known. A tape of the type described in the preamble has now been found which is characterised in that said tape contains LiCoO₂. A tape of this type can be produced in a manner known per se using LiCoO₂ and a binder. Expediently, a plasticiser and/or dispersant and/or anti-foam is used together with the binder, as is known per se for the preparation of tapes. Platelets can be produced from such a tape, which platelets can then be sintered, optionally after stack-ing. Sintering is expediently carried out in an atmos-phere consisting of 60 to 80% air and 40 to 20% carbon dioxide, in particular 68 to 72% air and 28 to 32% carbon dioxide. A suitable temperature programme is chosen for sintering. Good results are obtained by heating to 250°C at a heating rate of 100°C per hour, then heating to 450°C at a heating rate of 50°C per hour, then heating at a heating rate of 100°C per hour to the desired sintering temperature of 800 to 1000°C and finally, after sintering, cooling to room temperature at a rate of 100°C per hour. Of course, the invention also relates to fuel cells which are provided with a material according to the invention. Carbon is incorporated in the tape in order to give the material the desired porosity. The carbon is in the form of grains having an average size of 30 to 34 micrometers and is incorporated in an amount of 10 to 40% by weight. The carbon burns during sintering and then leaves openings behind. Example 1 The starting material used was 1 mol of metal nitrate solution consisting of 0.5 ml of Li⁺-ions originating from LiNO₃ and 0.5 mol of Co²⁺-ions originating from Co(NO₃)₂.6H₂O to which 1.5 mol of citric acid and 2.25 mol of ammonium nitrate have been added. The starting materials are dissolved in demineralised water, with stirring and gentle warming. A 1.5 litre stock solution is made in order to prepare 100 g of pyrolised powder. Per preparation 75 ml are introduced into the 3 l elongated (quartz) beaker. In order to prevent condensation on the walls, the beaker is wrapped in heating tape. The solution in water is evaporated with (magnetic) stirring until a viscous solution has formed. The stirrer disc is removed and the beaker is covered with a gauze. The solution is evaporated further until it starts to swell and spontaneous ignition takes place. After ignition, the heating is switched off and the powder formed is collected. The powder obtained, optionally in combination with the powder originating from other similar preparations, is kept at 500°C for 8 hours in order to remove the carbon formed from the citric acid during the pyrolysis. Determinations by X-ray diffraction after the carbon removal by burning to completion showed that LiCoO₂ has been formed. In order to prepare a suspension, the required amount of LiCoO₂ (50 g) is mixed in a polythene bottle (500 ml) with carbon now deliberately added as a large pore-former (20 g). 450 g ZrO₂ balls and an amount of binder (Cerbind) which is sufficient to allow the balls to move freely (100 g) are then added. This binder also contains plasticiser, dispersant, anti-foam and the like (that is to say the usual additives for the production of tapes). The amount of binder used depends on the amount of carbon (see Table A). Dichloromethane (CH₂Cl₂) is added for dilution. The mixture is then rolled for 2 hours on a roller bench (90 revolutions per minute). The suspension is poured off from the balls, freed from air under reduced pressure and then processed on a teflon®-coated glass plate to give a tape. The tape casting speed is 1.25 m/min. The leading blade is set at 2.25 mm and the second blade at 2.00 mm. After the tape has formed, the tape is dried in air for some time under a drying cap. Data on starting materials for suspension preparation Powder (g) Carbon (g) Binder (g) CH₂Cl₂ (g) 50.00 7.50 100.23 25.19 60.75 9.14 241.60 60.00 62.34 1.37 201.30 49.20 42.54 10.61 100.00 25.05 60.00 15.01 166.68 80.02 42.57 10.64 99.37 50.97 49.50 24.08 140.37 59.03 47.31 0.00 80.00 47.56 50.59 33.79 176.13 54.84 Prior to sintering, a number of circular platelets of the desired diameter (depending on shrinkage) are punched from the tape to be used. These platelets are placed on top of one another and, under a gas mixture of 70% air and 30% CO₂ (dry cathode gas) in a tubular furnace, are heated to 250°C at 100°C per hour, then from 250 to 450°C at 50°C per hour and finally to the desired sintering temperature (between 800°C and 1000°C) at 100°C per hour. After sintering, the stack is cooled to room temperature at 100°C per hour. The sintered platelets are characterised with the aid of X- ray diffraction, scanning electron microscopy, atomic absorption spectroscopy, and Hg-porosimetry. In the same way as LiCoO₂, LiFeO₂ was also produced and processed to form electrodes. Example 2 Cathodes were produced by means of tape casting from an LicoO₂ powder and an LiFeO₂ powder. The cathodes obtained were tested in laboratory cells having a surface area of 3 cm², The results obtained using these materials and the results obtained using the known NiO cathode are shown in Table B and the figure. For comparison, the figures for known, lithium-containing NiO cathodes are included in the Table. It can be seen from the data that LiFeO₂ cathodes show a poor cell performance, which is essentially independent of the porous microstructure. The ohmic losses are high (about 4 times those of a conventional NiO cathode). The poor performance is mainly the consequence of a high polarisation (6 times that of NiO). At 650°C the cell performance is poor. Raising the cell temperature to 700°C does give an improvement in the cell performance as a consequence of the reduction in the polari-sation, as a result of which a more linear IV characteristic is obtained. The LiFeO₂ cathodes used here are doped with 3 mol% magnesium. Repeating the test with cathodes to which Co has been added in place of Mg leads to hardly any change in the characteristics. An appreciably better performance is obtained in the case of the LiCoO₂ cathode. The polarisation is appreciably lower. Table C shows several current densities which are obtained for the total surface area as determined using Hg porosimetry. It can be seen from the results that the characteristics of NiO cathodes are predominantly controlled by the mass transfer (i o /i₁, approximately 5). It was indeed already known that the kinetic characteristic of NiO cathodes is fast. In the case of LiCoO₂ cathodes mass transfers and kinetic characteristic are approximately equally significant (i o /i₁ approximately 2). LiFeO₂ cathodes are mainly controlled by kinetic characteristic (i o /i₁ approximately 0.03). At a temperature of 700°C the characteristic of the LiCoO₂ cathode is more controlled by the mass transfer. The limiting current density i₁ is mainly determined by the transport characteristic of reactants and products in the carbonate (film) of the moistened electrode. Consequently it is expected that i₁ is dependent on the porous microstructure and only to a lesser extent on intrinsic material characteristics. The temperature will also have a small effect unless chemical reaction occur in the carbonate film, which reactions have a highly temperature-dependent rate of reaction. It is pointed out that the i₁ values which are obtained are all of the same order of magnitude. The porous microstructure of LiCoO₂ and LiFeO₂ are also very similar to one another. Performance of cells with LiFeO₂, LiCoO₂ or NiO cathode with a current density i=160mA/cm² Cathode material T = 650°C T = 700°C V cel (mV) η kath (mV) (iR) kath (mV) V cel (mV) η kath (mV) (iR) kath (mV) LiFeO₂ 435 357 148 530 250 140 LiCoO₂ 745 80 180 880 50 80 NiO 900 53 35 900 53 35 η kath is the cathode polarisation, (iR) kath is the ohmic loss of the cathode T = 650°C T = 700°C Cathode material A eff i₀/i₁ i₀ i₁ i₀/i₁ i₀ i₁ (m²) (mA/cm²) (mA/cm²) NiO 0.22 5.0 3.4 0.7 - - - LicoO₂ 0.15 2.0 1.0 0.5 41 36 0.9 LiFeO₂ 0.15 0.03 0.05 1.3 1.2 0.5 0.4

Claims: Method for preparing an electrode for a high temperature molten carbonate fuel cell, comprising the provision of a tape containing a binder and at least 42.54 % LiCoO₂ and subjecting said tape to a sintering treatment. Method according to claim 1, wherein said tape is sintered in an atmosphere consisting of 60 to 80% of air and 40 to 20% of carbon dioxide. Method according to claim 2, wherein sintering is carried out in a mixture consisting of 68 to 72% of air and 28 to 32% of CO₂. Method according to claim 3, wherein up to 250°C heating is at a heating rate of 100°C per hour, then up to 450°C heating is at a heating rate of 50°C per hour, then heating is at a rate of 100°C per hour up to the desired sintering temperature of 800-1000°C and finally, after sintering, cooling to room temperature is at a rate of 100°C per hour. Method according to one of the previous claims, wherein one or more stacked platelets produced from tape are sintered. Fuel cell comprising molten carbonate as electrolyte and at least one electrode prepared according to the method of one of the claims 1-5. Fuel cell according to claim 6, wherein said electrode comprises a binder. Fuel cell according to claim 6 or 7, wherein said electrode contains carbon and/or plasticiser and/or dispersant and/or anti-foam.

Inventors: PLOMP LAMBERTUS, SITTERS ERIC FRANCISCUS, PLOMP, LAMBERTUS, SITTERS, ERIC FRANCISCUS
Applicants: STICHTING ENERGIE, STICHTING ENERGIEONDERZOEK CENTRUM NEDERLAND(ECN)
Application year: 1991
Main classification: H01M4
IPC codes: H01M8, H01M4, C04B35