POLYCRYSTALLINE LITHIUM METAL OXIDE FIBERS

Abstract: A method for preparing polycrystalline lithium metal oxide fibers of the formula LixMyOz by filling micromold fibers of a desired inner diameter and length with a mixture composed of the desired metal salts or solutions of salts or alkoxides, optionally containing additional solvents, binders, plasticizers, and deflocculants, firing the filled micromold fibers at elevated temperatures but below temperatures of lithium oxide volatilization in air for at least one hour to simultaneously burn-out the micromold and yield the polycrystalline lithium metal oxide fiber.

Description: "POLYCRYSTALLINE LITHIUM METAL OXIDE FIBERS * This invention describes polycrystalline lithium metal oxide ceramic fibers of the formula Li x M v O z , where M is aluminum, silicon, or a transition metal with atomic numbers ranging from 22-31 and 40-52 and methods for their manufacture. Ceramic fibers are recognized as having utility in a variety of industrial composites. Composite materials are desired combinations of two or more con¬ stituent materials to form a bonded structure that has mechanical, physical and chemical advantages over each individual constituent. In particular, ceramic matrix composites contain a matrix component that may be a ceramic oxide and a reinforcing material like a ceramic fiber. Some of the various applications of these com¬ posites are cutting tools, armor, engine parts, electronic devices, catalysts, and medical implants. Electrolyte tiles in molten carbonate fuel cell prepared from gamma lithium aluminate powder and lithium carbonate/potassium carbonate electrolyte could be improved by incorporating suitable reinforcing fibers in the tiles. A typical tile is about 1 m 2 in area and from 0.5-2 mm in thickness. Reduction in tile thickness is desirable in order to reduce electrical resistance. This can be achieved by the addition of reinforcement fibers to increase the strength and durability of the tile structure and the overall life- time of the cell. Such reinforcing fibers must not only have high strength but the fibers must also be compatible with the matrix material, and be thermally stable at temperatures up to at least 650°C under the molten carbonate fuel cell environment. Alumina fibers have been tested but formation of lithium aluminate occurred. Ideally, lithium aluminate fibers are the best choice for the molten carbonate fuel cell electro¬ lyte tile. Other applications may potentially require other lithium aluminum oxide fibers such as lithium pentaaluminate, lithium dialuminate, or other lithium metal oxide fibers. Methods developed for the production of ceramic fibers include spinning, colloidal evaporation, vapor deposition, and drawing from a melt. Non-oxide fibers like silicon carbide fibers have been prepared by these processes but limitations have been observed when applied to compositions containing glass-forming oxides. An example is the production of ceramic refractory fibers like alumina-silica, alumina, and zirconia by a blowing method wherein a stream of the molten material is subjected to a jet of air or steam. The disadvantages of this method are the requirement for a huge capital investment in specialized plant machinery and the phase separation that may occur from rapidly cooling the drawn fiber to prevent devitrifi¬ cation or crystallization. In the solution spinning process currently used for the production of alumina fibers, control over the form of the fibers, such as fiber diameter, is done by spinning the alumina fibers at low temperature from a melt of pure raw materials containing not more than 60-65% alumina followed by heat treatment above 1000°C. The synthesis of polycrystalline lithium metal oxide fibers such as lithium aluminate fibers has been investigated but only a few successful processes have been reported. One of the major difficulties in the preparation of lithium aluminate fibers by drawing from a melt is the loss of lithium oxide due to evolution at elevated temperatures. Therefore, a lower temperature or shorter time would be more desirable for the synthesis of lithium aluminate fibers, conditions which do not generally lead to proper densification or proper phase of the lithium aluminate. atanabe and his co-workers disclosed in Japanese patent application 63-260812 a method for the prepara¬ tion of long, rod-shaped / 9-LiAl0 2 crystals in the Journal of the American Ceramic Society, Vol. 70:10, C- 268-269 (1987) . Raw materials were LiOH«H 2 0 : -AI2O 3 : NaOH in mole ratios of 4:1:4. Columnar test pieces were shaped from these mixed powders under 9.8 MPa pressure, fired at 600°C for three hours, cooled, and dipped into water for 24 hours to yield rod-shaped β- LiAlθ2 crystals that were 1.5 μ ~~ \ in diameter and 10 to 15 μm long. Examples cited showed the fiber properties of these crystals obtainable under various powder compositions and calcination conditions. The problems with this approach include the potential conversion of -LiA10 2 to other phases in the fuel cell. The small size of the crystal also limits its value as a reinforcement. In International Patent Application WO 90/04859, Smith and Kucera disclosed a method of preparing ceramic oxide fibers by spraying a slurry of the ceramic material perpendicularly into an ambient stream of air or other gas and then heating the resultant green fibers to remove the binders. Examples cited were lithium ferrite and lithium manganite fibers which are potential electrode materials in molten carbonate fuel cells. Application of this technology to the production of lithium aluminate fibers and subsequent benefits were demonstrated by P.M. Brown in the "Physical Property Optimization of Lithium Aluminates for Fabrication of Molten Carbonate Fuel Cell Matrices" which was presented at the 1990 Fuel Cell Seminar. The resultant molten carbonate fuel cell electrolyte tiles produced with inclusion of the fibers increased the tile strength. The need exists for improved fibers to yield further improvements in the electrolyte tile strength or in other applications. Charles C. Fain in U.S. Patents 4,798,815 and 4,820,664 disclosed the piggyback method of making ceramic fibers by wetting special carbon fiber micro- molds, which are non-ceramic fibers having elongated cavities, with a wet chemical precursor and subse- quently heating the wetted micromolds to produce ceramic fibers of various compositions. Although the 'piggyback*' method of producing polycrystalline oxide fibers is generally useful for producing otherwise difficult to produce fibers, U.S. Patents 4,798-,815 and 4,820,664 do not disclose the processing times, temperatures, procedures, or carrier media necessary for preparation of high quality dense lithium metal oxide fibers without loss of lithium through lithium oxide evolution which occurs at temperatures higher than 1000°C. The present invention provides polycrystalline lithium metal oxide ceramic fibers of the formula Li x M y 0 2 where M is aluminum, silicon or a metal with atomic numbers from 22-31, 40-52, and 72-84 and with the desired length and diameter and a method of pre¬ paring such fibers comprising: 1.) preparing a particulate oxide suspension composed of lithium metal oxide powder or the corresponding metal salts of the product oxide fiber in a solvent and which suspension can optionally contain binders, deflocculating agents and additional solvents needed to attain the proper viscosity and slurry characteristics; 2.) this fluid oxide suspension is filled into elongated, non-ceramic, fiber micromolds such as hollow or C-shaped carbon fibers by capillary action, ultrasonic packing, or other similar manner of filling the carbon fiber micromold; 3.) heating the filled micromold in a graphite cylinder containing lithium hydroxide or lithium oxide powder and firing under inert atmosphere at temperatures higher than 1000°C or close to the melting point of the product oxide fiber for at least five minutes whereby the lower melting lithium hydroxide vaporization effectively saturates the vapor phase with lithium oxide inhibiting evolution of lithium oxide from the lithium metal oxide in the micromold and followed by firing in air at 500-1000°C to burn-off the micromold or 4.) the ceramic fiber containing micromold is fired in air at 500-1000°C to simultaneously burn off the fiber micromold and yield the poly¬ crystalline lithium metal oxide fibers. The poly- crystalline fibers can also be separated from the micromold mechanically by using a separating agent or employing a shaking technique together with an abrasive agent or instrumentally. The 7 -LiA10 2 fibers of the present invention are thus prepared by a modification of the piggyback process developed by co-inventor C.C. Fain. In the present process, piggyback micromolds such as hollow or C-shaped carbon fibers, melt spun from the mesophase pitch, are used. The desired feed composition containing a mixture of metal salts, solvents, and optionally, binders, plasticizers and deflocculants, is introduced into the micromolds, followed by heating the filled micromolds in air to form the fiber while volatilizing the micromold or, optionally, the micro- molds are filled and heated in an inert environment to a temperature sufficient to sinter the filling material followed by heating the molded fiber in air to' volatilize the micromolds and yield polycrystalline lithium metal oxide fibers without volatilization of the lithium oxide. The dual ceramic/non-ceramic fiber is then heated in an oxygen-containing environment to burn away the carbon. Micromolds useful in the practice of this invention include but are not limited to hollow or C-shaped carbon fibers. Metal salts useful in the practice of this invention include but are not limited to hydroxides, oxides, carbonates, nitrates, or alkoxides of lithium and the corresponding metal, M. These metal salts are employed in mixtures in the amounts equivalent to desired molar ratios of the Li x My0 2 . The oxidation states of M and desired molar ratios fix the formula¬ tion values of x, y, and z. The metal M is preferably selected from the first row of transition metals in the periodic table having atomic numbers 22-31 and most preferably is aluminum or silicon. Solvents useful in the practice of this invention include but are not limited to water, alcohols, such as ethanol trichloroethylene and mixtures of solvents. Binders useful in the practice of this invention include but are not limited to polyvinylbutyrol resins (Butvar B 98) , acrylic resin based binders (Metoramic 73171) and the like. Plasticizers useful in the practice of this invention include but are not limited to butylbenzyl- phthalate (Santicizer 160) . Deflocculants useful in the practice of this invention include but are not limited to fish oil or dispersion agents such as ammonium polyelectrolytes, for example Darvan 821 A available from RT Vanderbilt Co. Inc. The desired ceramic slurries containing the ceramic material with a mixture of metal salts, solvents, binders, plasticizers and deflocculants are prepared by mixing together the selected materials under conditions to produce a dispersion or suspension of fine particles in a liquid. The term slurry as used herein includes both suspensions and dispersions of particulate matter on the order of a micron (10 ~3 mm.) to one millimicron (10~ 6 mm.) dispersed or suspended in a liquid. The micromolds are filled with the ceramic slurry by any suitable means such as capillary action, ultra¬ sonic packing, submersing the micromolds in the ceramic slurry and allowing the slurry to fill the micromolds which can be simply separated from the liquid slurry by filtering through a screen or such other separation means as may be convenient. The micromolds, filled with the fiber precursor ceramic slurry, are then heated in a non-oxidizing atmosphere in a suitable heating device such as a graphite lined furnace. When making fibers from which lithium oxide might evolve, lithium hydroxide or lithium oxide powder is placed in the oven and heated along with the micromolds to provide an atmosphere saturated with lithium oxide thus preventing the evolution of lithium oxide from filled micromolds during the fiber forming step. The filled micromolds are heated (fired) at temperatures between 1000°C and just below the melting point of the metal oxide fiber being formed for at least five (5) minutes but typically ten minutes to 30 minutes. Although further heating can be done, it is generally not necessary. The heating may initially be conducted at lower temperatures such as 100°C to 150°C to remove the slurry liquid from the outside of the micromolds. After the metal oxide ceramic fiber is formed the filled micromold is fired at 500°C to 1000°C in an oxidizing atmosphere, typically air, to burn off the fiber micromold. The following examples further illustrate this invention. EXAMPLE 1 Thirty grams of 7 ~LiA10 2 and forty milliliters of ethanol were mixed and ultrasonically deagglomerated. Hollow carbon fibers about 5 cm long and 20 μm inner diameter were added vertically into the mixture. The hollow carbon fibers were filled by capillary action with the 7 ~LiAl0 2 slurry. The dual component fibers were then dried initially in an oven at 100-150°C, placed in a graphite cylinder containing a powdered mixture of graphite (3 g) , lithium hydroxide monohydrate (1.5 g) and 7 -LiAl0 2 (1.0 g) , fired for 15 minutes at 1650°C under inert atmosphere, and fired in air at 1000°C for three hours. The resulting product was analyzed by x-ray powder diffraction for phase identification and by scanning electron microscopy for photomicrographs of fiber dimensions as shown in Figures 1-3. The fibers were purely 7 ~LiA10 2 . EXAMPLE 2 Sixty-four grams of Al(N03)3.9H20 and 12 grams of lithium nitrate were mixed with one hundred milliliters of distilled water. Hollow carbon fibers as described in Example 7 were placed vertically in the mixture to allow filling of the fibers with the nitrate mixture by capillary action. The dual component fibers were washed with distilled water to remove excess precursor mixture on the outside and then initially dried in an oven at 100-150°C prior to firing at 1000°C for at least three hours in air. The product fibers were evaluated by x-ray powder diffraction for phase identi¬ fication and scanning electron microscopy for photo- micrographs of powder dimensions as shown in Figures 4-5. The fibers were purely 7-LiA10 2 •

Claims: CLAIMS 1. A method for preparing polycrystalline lithium metal oxide fibers characterized by filling micromold fibers of a desired inner diameter and length with a fluid suspension of lithium oxides of the formula Li x M y O z wherein M is selected from aluminum, silicon or a metal having an atomic number of 22 to 31 or 40 to 52 or 72 to 84, the values of x, y and z being determined by the oxidation number of M, a solvent and optionally con¬ taining additional solvents, binders, plasticizers, and deflocculants, firing the filled micromold fibers at elevated temperatures but below temperatures of lithium oxide volatilization in air for at least one hour to simultaneously burn-out the micromold and yield the polycrystalline lithium metal oxide fiber. 2. A method for preparing polycrystalline lithium metal oxide fibers of the formula Li x MyO z characterized by filling micromold fibers of a desired inner diameter and length with a fluid mixture of a lithium salt and a metal salt in a solvent and optionally containing binders, plasticizers, deflocculants and additional solvents, placing the filled micromold fibers in a graphite cylinder containing lithium hydroxide or lithium oxide powder, firing the filled micromold fibers at elevated temperatures above temperatures of lithium oxide volatilization for at least 5 minutes under an inert atmosphere followed by firing in air at temperatures from 500-1000°C for at least one hour to burn-out the micromold and yield the polycrystalline lithium metal oxide fiber. 3. The method of Claim 2 characterized in that the metal M component in the lithium metal oxide fiber of the formula Li x MyO z is selected from aluminum, silicon, and metals with atomic numbers 22-31, 40-52, and 72-84 . 4. The method of Claim 2 characterized in that the lithium metal oxide fiber is a lithium aluminate fiber and the lithium salt is selected from lithium hydroxide monohydrate and lithium nitrate, and the aluminum salt is selected from aluminum hydroxide, alumina, aluminum nitrate, or aluminum alkoxide. 5. The method of Claim 2 characterized in that the first firing temperatures are at least 1000°C and close to the melting point of the lithium metal oxide fiber. 6. The method of Claim 2 characterized in that the first firing time is preferably 20 minutes to one hour and under an inert atmosphere such as nitrogen or argon. 7. The method of Claim 1 or 2 characterized in that the solvent is selected from water, ethanol, trichloroethylene and mixtures thereof. 8. The method of Claim 2 characterized in that the burn-out of the micromold is achieved by a second firing at 500-1000°C for at least one hour, but preferably at 1000°C for 30 minutes. 9. The method of Claim 1 or 2 characterized in that C-shaped carbon fibers or hollow carbon fibers are used as micromolds. 10. The method of Claim 1 or 2 characterized in that the micromold fibers are filled by ultrasonifi- cation or by capillary action. 11. The method of Claim 1 or 2 characterized in that the fiber micromolds may have dimensions at least 10 microns inner diameter and at most 2 cm long. 12. The method of Claim 1 or 2 characterized in that the resulting polycrystalline lithium metal oxide fibers have dimensions at least 5 microns inner diameter and 100 microns long. - Il ¬ ls. The method of Claim 1 or 2 characterized in that the polycrystalline lithium metal oxide fibers may be cut to the desired length by physical means. 14. The method of Claim 1 or 2 characterized in that the oxide used to make lithium aluminate fibers is gamma lithium aluminate or alpha lithium aluminate. 15. The method of claim 1 or 2 characterized in that the metal component M in the formula Li x M y O z is selected from transition metals whose atomic number are 22-31, 40-52 and 72-84. AMENDED CLAIMS [received by the International Bureau on 21 December 1993 (21 .12.93 ) ; original cl aims 1 -15 repl aced by amended cl aims 1 -12 (2 pages ) ] 1. A method of preparing polycrystalline 7 -lithium aluminate fibers of the formula 5 LiA10 2 characterized by filling micromold fibers with a fluid suspension of a lithium salt and an aluminum component selected from alumina and aluminum salts or a lithium 10 aluminate dispersion in a solvent, placing the filled micromold fibers in a non-reactive container containing lithium hydroxide or lithium oxide powder, heating the container containing the filled micromold fibers in an inert atmosphere at elevated temperatures above 15 temperatures of lithium oxide volatilization for at least 5 minutes to saturate the inert atmosphere with lithium oxide and to convert the fluid mixture to 7 -lithium aluminate fibers followed by firing in air to burn-off the micromolds and yield the polycrystalline 20 7 -lithium aluminate fibers. 2. The method of claim 1 characterized in that the lithium salt is selected from lithium hydroxide monohydrate, lithium nitrate, lithium carbonate, lithium peroxide, lithium oxide and lithium alkoxides 25 and the aluminum component is selected from alumina, aluminum hydroxide, aluminum nitrate, or aluminum alkoxides. 3. The method of claim 1 characterized in that the first firing temperatures are at least 1000°C and 30 below the melting point of the 7 -lithium aluminate fiber. 4. The method of claim 1 characterized in that the first firing time is 20 minutes to one hour and under an inert atmosphere. 35 5. The method of claim 1 characterized in that the solvent is selected from water, ethanol, trichloroethylene and mixtures thereof. 6. The method of claim 1 characterized in that the burn-off of the micromolds is achieved by a second firing at 500-1000°C for at least one hour in air. 7. The method of claim 1 characterized in that the micromolds are selected from C-shaped carbon fibers or hollow carbon fibers. 8. The method of claim 1 characterized in that the micromold fibers are filled by ultrasonification or by capillary action. 9. The method of claim 1 characterized in that the fiber micromolds dimensions are at least 5 microns inner diameter. 10. The method of claim 1 characterized in that the resulting polycrystalline 7 -lithium aluminate fibers have dimensions at least 5 microns diameter and are at least 100 microns long. 11. The method of claim 1 characterized in that the lithium aluminate used to make 7 -lithium aluminate fibers is selected from beta lithium aluminate, gamma lithium aluminate, alpha lithium aluminate or mixtures thereof. 12. The method of claim 1 characterized in that the micromolds are made of carbon and the burn-off of the carbon micromolds is achieved by a second firing of at least 1000°C for at least thirty minutes.

Inventors: FAIN CHARLES C, FRIANEZA-KULLBERG TERESITA NAI, LOWE GREGORY MARK, MCDONALD DANIEL P, FAIN, CHARLES, C., FRIANEZA-KULLBERG, TERESITA, NAILA, C., LOWE, GREGORY, MARK, MCDONALD, DANIEL, P.
Applicants: FMC CORP, FMC CORPORATION
Application year: 1993
Main classification: C04B35
IPC codes: C01F7, C04B35, D01F9