WO1999000326A1 - Procede de preparation d'oxydes de metal et d'oxydes de metaux melanges - Google Patents

Procede de preparation d'oxydes de metal et d'oxydes de metaux melanges Download PDF

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Publication number
WO1999000326A1
WO1999000326A1 PCT/US1998/013366 US9813366W WO9900326A1 WO 1999000326 A1 WO1999000326 A1 WO 1999000326A1 US 9813366 W US9813366 W US 9813366W WO 9900326 A1 WO9900326 A1 WO 9900326A1
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Prior art keywords
solution
metal
metal oxide
reducing agent
methods
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PCT/US1998/013366
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English (en)
Inventor
Sunity K. Sharma
Subhash C. Narang
Kuldip K. Bhasin
Susanna Ventura
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Sri International
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Publication date
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Priority to AU81725/98A priority Critical patent/AU8172598A/en
Publication of WO1999000326A1 publication Critical patent/WO1999000326A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G1/00—Methods of preparing compounds of metals not covered by subclasses C01B, C01C, C01D, or C01F, in general
    • C01G1/02—Oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/14—Methods for preparing oxides or hydroxides in general
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/14—Methods for preparing oxides or hydroxides in general
    • C01B13/32—Methods for preparing oxides or hydroxides in general by oxidation or hydrolysis of elements or compounds in the liquid or solid state or in non-aqueous solution, e.g. sol-gel process
    • C01B13/322—Methods for preparing oxides or hydroxides in general by oxidation or hydrolysis of elements or compounds in the liquid or solid state or in non-aqueous solution, e.g. sol-gel process of elements or compounds in the solid state
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C01D15/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/006—Compounds containing, besides manganese, two or more other elements, with the exception of oxygen or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/12—Manganates manganites or permanganates
    • C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/12—Manganates manganites or permanganates
    • C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
    • C01G45/1242—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [Mn2O4]-, e.g. LiMn2O4, Li[MxMn2-x]O4
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/40—Cobaltates
    • C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants

Definitions

  • the field of the invention is metal oxides.
  • Metal oxides have physical, chemical, electrical, magnetic, optical and other characteristics providing utility in many different applications. Among other things, metal oxides have been found to be useful as protective coatings, pigments, catalysts, electrode materials, conductors, insulators, inclusion materials such as grits and non-slip agents, ceramics, and electrochromic applications.
  • Mixed metal oxides are defined herein to be a subset of metal oxides in which different metals are bound together with oxygen in the same molecule.
  • the definition includes compounds having the general formula, M' x! . . . M n xn O y , where M' x ⁇ . . . M n n represents n different metals, and the various metal and oxygen species are present in relative atomic ratios given by xl . . . xn and y, respectively.
  • the definition also includes M' x ⁇ . . .
  • M n xn O y compounds that are "doped" by inclusion of other non-homogeneously distributed chemical species, such as metal, ceramic or other particulates, as well as the hydroxide and hydrated forms of such compounds.
  • mixed metal oxides used herein does not, however, include compositions in which individual mono-metallic metal oxides are merely present as a solid-solid or other mixture, rather than being chemically bonded together. The definition also does not extend to compounds such as metal alkoxides and alkanolamines.
  • Barium Titanate (BaTiO 3 ) is widely used in capacitors, transducers, thermistors and so forth, Yttrium Barium Copper Oxide (YBa 2 Cu 3 O x ) and other mixed valent spinels have been investigated as superconductors, and lithium niobium oxides (LiNbO 3 ) have been investigated as ferro-electric materials.
  • YBa 2 Cu 3 O x Yttrium Barium Copper Oxide
  • LiNbO 3 lithium niobium oxides
  • Metal oxide electrodes are also particularly advantageous in the production of secondary battery electrodes, where the life and energy efficiency of secondary batteries depend to a great extent upon the morphology and composition of the electrodes, and one class of such metal oxides, the lithiated metal oxides, LiM p ⁇ M q n...O x , (including, for example, LiAl 02 Mn ⁇ .8 Ox, LiCo0 2 , and LiMn 2 O 4 ) are increasingly used in the so-called re-chargeable rocking chair batteries. In such devices the metal oxides act as cathode materials by reversibly intercalating and deintercalating lithium during repetitive discharging and charging.
  • EP 0 366 313 Bl to Kourtakis discloses a process in which mixed metal oxides are formed from an aqueous solution of monometallic metal precursor salts, in which at least one of the monometallic salts is a nitrate, and another of the salts carries a reducing ligand, such as a formate, acetate or proprionate.
  • the mixture is spray dried, and heated to 400°C to initiate a redox reaction. Finaly, the product is heated to 900°C.
  • Both the Kourtakis and Greunter processes are still undesirable in that they require spray drying apparatus, and in that they introduce inhomogeneities by initiating the redox reaction among components disposed in a solid phase.
  • the present invention is directed to methods and apparatus in which a mixed metal oxide is prepared using a redox reaction which takes place in solution, wherein at least one of the oxidizing and reducing agents of the redox couple is derived from a metal precursor salt.
  • the redox reaction is initiated using microwave energy directed at the solution.
  • the metal precursor salt provides an oxidizing ligand.
  • the solution is aqueous.
  • Figure 1 is a flowchart of steps in a process according to the present invention.
  • FIG. 1 depicts steps in a process according to the present invention.
  • a plurality of metal salts is placed into a solution using an appropriate solvent.
  • Each of the salts have a ligand which is either an oxidizing agent or a reducing agent, and which forms part of a redox system.
  • an oxiding or reducing agent is added to the solution, which agent forms another part of the redox system.
  • step 30 sufficient energy is imparted to the solution to initiate a reaction between or among the agents of the redox system, and thereby produce a mixed metal oxide.
  • the solvent is removed, and in step 50 the mixed metal oxide is ground or otherwise subjected to further processing.
  • any metal can be utilized as part of a contemplated salt.
  • the salt can be solvated in an appropriate solvent, and further that the metal is capable of forming an oxide.
  • Appropriate metals specifically include the alkali metals, alkaline earth metals and transition metals, and their presence or absence will largely be application dependent.
  • metals such as Lithium, Manganese, Cobalt, Nickel, are particularly well suited for battery applications, while Barium, Titanium, and Lead are particularly well suited for piezoelectric applications.
  • the various salts may or may not be mono-metallic salts. Salts having two, three, four or even more different metals are specifically contemplated.
  • salts employed in step 10 may include multi-metallic salts including LiAl 02 Mn ⁇ 8 Ox, LiCo0 2 , and LiMn 2 O .
  • mixed metal oxides may include metals in either equal or unequal atomic concentrations, and the concentrations of the respective salts may range anywhere from exact equivalence to merely doped quantities.
  • the metals in the various salts may be complexed with their respective ligands in many different ways.
  • the metallic-ligand bonds may be more or less of an ionic nature, although complexes having bonds of relatively more ionic character are preferred because they generally result in increased solubility.
  • Metal nitrates and nitrites are both contemplated, as are acetates, nitrates, formates, citrates, oxalates, etc.
  • the ligand has a great deal to do with the solubility of the salt.
  • sodium and potassium salts are soluble in water, most silver salts are insoluble, and transition metal salts may or may not be soluble unless the ligand assists solubility.
  • Acetates except silver, mercury and bismuth are generally soluble, nitrates are almost always soluble, while sulfates are only usually soluble. Carbonates, sulfides and nitrides are generally disfavored because they tend to be insoluble
  • the ligands forming part of the metal salts also form part of a redox system which produces a gaseous end product, thereby removing the ligands from the solution. From this perspective, the nitrates and nitrites are especially preferred.
  • additional components can be added to the solution as well, and such additional components may or may not chemically react with the other ingredients.
  • additional components are suspended ceramic or metal particles.
  • Such included materials may be advantageously added to modify characteristics of the mixed metal oxide.
  • carbon black can be added to enhance electrical conductivity
  • iron powders can be added to enhance ferro-magnetic properties.
  • materials may be added which enhance brittleness, compression strength, or elasticity.
  • a viscosity modifier such as PEO or PEG may also be added.
  • the mixed metal oxide is still considered herein to have the nominal formula M' x ⁇ . . . M n xn O.
  • metal oxides as composites with carbon. This can be achieved by physically mixing a metal oxide with carbon which may be graphitic, soot or other allotropic form.
  • the mixing operation may be performed by grinding, for example in a ball mill.
  • a better mixing may be achieved by pyrolysing the metal salts of organic acids in absence of oxygen.
  • a few organic compounds are known to generate specific allotropic forms of carbon, for example, 3,4,9,10 - perylenetetracarboxylic acid is a precursor to graphitic carbon.
  • metal oxide composites having different amounts of graphite to metal oxide may be obtained.
  • Working Example 8 detailed below exemplifies the formation of TiO 2 as a composite with graphite.
  • the solvent employed in step 10 is contemplated to be any suitable solvent, provided that the solvent is capable of solvating the salts.
  • Water is a presently preferred solvent, both because of its superior solvating ability, and because it is inexpensive and non-hazardous.
  • Nitrates, for example, are almost always soluble in aqueous solutions.
  • non-aqueous solvent can be employed, such as various organic solvents.
  • Preferred organic solvents include alcohols, dimethyl sulphoxide, ethyl acetate, and formamide. Such organic solvents may be particularly useful for solvating transition and non-transition metal ions.
  • mixed solvents may be advantageously employed, such as mixtures of water with alcohols, dimethyl sulphoxide, ethyl acetate, and formamide.
  • Mixed solvents may be particularly useful for solvating metal organics, including metal carboxylates and transition metal, and non-transition metal complexes having organic ligands.
  • the absolute concentrations of the various components in the solvent will be appropriate for the intended reaction.
  • the metal salts may advantageously have an initial concentration of between about 1% w/w and 25% w/w, and separately added reducing or oxidizing agent may advantageously have an initial concentration falling between about 5% w/w and 90% w/w.
  • Higher concentrations are problematic in that the redox reaction is disfavored where grossly non-equivalent amounts of reducing and oxidizing agents are present.
  • Lower concentrations are also problematic in that the reaction tends to proceed too slowly, and unnecessary steps and energy may be required to remove excess of the non-equivalent amount.
  • Any suitable vessel may be employed to contain the salt solution. Considerations include suitable venting if it is desired to permit the solvent to volatilize, and sufficient radiative surface area, jacketing or other means for removing excess heat form the system. Obviously, the vessel must also be capable of handling the volumes contemplated to be processed. In this regard it is contemplated that both batch and continuous processes are contemplated. Suitable vessels for continuous processing, for example, may comprise a rotary furnace having an internal lining which is not easily corroded. It is still further contemplated that suitable vessels will be adapted to receive or permit passage of the activation energy to initiate the redox system. Thus, where microwaves are employed as the energy source, at least some portion of the vessel must be capable of passing the microwaves. In such cases, solvents capable of absorbing microwave energy, such as chlorobenzene, may also be used.
  • the oxiding or reducing agent will be selected to cooperate with the ligand(s) from the metal salts to form a suitable redox system.
  • Preferred redox systems are those which have an appropriate activation energy, usually at about 220 °C to about 550 °C, and that react substantially to completion under the reaction conditions without reacting too violently.
  • some redox systems would be explosive under the expected conditions, and are therefore highly disfavored.
  • Other disfavored redox systems may not be explosive, but are still so reactive that excess heat production is problematic.
  • Preferred redox systems are also those which generate a gaseous or liquid product which is readily removed from the solution. To this end redox systems are preferred that produce a gas, such as NOx, SOx, COx, N 2 and N O, or that produce water, alcohol or other readily evaporated substance.
  • the redox system will comprise a simple redox couple, such as nitrate and acetate. While it is possible that one or more of the metal salts will have a reducing ligand, and the oxidizing agent will be provided separately, it is preferred that at least one of the metal salts will have an oxidizing ligand, and that the reducing agent will be separately added to the solution.
  • Preferred reducing agents for this purpose are organic acids, including non-polymerizing carboxylic acids such as formic acid, citric acid, and ascorbic acids. Polymerizing organic acids such as methacrylic, acrylic, crotonic acid, etc. may also be used, although such acids may combine to produce a product which is difficult to separate from the mixed metal oxide product.
  • mixed metal oxides of the form M p ⁇ M q nM r ⁇ ...0(p/2+q+3r/2) can be produced by heating an aqueous mixture of metal nitrates and carboxylic acids at low temperature.
  • the formation of the metal oxide under these conditions is thought to be facilitated by spontaneous reaction between the oxidizing N0 3 -/N0 2 and the organic ligands such as acrylate, methacrylate, formate, citrate, acetate, ascorbate, picolinate, salicylate, etc.
  • a significant advantage of a nitrate-carboxylate system is the ability of these systems to undergo pyrolysis in an ordinary household microwave oven to give the ceramic, which may then be sintered to get the final product.
  • Working Example 4 (detailed below) illustrates the use of a microwave oven to obtain a desired ceramic.
  • complex redox systems there can be combinations of oxidizing and/or reducing agents.
  • Combinations of acids for example, can be used as reducing agents.
  • Contemplated examples of complex redox systems include tartaric acid and ascorbic acid.
  • the various salts themselves may provide both oxidizing and reducing agents.
  • the various ligands employed in the redox system are preferably included in stoichiometric proportions to react completely with each other.
  • the activation energy required to initiate reaction in the redox system can be provided by any suitable energy source.
  • any suitable energy source In our experiments reacting small quantities of materials, we have been most successful using microwave energy for this purpose. In such experiments the solution has generally been contained within a glass petri dish, and the microwaves have been provided using a common household microwave having a rated capacity of 1100 watts. We have also had good results using radiative or convective heat, such as that produced by a hot plate. Still further, other energy sources such as ultraviolet light, CO 2 laser, diode laser, infra red lamp, solar energy, and electric current are contemplated.
  • the amount and intensity of the activating energy is preferably also a function of other reaction conditions. Under the concentrations discussed above, microwave energy for about 10 minutes is generally sufficient to initiate many redox systems, during and after which the reaction is self perpetuating due to the exothermic nature of the reaction.
  • the temperature of the mixture during processing can fall anywhere between about 50 °C and about 500 °C, and may vary or remain constant during processing. It is further contemplated that the reaction time will fall within the several hours to several days range. Stirring or other mixing is clearly advantageous during the reaction to increase homogeneity of the final product, but there are wide limits on such mixing. In some cases, especially when polymerizing acids are used it may be advantageous to age the contents for a short period ranging from an hour to several hours. However, over-aging may be avoided to preclude the possibility of phase separation.
  • the solvent can be separated from the mixed metal oxide product in several different ways.
  • the redox reaction is carried out until a substantial increase in viscosity is attained, during which time the solvent is largely evaporated from the reacting mixture.
  • the solvent can be removed by filtration. In some instances, removal of the remaining solvent may be augmented by addition of an azeotropic substance. It is also contemplated that solvent can be removed using microwave radiation.
  • the methods disclosed herein can be used to prepare any combination of amorphous, crystalline pure and mixed metal oxide powders.
  • amorphous products it is advantageous that no sintering is carried out subsequent to microwaving.
  • crystalline pure products it is advantageous that prolonged sintering at 500°C to 900°C is carried out for one to several hours.
  • atomic level mixing can be achieved relatively simply, and at relatively low temperature and moderate reaction conditions. It therefore will not generally be necessary, for example, to further process the mixed metal oxides by repeated grinding and calcination, or subjecting the oxides to temperatures above about 500 °C.
  • step 50 it is contemplated that mixed metal oxide products can be further processed into flakes, pellets, and other morphologies.
  • the metal oxide is taken along with a polymer (such as polymethyl methacylate) in a solvent (such as chloroform) compatible with the polymer, and then sprayed onto a substrate using an air brush or an ultrasonic sprayer.
  • the polymer/metal oxide may be coated onto a substrate using a doctor blade or dip coater.
  • the substrate may advantageously be pretreated with a surfactant which does not leave a residue. This treatment of the substrate assists in dislodging the flaky ceramic from the substrate.
  • Plastic substrates such as KaptonTM, KevlarTM, and TeflonTM may be used for this purpose.
  • the solvent may be removed by warming as necessary, and the flakes of the material may then be readily dislodged from the substrate and sintered.
  • Working Example 3 (detailed below).
  • metal acrylate it is not absolutely necessary to always use a metal acrylate, especially due to the lower solubility of metal acrylates in water. In such circumstances a solution of metal nitrates and acrylic acid in aqueous or mixed aqueous solutions may be microwaved to get the metal oxide.
  • a solution of metal nitrates and acrylic acid in aqueous or mixed aqueous solutions may be microwaved to get the metal oxide.
  • Mixed metal oxide products prepared as disclosed herein may also be further processed by extrusion, spun into fibers, or deposited as films. It is also contemplated that mixed metal oxide products can be further processed during the solvent removal stage, such as by various forms of atomizing, electro-spraying, and thermal spraying. In short, it is contemplated that mixed metal oxide products prepared as disclosed herein may be processed in any manner in which metal oxide products in general may be processed.
  • Example 1 In a particular experiment, 7.54 gm lithium nitrate, 54.95 gm manganese(II) nitrate tetrahydrate and 40 gm acrylic acid were combined in 80 ml of water and stirred overnight to let the viscosity of the solution increase due to partial polymerization. This solution is burnt at 300- 400 °C to yield a partially sintered material with reasonable crystallinity. A final sintering at 800 °C for 2 hours gives a highly crystalline material as seen by its x-ray diffractogram (not shown).
  • a doped mixed metal oxide we prepared the aluminum doped lithium manganese oxide, LiAl 02 Mni . g0 x by taking a mixture of the respective metal nitrates and acrylic acid in water, followed by low temperature pyrolysis and then short sintering at high temperature. Similar procedures can be used to dope a wide range of metal oxides, for example, LiMn 2 O 4 , with dopants from the metals of groups IB, IIB, IIIA&B, IVA&B, VA&B, VIA&B, VIIA and VIII and the lanthanides and the actinides.
  • Example 4 0.79 gm of lithium acrylate and 5.16 gm of Mn(NO ) 2 4.4 H 2 O were taken in about 8 ml of water in a 50 ml beaker. The contents of the beaker were agitated and heated to 40 - 45C for 10 minutes. The resulting solution had minor suspension in it and was not removed. About one ml of the solution was placed in a pyrex petri dish and the dish was placed in a house hold microwave (Sharp, Carousel, 1100 watt, 1.3 cubic feet). The contents were microwaved at full power for 5 minutes. This lead to scintillations and "burning' of the contents and the formation of the metal oxide.
  • metal oxides by this method can be extended to other alkali metals, transition and non-transition metals as well.
  • Another example of a transition metal oxide is that using cobalt(II) nitrate as described in Working Example 7 below.
  • the methods are applicable to production of a wide range of doped or undoped electrodes, and can also be used in the synthesis of super conductors, semiconductors, piezeoelectric materials, etc.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

L'invention concerne la préparation d'oxydes de métal et d'oxydes de métaux mélangés au moyen d'une réaction redox entre composants mélangés à l'échelle atomique dans une solution, et de l'irradiation de la solution à l'aide d'une source d'énergie appropriée. Dans un aspect de modes de réalisation préférés, la réaction redox est amorcée au moyen d'énergie hyperfréquences dirigée sur la solution. Dans un autre aspect de modes de réalisation préférés, le sel précurseur de métal renferme un ligand oxydant. Dans un autre aspect encore, la solution est aqueuse.
PCT/US1998/013366 1997-06-26 1998-06-25 Procede de preparation d'oxydes de metal et d'oxydes de metaux melanges WO1999000326A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU81725/98A AU8172598A (en) 1997-06-26 1998-06-25 Method of preparing metal and mixed metal oxides

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US5083697P 1997-06-26 1997-06-26
US60/050,836 1997-06-26

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1209124A1 (fr) * 2000-11-27 2002-05-29 National Institute for Materials Science Oxyde de sodium-cobalt-manganese de structure lamellaire et procédé de fabrication
EP1693107A1 (fr) * 2005-02-11 2006-08-23 Rohm And Haas Company Catalyseur à base d'oxydes metalliques mixtes et procédé pour sa fabrication
EP1896178A1 (fr) * 2005-06-29 2008-03-12 Samsung Engineering Co., Ltd. Catalyseur a oxyde metallique pour la production d'hydrogene et procede d'elaboration
EP1947055A1 (fr) * 2007-01-08 2008-07-23 Afton Chemical Corporation Procédés pour la fabrication de nanoparticules contenant du métal de taille et de forme contrôlées
US8333945B2 (en) 2011-02-17 2012-12-18 Afton Chemical Corporation Nanoparticle additives and lubricant formulations containing the nanoparticle additives
US8741821B2 (en) 2007-01-03 2014-06-03 Afton Chemical Corporation Nanoparticle additives and lubricant formulations containing the nanoparticle additives

Citations (4)

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Publication number Priority date Publication date Assignee Title
US4395436A (en) * 1979-12-20 1983-07-26 Oronzio De Nora Impianti Elettrochimici S.P.A. Process for preparing electrochemical material
US5720859A (en) * 1996-06-03 1998-02-24 Raychem Corporation Method of forming an electrode on a substrate
US5728362A (en) * 1994-09-22 1998-03-17 Asea Brown Boveri Ag Method of producing a mixed metal oxide powder and mixed metal oxide powder produced according to the method
US5770018A (en) * 1996-04-10 1998-06-23 Valence Technology, Inc. Method for preparing lithium manganese oxide compounds

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4395436A (en) * 1979-12-20 1983-07-26 Oronzio De Nora Impianti Elettrochimici S.P.A. Process for preparing electrochemical material
US5728362A (en) * 1994-09-22 1998-03-17 Asea Brown Boveri Ag Method of producing a mixed metal oxide powder and mixed metal oxide powder produced according to the method
US5770018A (en) * 1996-04-10 1998-06-23 Valence Technology, Inc. Method for preparing lithium manganese oxide compounds
US5720859A (en) * 1996-06-03 1998-02-24 Raychem Corporation Method of forming an electrode on a substrate

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1209124A1 (fr) * 2000-11-27 2002-05-29 National Institute for Materials Science Oxyde de sodium-cobalt-manganese de structure lamellaire et procédé de fabrication
EP1693107A1 (fr) * 2005-02-11 2006-08-23 Rohm And Haas Company Catalyseur à base d'oxydes metalliques mixtes et procédé pour sa fabrication
CN100413589C (zh) * 2005-02-11 2008-08-27 罗门哈斯公司 制备催化剂的方法以及由此制得的催化剂
EP1896178A1 (fr) * 2005-06-29 2008-03-12 Samsung Engineering Co., Ltd. Catalyseur a oxyde metallique pour la production d'hydrogene et procede d'elaboration
EP1896178A4 (fr) * 2005-06-29 2011-10-05 Samsung Eng Co Ltd Catalyseur a oxyde metallique pour la production d'hydrogene et procede d'elaboration
US8741821B2 (en) 2007-01-03 2014-06-03 Afton Chemical Corporation Nanoparticle additives and lubricant formulations containing the nanoparticle additives
EP1947055A1 (fr) * 2007-01-08 2008-07-23 Afton Chemical Corporation Procédés pour la fabrication de nanoparticules contenant du métal de taille et de forme contrôlées
US8333945B2 (en) 2011-02-17 2012-12-18 Afton Chemical Corporation Nanoparticle additives and lubricant formulations containing the nanoparticle additives

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