CA2906009C - Complexometric precursor formulation methodology for industrial production of high performance fine and ultrafine powders and nanopowders for specialized applications - Google Patents

Abstract

A method of forming a powder MjXp wherein Mj is a positive ion or several positive ions selected from alkali metal, alkaline earth metal or transition metal; and Xp is a monoatomic or a polyatomic anion selected from Groups IIIA, IVA, VA, VIA or VIIA; called complexometric precursor formulation or CPF. The method includes the steps of: providing a first reactor vessel with a first gas diffuser and an first agitator; providing a second reactor vessel with a second gas diffuser and a second agitator; charging the first reactor vessel with a first solution comprising a first salt of Mj; introducing gas into the first solution through the first gas diffuser, charging the second reactor vessel with a second solution comprising a salt of Xp; adding the second solution to the first solution to form a complexcelle; drying the complexcelle, to obtain a dry powder; and calcining the dried powder of said MjXP.

Description

COMPLEXOMETRIC PRECURSOR FORMULATION METHODOLOGY FOR
INDUSTRIAL PRODUCTION OF HIGH PERFORMANCE FINE AND ULTRAFINE
POWDERS AND NANOPOWDERS FOR SPECIALIZED APPLICATIONS
BACKGROUND
[0001] The present application is related to an improved method of forming fine and ultrafine powders and nanopowders. More specifically, the present invention is related to the formation of fine and ultrafine powders and nanopowders through complexometric precursors formed on bubble surfaces.

[0002] Our present society is advancing very rapidly in new technologies especially in the areas of biotechnology, medicine, electronics, pharmaceuticals and energy. These require significant improvements in raw material processing and in the production of high performance products of advanced chemical formulations without compromising cost relative to commercial scale-up for industrial production (Fig. 1). Thus, this requires a combination of structure-processing-property correlations that will lead to specialized high performance materials in order to sustain these modern technically demanding criteria.

[0003] Starting with a desired specific application, the process must be tailored to obtain the characteristics, both physical and chemical, in order to meet the end performance result. It is imperative to uniquely combine both well-established properties of the compounds and/or raw materials with the new, unique, unusual or desirable properties of the advanced materials. For example, traditional ceramics are well-known to be electrical insulators yet it is possible to utilize this property such that the special ceramics will provide high thermal conductivity allowing their use as heat sinks in substrates for microelectronics. Ceramic composites of inorganic glass fibers and plastics have been used for thermal and sound insulation traditionally but now are also used as optical fibers replacing the traditional copper wire. Ceramic engines replacing the traditional steel engines can withstand higher temperatures and will burn energy more effectively. This requires that the ceramics used for engine manufacture be of very fine particles such that strength and toughness to withstand the elevated temperatures and ruggedness required for these applications. Furthermore, nanosize powders when fabricated into the ceramic parts for these vehicles will be more dense, have less defects, and can be fabricated in thinner and smaller, lightweight sizes for practical use.

[0004] Increased energy consumption today necessitates discovery of new resources but also improvement in current materials to satisfy the energy infrastructure such as solar cells, fuel cells, biofuels, and rechargeable batteries. For example, the lithium ion battery that has been in use in consumer electronic devices but is now commanding a significant role in larger transport vehicles. These alternative energy resources must be more practical, and price competitive with fossil fuels, for wider acceptability in high-performance applications. As a consequence, sophisticated devices require specially designed microstructures that will enhance the physical and chemical properties of the materials utilized. Often, these materials are more expensive to produce on an industrial scale. Furthermore, these specialty powdered materials such as oxides, phosphates, silicates and the like, require not only a nanosize material but also a narrow particle size distribution with high porosity, high surface area and other characteristics to achieve enhanced performance. For instance, a nanostructured lithium cathode powder for the lithium ion battery would be expected to have improved mass and charge transport due to shorter diffusion paths and higher amount of active sites resulting from its finer smaller particle size. However, this added cost for the added value may not be acceptable to the end consumer resulting in reduced sales.

[0005] Other challenges are medical applications such as the use of calcium phosphate for bone substitution. While several calcium phosphate powders are available in the market, the requirements of less than one micron discrete particles as described in US Patent No. 8,329,762 B2 are important for making a biocompatible synthetic bone.
US Patent No. 5,714,103 describes bone implants based on calcium phosphate hydraulic cements, called CHPCs, made of a succession of stacked layers with a macroporous architecture mimicking the natural porosity of spongious bone. This medical field would definitely benefit from improved powders with better performance and lower cost.
Another example is a dermal patch wherein the pharmaceutical drug is released to the body. Both dermal patch and drug material combined would be more compatible if their particle sizes were nanosize with narrow particle size distribution.
Nanopowders can also significantly impact high performance dental applications, for example, such as teeth filling materials as well as enamel coating materials to aesthetically enhance and strengthen the tooth structure. In order to widen the usage of nanomaterials in the medical field, both cost and performance value should be compatible to both producer and end-user.

[0006] Distinctive characteristics clearly differentiate between advanced materials and traditional materials in several aspects, notably in raw materials, processing, chemical and physical characteristics, novel applications and specialized markets.
Conventional powder processes are made without strict chemical control and are generally made from grinding and segregating naturally occurring materials through physical means. These result in neither ultrapure nor ultrahomogeneous particles such that fabrication of a product using such heterogeneous and impure substances gives grain boundary impurities that may reduce mechanical strength or optical deformations and other limitations. Chemical processing solves this problem by controlling the composition of the powder at the molecular level to achieve a special ultrastructure for the preferred performance application. Specialized properties such as conductivity, electrochemical capacity, optical clarity, dielectric value, magnetic strength, toughness and strength are met only with specialized processing methods to control microstructure.
However, these demands necessitate an economically commercial viable process for large scale production. The dual requirements of cost and performance must be met to successfully commercialize these advanced materials.

[0007] A significant improvement in available raw materials is needed to meet many objectives. One objective is high purity, no longer 90% but >99% and even 99.999%, which entails chemical processing to remove undesirable impurities that affect performance. Another objective is particle size which preferably has a narrow, homogeneous particle size distribution with finer particle sizes of no longer 50 microns but 1 micron and preferably, nanosize. The addition of dopants which are deemed to enhance the specialized properties, like electronic conductivity and others, must be homogeneously distributed but also preferably distributed on the surface of the powder in some applications. Cobalt, aluminum and gadolinium are suitable dopants.
Aluminum and gadolinium are particularly suitable.

[0008] Innovations in processing these advanced materials to the final product are also necessary. As such, combinations of different processing techniques are often utilized. For example, inorganic powders have been usually made by traditional ceramics like solid state sintering. However, the resulting powder obtained by this method alone generally has a wider and larger particle size distribution. To obtain a homogeneous nanosize distribution, several grinding and milling steps have been employed. The generic types are ball mills, rod mils, vibratory mills, attrition mills, and jet mills. Disadvantages of these methods include energy and labor intensive production cycles and possibility of contamination from grinding balls utilized. Defects in the microstructure also occur causing degradation in the required performance targets.
Chemical vapor deposition, emulsion evaporation, precipitation methods, hydrothermal synthesis, sol-gel, precipitation, spray drying, spray pyrolysis and freeze drying are some of the other methods used for these types of preparations, each with advantages and disadvantages.

[0009] The technical drivers today call for particles less than one micron, and even to less than 100 nanometers. To date, the significance of the initial powder synthesis steps have been overlooked but these initial reactions clearly define the final finished powder microstructure and also determines scalability controls and finally, cost and performance. Careful selection of the starting reactants and the media- solid, liquid or gas- plays a unique role in the formulation of low cost, high performance powders.

[0010] An example is the formation of colloidal consolidated structures by initial dispersion of particles in a liquid medium. When the particle concentration is low, dispersed colloidal suspensions can be used to eliminate flow units larger than a certain size through sedimentation or classification. The surface chemistry of the particles can be modified through the adsorption of surfactants. The mixing of multiphase systems can be achieved at the scale of the primary particle size. Once the desired modifications are achieved, the transition from dispersed to consolidated structure is accomplished by either increasing the particle-particle attraction forces, such as by flocculation, or by increasing the solids content of the suspension for forced flocculation. This whole process results in going from a fluid state ("slip") to a solid phase transition ("cast"). While this has been found to occur in the micron to sub-micron size range, highly concentrated suspensions with nanometer size particles have not been as successful. Thus, some innovation is needed in traditional colloidal techniques in order to achieve nanosize powders.

[0011] Such nanoparticles possess crystalline properties and other nanoscale features that dramatically result in unique mechanical, magnetic, thermal, optical, biological, chemical and electrical properties. Considerable growth is expected in all these markets. Therefore, achievement of an economically viable industrial production of these specialized materials entails innovations in conventional processing techniques and distinct improvements in present industrial equipment.

[0012] Traditionally, powders are made using a solid state route. By this method, the raw materials are ground and milled to the same size and with a narrow size distribution, blended and fired to obtain the final product as shown:
A solid + B solid-i C solid product

[0013] In US Patent No. 6,277,521 B1, Manev et al. describe the preparation of lithium metal oxides such as LiNiiCoyMaM'1302 where M is Ti or Zr and M' is Mg, Ca, Sr, Ba, and combinations thereof. To prepare LiNio.?Coo.zTio.osMgo.osOz, stoichiometric amounts off Li0H, NiO, C0304, TiO2 and Mg(OH)2 are weighed, mixed and fired for 10 hours at 550 C followed for an additional 10 hours at 800 C. Milling after the firing step is done to produce the fine powders of micron size. Furthermore, to obtain a narrow particle distribution, sizing selection is also done in line with the milling step.
Larger size fractions are then re-milled.

[0014] One of the problems with obtaining nanopowders via the solid state method is the considerable milling process that can be time and labor intensive. The quality of the final product is a function of time, temperature and milling energy. Achieving nanometer grain sizes of narrow size distribution requires relatively long processing times in smaller batches, not just for the final sintered product but also for the starting materials, as these materials should have particle sizes within the same distribution for them to blend more homogeneously in order to have the right stoichiometry in the final product.
Hence, it may become necessary to correct the stoichiometries of the final product after firing by reblending additional starting raw materials and then refiring. As a result, successive calcinations make the processing time longer and more energy intensive which increases production cost. Production of nanopowders by mechanical attrition is a structural decomposition of the coarser grains by severe plastic deformation instead of by controlled cluster assembly that yields not only the right particle size and the required homogeneous narrow size distribution but also significant nanostructures or microstructures needed for effective performance benchmarks. As such, some higher performance standards required for specialized applications are not attained. C.C. Koch addresses these issues in his article "Synthesis of Nanostructured Materials by Mechanical Milling:
Problems and Opportunities", Nanostructured Materials, Vol. 9, pp 13-22, 1997.

[0015] Obtaining fine powders and nanopowders by milling has improved with modern grinding machines such as stirred ball mills and vibration mills for wet grinding or jet mills for dry grinding processes. However, achieving a narrow particle size distribution still remains a difficult task today. Classifiers have to be integrated with the milling system and this repetitive sizing and milling procedures increase the processing time in making fine powders and even much longer for nanopowders. Another drawback is potential contamination of the final product from the milling media used. US
Patent No.
7,578,457 B2, to R. Dobbs uses grinding media, ranging in size from 0.5 micron to 100 mm in diameter, formed from a multi-carbide material consisting of two or more carbide forming elements and carbon. These elements are selected from the group consisting of Cr, Hf, Nb, Ta, Ti, W, Mo, V, Zr. In US Patent Application No. 2009/0212267 Al, a method for making small particles for use as electrodes comprises using a first particle precursor and a second particle precursor, milling each of these precursors to an average size of less than 100 nm before reacting to at least 500 C. As an example, to make lithium iron phosphate, one precursor is aluminum nitrate, ammonium dihydrogen phosphate and the like and the other precursor is lithium carbonate, lithium dihydrogen phosphate and the like. In US Patent Application No. 2008/0280141 Al, grinding media with density greater than 8 g/mL and media size from 75-150 microns was specially made for the desired nanosize specification and the hardness of the powder to be milled.
The premise is that finer, smaller size, specialized grinding media can deliver the preferred nanosize particles. Time and energy consumption are high using this modified solid state route to nanopowders. Moreover, after milling, the grinding media and the nanopowders must be separated. Since nanopowders are a health risk if inhaled, the separation will have to be done under wet conditions. The wet powders will then have to be dried again which adds to the number of processing steps.

[0016] Chemical vapor deposition, physical vapor deposition, plasma synthesis are all synthesis of powders in the gas phase. In this process, the starting raw materials are vaporized in the gas phase then collected in a cooling step on a chosen substrate.
Controlled nucleation yields excellent powders that easily meet the rigorous requirements for specialized applications but the cost of the energy source and the equipment required for this method can significantly impact the final cost of the powder. More information on these processes is discussed by H. H. Hahn in "Gas Phase Synthesis of Nanocrystalline Materials, "Nanostructured Materials, Vol. 9, pp 3-12, 1997. Powders for the semiconductor industry are usually made by this type of processing.

[0017] In US Patent No. 8,147,793 B2, S. Put et al. disclose a method of preparing nano-sized metal bearing powders and doped powders by using a non-volatile metal bearing precursor and dispersing this precursor in a hot gas stream. This hot gas stream may be generated by a flame burner or a DC plasma arc with nitrogen as a plasma gas, for example. Thus, coarse size ZnO powder that is injected is reduced to Zn vapor.
When air is introduced, Zn is oxidized to ZnO with nano-size particles.

[0018] Among the wet solution methods for fine powder synthesis are precipitation, sol-gel, and variants of these using complexing agents, emulsifiers and/or surfactants.
In WO 2010/042434 A2, Venkatachalam et al. describe a co-precipitation process involving metal hydroxides and sol-gel approaches for the preparation of LiiNiaMnI3CoyMot02,F0 where M is Mg, Zn, Al, Ga, B, Zr, Ca, Ce, Ti, Nb or combinations thereof. In one example cited, stoichiometric amounts of nickel acetate, cobalt acetate, and manganese acetate were dissolved in distilled water to form a mixed metal acetate solution under oxygen-free atmosphere. This mixed metal acetate solution was added to a stirred solution of lithium hydroxide to precipitate the mixed metal hydroxides. After filtration, washing to remove residual Li and base, and drying under nitrogen atmosphere, the mixed metal hydroxides were mixed with the appropriate amount of lithium hydroxide powder in a jar mill, double planetary mixer or a dry powder mixer. The mixed powders were calcined at 400 C for 8 hours in air, cooling, additional mixing, homogenizing in the mill or mixer, and then recalcined at 900 C for 12 hours to form the final product Li12Ni0.175C00.10Mn0.52502. The total time from start to finish for their method is 20 hours for the calcination step alone plus the cooling time, the times for the initial mixed metal hydroxide precipitation, milling and blending to homogenize, and the filtration and washing steps. All these process steps add up to a calcination time of 20 hours excluding the cooling time for the furnace and the time from the other processing steps which will have a combined total of at least 30 hours or more.
Furthermore, in their process, the second part after the co-precipitation is a solid state method since the mixed metal hydroxides and the lithium hydroxides are mixed and then fired.
The final calcined powder size obtained from a solid state route is usually in the micron size range which will entail additional intensive milling to reduce the particles to a homogeneous narrow size distribution of nanopowders. This processing has numerous steps to obtain the final product which can impact large scale production costs.

[0019] Another example of co-precipitation is described in US 6,241,959 81.
Nitrates of nickel, cobalt and magnesium were mixed in a mole ratio of 0.79:0.19:0.02 and dissolved in solution. Aqueous ammonia was added to precipitate the hydroxides and the pH was further adjusted using 6M NaOH till pH 11. After 6 hours of addition time, the Ni-Co composite hydroxide was separated. Lithium hydroxide was mixed with this Ni-Co hydroxide and heated to 400 C and maintained at this temperature for 6 hours.
After cooling, the product was then reheated to 750 C for 16 hours. The battery cycling test was done at a low C rate of 0.2 C. Discharge capacity was 160 mAh/g. Only 30 cycles were shown. Note that the coprecipitation process is only for the Ni-Co hydroxides. The second part of this process is a solid state synthesis where the starting raw materials, Ni-Co hydroxide and the lithium hydroxide are mixed and then fired. The addition of NaOH to raise the pH to 11 as well as provide a source of hydroxide ions would leave residual Na ions in the final product unless the excess Na+ is washed off. This excess Na+
will affect the purity of the material and have some deleterious effect in the battery performance.
The total process time is 6 hours addition time for the co- precipitation step, 22 total hours for the holding time at the two heating steps and additional time for the other steps of cooling, separating, mixing and others which sums up to at least 40 hours of processing time.

[0020] Sol-gel synthesis is a variant of the precipitation method. This involves hydrolysis followed by condensation to form uniform fine powders. The raw materials are expensive and the reaction is slow since the hydrolysis-condensation reactions must be carefully controlled. Alkoxides are usually the choice and these are also air sensitive; thus requiring the reactions to be under controlled atmosphere.

[0021] Hydrothermal synthesis has also been used to prepare these powders.
This involves crystallization of aqueous solutions at high temperature and high pressures. An example of this process is disclosed in US Patent Publication No. 2010/0227221 Al. A
lithium metal composite oxide was prepared by mixing an aqueous solution of one or more transition metal cations with an alkalifying agent and another lithium compound to precipitate the hydroxides. Water is then added to this mixture under supercritical or subcritical conditions, dried then followed by calcining and granulating then another calcining step to synthesize the lithium metal oxide. The water under supercritical or subcritical conditions has a pressure of 180-550 bar and a temperature of 200-700 C.

[0022] The use of agents like emulsifiers, surfactants, and complexing agents to form nanosize powders has been demonstrated. In microemulsion methods, inorganic reactions are confined to aqueous domains called water-in-oil or surfactant/water/oil combination. A
problem is separation of the product particle from the oil since filtration of a nanosize particle is difficult. Reaction times are long. Residual oil and surfactant that remain after the separation still have to be removed by other means such as heating. As a result, the batch sizes are small.

[0023] A variety of structures are formed by the surfactant with another particle dispersed in solution. Micelles are formed at high concentrations of the surfactant and the micelle diameter is determined by the length of the surfactant chain which can be from 20-300 angstroms. US Patent No. 6,752,979 B1 describes a way of making metal oxide particles with nano-sized grains using surfactants. A concentrated aqueoussolution of at least one or more metal cations of at least 90% of its solubility is mixed with surfactant to form micelles at a given temperature. Optionally, this micellar liquid forms a gel. This mixture is heated to form the metal oxide and remove the surfactant. A disadvantage is the long heat treatment times.

[0024] US Patent No. 6,383,285 B1 discloses a method for making cathode materials for lithium ion batteries using a lithium salt, a transition metal salt, and a complexing agent in water then removing water by spray-drying to form a precursor.
These complexing agents were citric acid, oxalic acid, malonic acid, tartaric acid, maleic acid and succinic acid. The use of these agents increases the processing cost of the product. The precursor is formed from the lithium, transition metal and the complexing agent after spray drying. Battery capacities were only given for the first cycle. The C-rate was not defined. For electric vehicle applications, lithium ion battery performance at high C-rate for many cycles is an important criterion.

[0025] A method for making lithium vanadium phosphate was described in US
Patent Publication No. 2009/0148377 Al. A phosphate ion source, a lithium compound, V205, a polymeric material, solvent, and a source of carbon or organic material were mixed to form a slurry. This wet blended slurry was then spray dried to form a precursor which was then milled, compacted, pre-baked and calcined for about 8 hours at 900 C. The particle size after spray drying was about 50-100 microns. The final product was milled to 20 microns using a fluidized bed jet mill.

[0026] Nanosize Li4Ti5012 was prepared by preparing this lithium titanate as a first size between 5 nm to 2000 nm as described in US Patent No. 6,890,510 82 from a blend of titanium and lithium, evaporating and calcining this blend, milling this powder to a finer size, spray drying then refiring this lithium titanate, then milling again. There are several milling and firing sequences in this process to obtain the nanosize desired which increase the number of processing steps which consequently increases the cost of processing.

[0027] In spite of the significant efforts and advances in the art the art is still lacking a method of preparing small, nanoparticles with narrow particle size distributions, controllable particle size and which can be prepared economically.
SUMMARY OF THE INVENTION

[0028] It is the objective of this invention to describe an economically scalable process useful for several high value-added inorganic powders tailored to meet the desired performance specifications. It is a further objective of this invention to produce the selected narrow size particle distribution of these powders and to produce the desired particle size needed for the selected application, such size ranging from fine micron size particles to ultrafine powders and the nanosize powders. It is also the objective of this invention to produce these powders that meet or exceed presently available materials.

[0029] It is an object of this invention to provide a methodology for industrial production of special fine, ultrafine and nano powders without compromising performance.

[0030] A particular advantage of the invention is the ability to prepare fine, ultrafine and nano- powders in large scale production.

[0031] It is an object of the invention to produce these specialized powders that outperform presently available powders.

[0032] It is an object of the invention to utilize low cost starting raw maerials and to incorporate any purification within the process steps as required.

[0033] These and other advantages, as will be realized, are provided in a method of forming a powder Nix wherein NA; is a positive ion or several positive ions selected from alkali metal, alkaline earth metal or transition metal; and ; is a monoatomic or a polyatomic anion selected from Groups IIIA, IVA, VA, VIA or VIIA; called complexometric precursor formulation or CPF. The method includes the steps of:
providing a first reactor vessel with a first gas diffuser and a first agitator;
providing a second reactor vessel with a second gas diffuser and a second agitator;
charging the first reactor vessel with a first solution comprising a first salt of MjXp;
introducing gas into the first solution through the first gas diffuser, charging the second reactor vessel with a second solution comprising a second salt of MX;
adding the second solution to the first solution to form a complexcelle;
drying the complexcelle, to obtain a dry powder; and calcining the dried powder of said MjXp.
FIGURES

[0034] FIG. 1 is a diagram of advanced technical materials which require specialized processing to obtain composites, whiskers, fibers and powders.

[0035] FIG. 2 is a comparison of preparative methods for powders.

(0036] FIG. 3 is a flow chart of two reactants via the complexometric precursor formulation methodology for the synthesis of specialized powders.

[0037] FIG. 4 illustrates of a reactor vessel with gas inlet tubes and agitator with special blades.

[0038] FIG. 5A schematically illustrates agitator blades with wound concentric rings.

[0039] FIG. 5B is a side schematic partial view of the concentric rings of the agitator blade.

[0040] FIG. 5C schematically illustrates one set of propellers with three blades, concentric rings are not shown, attached to the mixer shaft, each blade rotating on its own axis horizontally and vertically on the mixer axis.

[0041] FIG. 5D schematically illustrates two sets of propellers with three blades arranged on the mixer shaft.

[0042] FIG. 5E schematically illustrates one set of propellers with three blades arranges alternately on the mixer shaft.

[0043] FIG. 5F schematically illustrates one set of propellers with four blades on the mixer shaft.

[0044] FIG. 5G schematically illustrates one set of propellers with four blades arranged alternately on the shaft of the reactor.

[0045] FIG. 6A schematically illustrates a bubble surface above the bulk of the solution showing small and large bubbles.

[0046] FIG. 6B is a top schematic view of the bubble surface interface showing the reactants on the surface interface.

[0047] FIG. 7 is a schematic representation of the steps during complexcelle formation and separation from the bulk of the solution.

[0048] FIG. 81 is a scanning electron micrograph at 5000 X of a commercial LiCo02 in Example 1.

[0049] FIG. 8B is a scanning electron micrograph at 25000 X of a commercial L1Co02 in Example 1.

[0050] FIG 9 is an x-ray powder diffraction pattern of a commercial LiCo02 in Example 1.

[0051] FIG. 10 is a scanning electron micrograph at 5000 X of air dried LiCo02 feed precursor to the spray dryer for Example 2.

[0052] FIG. 11A is a scanning electron micrograph at 10000 X of spray dried LiCo02 described in Example 2 prior to calcination.

[0053] FIG. 11B is a scanning electron micrograph at 25000 X of spray dried LiCo02 described in Example 2 prior to calcination.

[0054] FIG. 12 is a scanning electron micrograph at 10000 X of spray dried LiCo02 described in Example 2 after calcination.

[0055] FIG. 13 is an x-ray powder diffraction pattern of LiCo02 in Example 1.

[0056] FIG. 14 is battery cycling data for Examples 1 and 2 at C/20 for 500 cycles.

[0057] FIG. 15 is battery cycling data at 1C for 500 cycles for Examples 1 and 2 after recalcination for 5h at 900 C.

[0058] FIG. 16 is a scanning electron micrograph at 10000 X of recalcined LiCo02 from Example 2.

[0059] FIG. 17 is a scanning electron micrograph at 10000 X of recalcined commercial LiCo02 from Example 1.

[0060] FIG. 18A is a scanning electron micrograph at 2000 X of air-dried Lii2oNio.leMnos)C00.1202 from Example 4.

[0061] FIG. 18B is a scanning electron micrograph at 10000 X of air-dried Lii2oNiveMna5oCo0.1202from Example 4.

[0062] FIG. 19A is a scanning electron micrograph at 5000 X of spray dried Lil2oNio.18Mno.50C00.1202from Example 4.

[0063] FIG. 19B is a scanning electron micrograph at 10000 X of spray dried Lit2oNicrisMno.50000.1202frcm Example 4.

[0064] FIG. 20A is a scanning electron micrograph at 10000 X of calcined Lii.20NiaisMno.50Coo.1202ficm Example 4.

[0065] FIG. 20B is a scanning electron micrograph at 25000 X of calcined Li120Ni0.18Mn0.50C00.1202 from Example 4.

[0066] FIG. 21 is an x-ray powder diffraction pattern of calcined LitzoNimeMno.50C00.1202frum Example 4.

[0067] FIG. 22 is battery Cycling Data for calcined Lit2oN1318Mno.50030.1202from Example 4 at RT for 500 cycles at 1C.

[0068] FIG. 23A is battery Cycling Data for calcined Li12oNicrieMno.5oC00.1202from Example 4 at 30 C for 500 cycles at different C rates from C/20 to 1C.

[0069] FIG. 23B is battery Cycling Data for calcined Li1.203.18Mno.5oC00.1202from Example 4 at 30 C for 500 cycles at different C rates from C/10, 0/3 and 1C.

[0070] FIG. 24A is battery Cycling Data for calcined Lii2oNia-i8Mno.50C00.1202from Example 4 at 25 C for 500 cycles at from 0/20 to 1C.

[0071] FIG. 240 is battery Cycling Data for calcined LiuoNialeMno.50Cool202frtri Example 4 at 25 C for 500 cycles at 1C.
DESCRIPTION

[0072] The instant invention is specific to an improved method of forming nanoparticles. More specifically, the instant invention is specific to a method of forming particles through formation of a complexometric precursor formed on a bubble surface thereby allowing for careful control of nucleation and crystal growth.

[0073] The invention will be described with reference to the various figures which form an integral non-limiting component of the disclosure. Throughout the disclosure similar elements will be numbered accordingly.

[0074] This invention described herein is a complexometric precursor formulation methodology, hereinafter referred to as "CPF", suitable for large scale industrial production of high performance fine, ultrafine and nanosize powders requiring defined unique chemical and physical properties that are essential to meet performance specifications for specialized applications.

[0075] The CPF method proceeds in the formation of a complex precursor, herein called complexcelle, on a bubble surface thereby providing for the controlled formation of specialized microstructures or nanostructures and a final product with particle size, surface area, porosity, phase purity, chemical purity and other essential characteristics tailored to satisfy performance specifications. Powders produced by CPF are obtained with a reduced number of processing steps relative to currently used technology and can utilize presently available industrial equipment. CPF is simple to implement and preferred design configurations are further described and illustrated in Figures 4 and 5.
CPF methodology is applicable to any inorganic powder and organometallic powders with electrophilic or nucleophilic ligands. The CPF procedure can use low cost raw materials as the starting raw materials and if needed, additional purification or separation can be done in-situ. Inert or oxidative atmospheric conditions required for powder synthesis are easily achieved with the equipment for this method. Temperatures for the reactions forming the complexcelle are ambient or slightly warm but preferably not more than 100 C. The CPF process can be a batch process or a continuous process wherein product is moved from one piece of equipment to the next in sequence. A
comparison of traditional methods and other conventional processing is diagrammed in Figure 2 with this CPF methodology. Representative examples are discussed and compared with commercially available samples showing both physical properties and performance improvements of powders synthesized using this CPF methodology.

[0076] The CPF method produces fine, ultrafine and nanosize powders in a simple efficient way by integrating chemical principles of crystallization, solubility, transition complex formation, phase chemistry, acidity and basicity, aqueous chemistry, thermodynamics and surface chemistry.

[0077] It is preferred to produce these powders with the selected properties at the onset of the contact among the elements as these are combined to make the desired compound. The time when crystallization begins and, in particular, when the nucleation step begins, is the most crucial stage of formation of nanosize powders. A
particular advantage provided by CPF is the ability to prepare the nanosize particles at the onset of this nucleation step. The solute molecules from the starting reactants are dispersed in a given solvent and are in solution. At this instance, clusters begin to form on the nanometer scale on the bubble surface under the right conditions of temperature, supersaturation, and other conditions. These clusters constitute the nuclei wherein the atoms begin to arrange themselves in a defined and periodic manner which later defines the crystal microstructure. Crystal size and shape are macroscopic properties of the crystal resulting from the internal crystal structure.

[0078] After the nucleation begins, crystal growth also starts and both nucleation and crystal growth may occur simultaneously as long as supersaturation exists. The rate of nucleation and growth is determined by the existing supersaturation in the solution and either nucleation or growth occurs over the other depending on the supersaturation state.
It is critical to define the concentrations of the reactants required accordingly in order to tailor the crystal size and shape. If nucleation dominates over growth, finer crystal size will be obtained. The nucleation step is a very critical step and the conditions of the reactions at this initial step define the crystal obtained. By definition, nucleation is an initial phase change in a small area such as crystal forming from a liquid solution.
It is a consequence of rapid local fluctuations on a molecular scale in a homogeneous phase that is in a state of metastable equilibrium. Total nucleation is the sum effect of two categories of nucleation-primary and secondary. In primary nucleation, crystals are formed where no crystals are present as initiators. Secondary nucleation occurs when crystals are present to start the nucleation process. It is this consideration of the significance of the initial nucleation step that forms the basis for thisCPF
methodology.

[0079] In the CPF methodology, the reactants are dissolved in a solution preferably at ambient temperature or if needed, at a slightly elevated temperature but preferably not more than 100 C. Selection of inexpensive raw materials and the proper solvent are important aspects of this invention. The purity of the starting materials are also important since this will affect the purity of the final product which may need specified purity levels required for its performance specifications. As such, low cost starting materials which can be purified during the preparation process without significantly increasing the cost of processing must be taken into consideration. For instance, if a preferred starting raw material is a carbonate salt, one can start with a chloride salt as most reactants from rock processing are chloride salts. There may be some impurities in this chloride salt that may need to be removed and depending on the ease of impurity reduction, this chloride salt can be converted to the carbonate salt and at the same time remove any impurity or reduce the impurity levels.

[0080] CPF uses conventional equipment in an innovative way to produce the nanosize nuclei required for the final product. CPF utilizes a reactor fitted with a gas diffuser to introduce gas into the solution thereby creating bubbles. An agitator vigorously disperses the solution simultaneously with the bubble formation, as the second reactant is introduced into the first solution. The combination of gas flow and agitation provides a bubble surface. The bubble surface serves as the interface of contact between the molecules of the first solution and the molecules of the second solution thereby providing a surface reaction.

[0081] A surface reaction is the adsorption of one or more reactants from a gas, liquid or dissolved solid on a surface. Adsorption may be a physical or chemical adsorption.

[0082] The CPF process creates a film of the adsorbate on the bubble surface of the adsorbent. The bubble surface is the adsorbent and the adsorbates are the reactants in the solution. As illustrated in Figure 6A, a bubble is formed from solution due to the simultaneous introduction of gas and agitator speed. Different size bubbles can be formed depending on gas flow rates. The size of the bubbles defines the surface area of contact between the molecules and this relates to the degree of nucleation which influences the particle size.

[0083] In Figure 6B, the top view of this complexcelle is shown schematically. The complexcelle comprises gas bubble, 61, with a bubble surface, 62, shown above the surface of the solution, 68. The first reactant cation, 63, the first reactant anion, 64, the second reactant cation, 65 and the second reactant anion, 66, are all on the bubble surface. Solvent is not illustrated in the schematic diagram but it is understood that the solvent molecules are present. In Figure 7, an illustration of this surface pathway is diagrammed showing the start of bubble formation, 61, from the bulk of the solution, the surface nucleation on the bubble surface, 62, which forms the complexcelle having reactants ions, 63 -66, and the separation of this complexcelle from the bulk of the solution. The water molecules, 67, or solvent molecules are shown. This is a very dynamic state as the solution is vigorously and continuously mixed during the time of the addition of the second reactant solution into the first reactant solution.
Furthermore, bubbles are formed within the bulk of the solution and the general direction is for these bubbles to move towards the top surface of the solution. The agitation rate enhances the rise of these bubbles to the surface and mixes the solution vigorously so that there is significant turnover of these reactants and their bubbles allowing fresh surface bubbles to continually be available for complexcelle formation. It will be realized that the above mechanism is a postulated mechanism and the present invention should not be construed as being limited to this particular pathway.

[0084] It is preferred that the gas be introduced directly into the solution without limit to the method of introduction. The gas can be introduced into the solution within the reactor by having several gas diffusers, suchas tubes, located on the side of the reactor, wherein the tubes have holes for the exit of the gas as illustrated in Figure 4. Another configuration is to have a double wall reactor such that the gas passes through the interior wall of the reactor. The bottom of the reactor can also have entry ports for the gas. The gas can also be introduced through the agitator shaft, creating the bubbles upon exiting. Several other configurations are possible and the descriptions of these arrangements given herein are not limited to these. Throughout the description the point of gas being introduced into the liquid is a gas diffuser.

[0085] In one embodiment an aerator can be used as a gas diffuser. Gas diffusing aerators can be incorporated into the reactor. Ceramic diffusing aerators which are either tube or dome-shaped are particularly suitable for demonstration of the invention.
The pore structures of ceramic bubble diffusers produce relatively fine small bubbles resulting in an extremely high gas to liquid interface per cubic feet per minute (cfm) of gas supplied. This ratio of high gas to liquid interface coupled with an increase in contact time due to the slower rate of the fine bubbles accounts for the higher transfer rates. The porosity of the ceramic is a key factor in the formation of the bubble and significantly contributes to the nucleation process. While not limited thereto for most configurations a gas flow rate of at least one liter of gas per liter of solution per minute is suitable for demonstration of the invention.

[0086] A ceramic tube gas diffuser on the sides of the reactor wall is particularly suitable for demonstration of the invention. Several of these tubes may be placed in positions, preferably equidistant from each other, to create bubbling more uniformly throughout the reactor. The gas is preferably introduced into the diffuser within the reactor through a fitting connected to the header-assembly which slightly pressurizes the chamber of the tube. As the gas permeates through the ceramic diffuser body, fine bubbles start being formed by the porous structure of the material and the surface tension of the liquid on the exterior of the ceramic tube. Once the surface tension is overcome, a minute bubble is formed. This small bubble then rises through the liquid forming an interface for transfer between gas and liquid before reaching the surface of the liquid level.

[0087] A dome-shaped diffuser can be placed at the bottom of the reactor or on the sides of the reactor. With dome shape diffusers a plume of gas bubbles is created which is constantly rising to the surface from the bottom providing a large reactive surface.

[0088] A membrane diffuser which closes when gas flow is not enough to overcome the surface tension is suitable for demonstration of the invention. This is useful to prevent any product powder from being lost into the diffuser.

[0089] In order to have higher gas efficiencies and utilization, it is preferred to reduce the gas flow and pressure and expend less pumping energy. A diffuser can be configured such that for the same volume of gas, smaller bubbles are formed with higher surface area than if fewer larger bubbles are formed. The larger surface area means that the gas dissolves faster in the liquid. This is advantageous in solutions wherein the gas is also used to solubilize the reactant by increasing its solubility in the solution.

[0090] Smaller bubbles also rise more slowly than the larger bubbles. This is due to the friction, or surface tension, between the gas and the liquid. If these bubbles start from the same position or depth in the reactor, the larger bubbles reach the surface more quickly than several smaller bubbles. The smaller bubbles will have more liquid as it rises.
The bubble surface interface between the two reactants determines the nucleation rate and size can therefore be tailored by controlling the bubble size formation.

[0091] Nozzles, preferably one way nozzles, can be used to introduce gas into the solution reactor. The gas can be delivered using a pump and the flow rate should be controlled such that the desired bubbles and bubble rates are achieved. A jet nozzle diffuser, preferably on at least one of the sides or bottom of the reactor, is suitable for demonstration of the invention.

[0092] The rate of gas introduction is preferably sufficient to increase the volume of the solution by at least 5% excluding the action of the agitator. In most circumstances at least about one liter of gas per liter of solution per minute is sufficient to achieve adequate bubble formation. It is preferable to recycle the gas back into the reactor.

[0093] Transfer of the second reactant solution into the first reactor solution is preferably done using a tube attached to a pump connecting the solution to be transferred to the reactor. The tube into the reactor is preferably a tube with a single orifice or several orifices of a chosen predetermined internal diameter such that the diameter size can deliver a stream of the second solution at a given rate. The tube may have an inner diameter of at least 2 mm. Atomizers with fine nozzles are suitable for delivering the second solution into the reactor. The tip of this transfer tube can comprise a showerhead or sprinkler thereby providing several streams of the second solution reacting on several surface bubbles simultaneously. Nucleation is influenced not only by the concentration of the second solution but also by the instantaneous concentration of this solution as it reaches the surface bubble interface to form the complexcelle. In large scale production, the rate of transfer is a time factor so the transfer rate should be sufficiently rapid enough to produce the right size desired.

[0094] The agitator can be equipped with several propellers of different configurations, each set comprising one or more propellers placed at an angle to each other or on the same plane. Furthermore, the mixer may have one or more sets of these propellers. The objective is to create enough turbulence for rapid bubble formation and turnover. Examples of the agitator arrangements are shown in Figures 5 A-G but other similar formations are also possible and not limited to these. The function of this mixer is not only to insure homogeneity of the reaction mixture but also to assist in the bubble surface interaction which further influences the nucleation and is a determining factor in the size of the final particle.

[0095] Straight paddles or angled paddles are suitable. The dimensions and designs of these paddles determine the type of flow of the solution and the direction of the flow.
One preferred blade design for CPF methodology is shown in Figure 5 where the paddles consist of concentric rings wired around the paddle that create a frothing effect in the solution. In addition, the paddle can rotate on its own axis as well as rotate vertically by the axis of the mixer. This maximizes the bubbling effect even under slower agitation speed. A speed of at least about 100 rotations per minute (rpm's) is suitable for demonstration of the invention.

[0096] The CPF process steps are demonstrated in the following examples below for a desired final product MX p such that M = M1 M2 M3 (dual metal cation) or more and Xp = 0. The flow chart in Figure 3 shows a schematic outlay of the application of the CPF
methodology to powders MX p as defined earlier for two reactants. It is obvious to someone skilled in the art that some modifications of these process steps would be done depending on the starting reactants, the desired precursor and the final desired product.

[0097] The starting raw materials for this process are chosen from Groups IA, IIA, Ii1A, IVA and transition metals with the anion being monatomic or a polyanion selected from Groups IIIA, IVA, VA, VIA and VIIA. The final powders are cation compounds of anions or polyanions such that the formula is MX where Mi may be a single cation or a mixture of metal cations and Xp may be a single anion, a single polyanion or a mixture of mixed anions and polyanions. M, may be M1 M2 M3 or more which are in stoichiometric or non-stoichiometric ratios and one or two may be small dopant amount not more than 10 weight % of the final powder. The anion and polyanions may be oxides, carbonates, silicates, phosphates, borates, aluminates, silicophosphates, stannates, hydroxides, nitrates, oxycarbonates, hydroxycarbonates, fluorides, oxyfluorides without limited thereto. Examples of these desired high performance powders are utilized in lithium ion battery applications, rechargeable batteries, bone implants, dental implants, structural ceramics, optical communication fibers, medical patches for drug delivery and specialized composites of metal-metal, metal-ceramic, glass-ceramic, glass-metal and others but not limited to these. The following discussion will illustrate the complexometric precursor formulation technology as applied to the synthesis of a lithium cathode material for lithium ion batteries. It is known that this art is not limited to this illustrative example but is applicable to numerous specialized high performance powders which are very expensive to manufacture today. The reactants in each solution are preferably no more than 30 wt.% of the solution.

[0098] A first reactant solution A, or MAI is prepared by dissolving the solid in a selected solvent, preferably a polar solvent such as water but not limited thereto. It is understood that the choice of solvent depends on the type of final powder product desired, the formulated composition of the final powder and the physical characteristics required for achieving the performance of the final powder. The choice of the solvent is determined by the solubility of the solid reactant A in the solvent and the temperature of dissolution. It is preferred to dissolve at ambient temperature and to dissolve at a fast rate so that solubilization is not energy intensive. The dissolution may be carried out at a slightly higher temperature but preferably below 100 C. Only if other dissolution methods fail should a higher temperature be used. Other dissolution aids may be addition of an acid or a base. The solution concentration is preferably low as this influences concentration at the surface bubble interphase during the nucleation which determines the final powder size. It is important to select the proper chemical environment in order to produce the right nucleation to yield the desired final powder characteristics.

[0099] The cost of the starting materials should also be considered in the sum total of the process cost. Generally, lower cost raw materials are the salts of chlorides, nitrates, hydroxides and carbonates. Acetate salts and other compounds are usually prepared from these so these downstream compounds will be at higher cost.
Nitrates and sulfates are readily soluble in water but they also release noxius gases during high temperature calcination. The purity of the starting materials is also a cost consideration and technical grade materials should be the first choice and additional inexpensive purification should be factored in the selection of the starting materials.

[00100] A second reactant solution B is also prepared in the same way as reactant solution A. The solid starting material and the solvent selected for dissolution should yield the fastest dissolution under mild conditions as possible.

[00101] The reactor, 1, set-up for both solutions A and B is diagrammed in Figure 4.
Baffles, 2, are preferred and are preferably spaced at equal distance from each other.
These baffles promote more efficient mixing and prevent build-up of solid slags on the walls of the reactor. A top cover, 5, is latched to the bottom section of the vessel using a flange or bolts, 4. An 0-ring, 3, serves to seal the top and bottom sections of the reactor.
The mixer shaft, 7, and the propeller, 8-9, are shown in Figure 4 and in more detail in Figure 5. The mixer shaft is preferably in the center of the reactor vessel and held in place with an adaptor or sleeve, 6. Gas is introduced through a gas diffuser such as gas tubes,10, which have small outlets on the tube for exit of the gas. These gas tubes are placed vertically into the reactor through the portholes of the top cover and held in place with adaptors, 6. The gas used for bubbling is preferably air unless the reactant solutions are air-sensitive. In this instance, inert gas is employed such as argon, nitrogen and the like. Carbon dioxide is also used if a reducing atmosphere is required and it can also be used as a dissolution agent or as a pH adjusting agent. Ammonia may also be introduced as a gas if this is preferable to use of an ammonia solution. Ammonia can form ammonia complexes with transition metals and a way to dissolve such solids. Other gases such as SF6, HF, HCI, NH3, methane, ethane or propane may also be used. Mixtures of gases may be employed such as 10% 02 in argon as an example. Another porthole on the top cover of the reactor is for the transfer tube (not shown) and another porthole can be used for extracting samples, adding other reactant, as Reactant C for pH adjustment or other, and also or measurements of pH or other needed measurements.

[00102] The agitator blade illustrated in Figure 5 with a concentric wire design is preferred over the regular paddle type since this assists in bubble formation and allows the solution system to be in a dynamic motion such that fresh bubble surfaces are continuously and rapidly produced as the second solution of reactant B is being transferred into the reactor containing solution of reactant A. The agitator blade has concentric wire wound, 9, and it can rotate on its axis, 10, as shown in a top view in Figure 5A. A side view of this design is shown in Figure 5B. Figures 5C-5G
illustrate different arrangements of blades. The concentrically wound wires are not shown to simplify the diagrams. The blade is attached to the mixer shaft (7) as shown in Figure 5C
and one set of propellers with three blades rotate horizontally on their own axes (Fig. 5C-10) and also rotate vertically (Fig. 5C-11) simultaneously on the mixer shaft axis, 11. In Figure 5D, two sets of propellers with three blades each are drawn which move as in Fig.
5C. There are three blades arranged alternately on the mixer shaft in Fig. 5E.
In Figure 5F, the arrangement is similar to Figure 5C but there are two sets of propellers with four blades. In Figure 5G, the four blades are arranged one above the other on the mixer shaft as in Figure 5C. There can be many variations of these configurations with different number of blades, different blade dimensions, different plurality of blades in a set, several sets of blades, different angular orientation relative to each other, different number of coils per blade, etc. The blade configurations are not limited to these illustrations in Figure 5.

[00103] The rate of transfer has a kinetic effect on the rate of nucleation. A preferred method is to have a fine transfer stream to control the concentration of the reactants at the bubble surface interface which influences the complexcelle formation and the rate of nucleation over the rate of crystal growth. For smaller size powder, a slower transfer rate will yield finer powders. The right conditions of the competing nucleation and growth must be determined by the final powder characteristics desired. The temperature of reaction is preferably ambient or under mild temperatures if needed.

[00104] Upon completion of the reaction of reactant A and reactant B, the resulting slurry mixture containing the intermediate complexcelle is dried to remove the solvent and to obtain the dried powder. Any type of drying method and equipment can be used and such drying is preferably at less than 350 C. Drying can be done using an evaporator such that the slurry mixture is placed in a tray and the solvent is released as the temperature is increased. Any evaporator in industrial use can be employed.
The preferred method of drying is by using a spray dryer with a fluidized nozzle or a rotary atomizer. These nozzles should be the smallest size diameter although the size of the powder in the slurry mixture has already been predetermined by the reaction conditions.
The drying medium is preferably air unless the product is air-sensitive. The spray dryer column should also be designed such that the desired moisture content is obtained in the sprayed particulates and are easily separated and collected.

[00105] The spray dried particles obtained by the CPF methodology are very fine and nanosize. Definitive microstructures or nanostructures by the CPF process are already formed during the mixing step. Novel microstructures or nanostructures looking like flowers or special layering such that these structures are called nanorose, nanohydrangea, or nanocroissant or other description depending on the formulation of the = powder. Such structures also translate to the final powder after the calcination step.

[00106] After spray drying, the powder is transferred to a calciner.
No crushing or milling is required since the spray dried powders are very fine. In large scale production, this transfer may be continuous or batch. A modification of the spray dryer collector such that an outlet valve opens and closes as the spray powder is transferred to the calciner can be implemented. Batchwise, the spray dried powder in the collector can be transferred into trays or saggers and moved into a calciner like a box furnace although protection from powder dust should also be implemented. A rotary calciner is also another way of firing the powder. A fluidized bed calciner is also anotherway of higher temperature heat treatment of the spray dried powder. The calcination temperature is determined by the composition of the powder and the final phase purity desired. For most oxide type powders, the calcination temperatures range from as low as 400 C to slightly higher than 1000 C. After calcination, the powders are crushed as these are soft and not sintered.
The CPF process delivers non-sintered material that does not require long milling times nor does the final CPF process require classifiers to obtain narrow particle size distribution. The particle sizes achievable by the CPF
methodology are of nanosize primary and secondary particles and up to small micron size secondary particles ranging to less than 50 micron aggregates which are very easily crushed to smaller size. It should be known that the composition of the final powder influences the morphology as well. The powder may have a surface area of more than 1 m2/gm.

[00107] A brief stepwise summary of the CPF methodology is given below.

[00108] A first solution or slurry solution of M = M1 chosen from the metal chlorides, metal nitrates, metal hydroxides, metal acetates, metal carbonates, metal hydrocarbonates, metal hydroxyl phosphates and metal hydroxysilicates but not limited to these would be prepared. The purity of the starting reactant for MI should be defined by the final purity desired and the degree of purification that may be done in a preliminary step.

[00109] A second solution or slurry solution of M = M2 also chosen from the same metal salts as for the first solution. The purity of the starting reactant for M2 should also be chosen on the basis of the final purity of the final product and the degree of purification needed in a preliminary step.

[00110] The solvent in both the first and second solution is preferably deionized water at acidic or basic pH and ambient temperature. An acid or a base may be added to the first or second solution to aid in solubilizing the reactants and/or the temperature may be increased but preferably not more than 100 C, and/or the solubilizing mixing rate be more vigorous and solubilizing time increased. If conditions require more adverse temperature and time, then the process may proceed as slurry solutions. Other solvents to dissolve the starting materials may also be used if water is insufficient for dissolution. Such solvents may be polar solvents as alcohols or non-polar solvents typically used in general organic preparations. It is important to consider raw material costs during the evaluation of the process so that production cost does not decrease the value-added performance advantages of the CPF powder. [00111] A CPF reactor designed or configured so that gas may be introduced into the vessel is charged with the first solution. The gas may be air, argon, carbon dioxide, nitrogen, or mixtures of these preferably of normal purity. The gas may be inert for reactions that are adverse in air. Likewise, the gas may also be a possible reactant such as, for example, those reactions wherein carbon dioxide is utilized to produce carbonates or bicarbonates, or hydroxycarbonates and oxycarbonates but not limited to these.
[00112] The gas may be introduced by a gas diffuser such as gas tubes having holes in the tube from which the gas introduced from the inlet exits into the reactor vessel creating a vigorous flow and a bubbling solution with numerous fine micro-bubbles. The holes may be sized to insure bubbles are generated over the entire length of the tube.
[00113] The gas may also be introduced by mechanical gas diffusers with pumps that may circulate both gas and solution which also improves mixing of the solutions.
[00114] The gas flow rate, in conjunction with the mixing speed of the agitator, should be enough to create suspended micro bubbles such as a foamy solution.
[00115] An agitator blade is configured to produce vigorous mixing to produce a frothy slurry solution or frothy solution. The agitator blade may be a concentric loop to promote incorporation of the gas and the formation of fine bubbles. The concentric loop may rotate horizontally and vertically. In addition, the agitator blade may be dual, triple, quadruple, quintuple or other configuration and not limited to these.
Depending on the height of the reactor vessel, several agitator blades may be used.
[00116] The mixing speed should be fast enough to maintain bubbles of first solution such that the second solution being added drops into the bubbles of the first solution creating a micro or nano contact onto the surface of the bubbles of the second solution.
[00117] The first solution may be added to the second solution. The resulting product performance may be different depending on the method of addition.
[00118] The mixing temperature is preferably ambient or slightly elevated but not more than 100 C.
[00119] The resulting mixture of first and second solutions may be a solution or a slurry mixture.
[00120] The resulting reaction product is dried by any drying method using known industrial equipment including spray dryers, tray dryers, freeze dryers and the like, chosen depending on the final product preferred. The drying temperatures would be defined and limited by the equipment utilized. The desired drying temperatures are usually from 200 ¨ 325 C.
[00121] The resulting mixture is continuously agitated as it is pumped into the spray dryer head if spray dryers, freeze dryers or the like are used. For tray dryers, the liquid evaporates from the surface of the solution.
[00122] The dried powders are transferred into the next heating system batch-wise or by means of a conveyor belt. The second heating system may be a box furnace utilizing ceramic trays or saggers as containers, a rotary calciner, a fluidized bed, which may be co-current or counter-current, a rotary tube furnace and other similar equipment but not limited to these. The calcination temperature depends on the final product requirements and could be as high as 1000 C and up to as much as 3000 C or more as in the case of glassy silicates.
[00123] The heating rate and cooling rate during calcinations depend on the type of final product desired. Generally, a heating rate of about 10 C per minute is preferred but the usual industrial heating rates are also applicable.
[00124] Calcining may also require inert gases as in the case of those materials that are sensitive to oxidation. As such, a positive flow of the inert gas may be introduced into the calcining equipment.
[00125] The final powder obtained after the calcining step is a fine, ultrafine or nanosize powder that does not require additional grinding or milling as is currently done in conventional processing. Particles are relatively soft and not sintered as in conventional processing.
[00126] The final powder is preferably characterized for surface area, particle size by electron microscopy, porosity, chemical analyses of the elements and also the performance tests required by the preferred specialized application.
[00127] The CPF methodology for the production of fine, ultrafine and nanosize powders offers several advantages. One of the improvements is reduction in the number of processing steps. There is no significant milling and firing sequence in the CPF
method. The total production time for this CPF methodology route to fine, ultrafine and nanosize powders is less than or equal to 25% of current conventional processing technologies for such similar powders. Final powder production cost using CPF
methodology can be significantly reduced by as much as 75-80% of current conventional processing. Performance improvements of these powders produced by CPF are at least 15% or more than those traditional ceramic powders currently produced by presently known technologies. The CPF process can be utilized for the preparation of different types of powders and is not limited to a group of powder formulations.
[00128] This CPF process can be applied to make the desired powder for the lithium ion batteries, such as lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide and the doped lithium metal oxides of this type, the mixed lithium metal oxides of said metals and the doped derivatives, lithium iron-phosphate and-the doped lithium iron phosphates as well as other lithium metal phosphates, lithium titanates and other materials for the storage batteries. The CPF process can be applied to produce medical powders such as the specialized calcium phosphates for medical applications like bone implants.
The CPF process can also be used for the preparation of other advanced ceramic powders such as lithium niobates and lithium tantalates, lithium silicates, lithium aluminosilicates, lithium silicophosphates and the like. Semiconductor materials can also be prepared by the CPF process as well as specialized pharmaceutical drugs.
High surface area catalysts can be made by the CPF process and such catalysts would have higher catalytic activity as a result of a finer particle size, higher surface area and higher porosity made possible by the CPF methododology. Specialized coatings requiring nanosize powders can be economically prepared by the CPF method. This CPF
process can also be used for the preparation of non-lithium based materials. The versatility of this methodology allows itself to be easily modified in order to achieve the customized, tailored powder needed. Furthermore, this methodology is easily adapted for large scale industrial production of specialized powders requiring a narrow particle size distribution and definitive microstructures or nanostructures within the fine, ultrafine or nanosize powders.
Having a cost effective industrial scale powder for these specialized applications will allow commercial development of other devices otherwise too costly to manufacture.

[00129] The complexometric precursor formulation methodology or CPF, creates a fine, ultrafine or nanosize powders via the formation of a complexcelle of all the ions of the desired powder composition on a bubble surface interface. CPF has many advantages over known prior art.
[00130] Only the main reactants for the chemical formula of the compound to be synthesized are used. This will reduce the cost of the raw materials. The starting raw materials can be low cost. Technical grade materials can be used and if needed, purification can be done in-situ.
[00131] Total processing time is significantly less, about 1/5 to 1/2 of the processing times for the present industrial processes.
[00132] Special nanostructures are preformed from the complexcelle which are carried over to the final product thus enhancing the performance of the material in the desired application. For the purposes of the present invention nanostructures are defined as structures having an average size of 0.1 to 100 nm.
[00133] Neither surfactants nor emulsifiers are used. The initiation reaction occurs at the surface of the bubble interface. In fact, it is preferable that surfactants and emulsifiers are not used since they may inhibit drying.
[00134] Size control can be done by the size of the bubbles, concentration of the solutions, flow rate of the gas, transfer rate of second reactant into the first reactant.
[00135] No repetitive and cumbersome milling and classification steps are used.
[00136] Reduced calcination time can be achieved and repetitive calcinations are typically not required.
[00137] Reaction temperature is ambient. If need for solubilization, temperature is increased but preferably not more than 100 C.
[00138] Tailored physical properties of the powder such as surface area, porosity, tap density, and particle size can be carefully controlled by selecting the reaction conditions and the starting materials.
[00139] The process is easily scalable for large scale manufacturing using presently available equipment and/or innovations of the present industrial equipment.
EXAMPLES
PREPARATION OF COIN CELLS
[00140] The standard practice for coin cell testing has been used in all example and is described herein for reference. The material was made into electrodes in the same way and tested in an Arbin battery cycler (BT-2000) under the same cycling conditions of voltage and current. As such, side-by-side comparison of the battery cycling performances definitively exemplifies the advantages of the CPF methodology over current industrial production processes.
[00141] Electrodes were prepared by mixing 80 wt. % of active material, 10 wt. %of carbon black, and 10 wt.% PVDF (polyvinylideneflouride) in NMP (1-methyl-2 pyrrolidone). The resulting slurry was cast on aluminum foil and dried in a vacuum oven at 115 C for 24 h. CR2032-type coin cells were fabricated in an argon-filleglove box using lithium metal as the counter electrode. The cathode weight was around 4 mg per electrode. The electrolyte was a 1 M solution of LiPFs (lithium hexafluorophosphate) in a 1:1:1 volume mixture of EC: DMC: DEC (ethylene carbonate, dimethyl carbonate, and diethyl carbonate). The separator (Celgard 2400) was soaked in the electrolyte for 24 h prior to battery testing. Coin-cells were galvanostatically charged/discharged on the Arbin battery cycler at the stipulated current densities. Tests were done at ambient temperature. Both comparative example and the example coin cells were done at the same time under the same conditions.
EXAMPLES

[00142] Commercially available lithium cobalt oxide powder was obtained from Sigma Aldrich and characterized by field emission SEM (Figs. 8A arid 8B) and XRD
(Fig. 9) as well as by coin cell testing.
[00143] The scanning electron micrograph of this commercial LiCo02 in Figure 8A has a magnification of 2000 x and was taken as received. A second micrograph in Figure 8B
has a magnification of 25000 x. In Figure 8A, the particles are acicular and have several large agglomerates more than 10 microns that fused together during the calcination stage.
On higher magnification, layers of the particles are noted for some particles that were not fused but it is also shown that there are smooth areas from fusion of particles. This is often found in solid state processes which are a calcination of blended mixed solids of the reactants that combine by sintering at high temperature. It is expected that the particles so derived would be large in size and will need to be milled and classified to obtain the size distribution preferred.
[00144] The X-ray powder diffraction in Figure 9 shows a single phase crystalline LiCo02.
[00145] The capacity of this lithium cobalt oxide prepared commercially is shown in Fig. 14 together with Example 2 prepared by CPF.

[00146] Lithium cobalt oxide was prepared using a reactor vessel as shown in Fig. 4 with a mixer having an agitator blade as shown in Fig. 5. In one reactor, a weighed amount of lithium carbonate (46.2 grams, 99% purity) was added to the reactor containing one liter of deionized water. Carbon dioxide gas was allowed to flow through the reactor using a gas tube bubbler on the side or a diffuser bubbler at the bottom of the vessel. A
second reactor also equipped with a tube bubbler or a diffuser bubbler contained a weighed amount of cobalt carbonate (120.2 grams, 99% purity) and one liter of deionized water.
Carbon dioxide gas was allowed to flow through the bubblers. Ammonia, 250 ml,was added to the second reactor. After a given amount of time to allow dissolution or vigorous mixing of the corresponding reactants, the cobalt solution was pumped into the lithium solution at a rate of at least 1 L/h. Reaction temperature was ambient and gas flow maintained a sufficient amount of bubbles. The resulting mixture was passed through a spray dryer. The outlet temperature was 115 C. The dried powder was collected and placed in a sagger and fired in a box furnace in air for 5h at 900 C. Scanning electron micrographs (Figs. 10-12) and X-ray powder diffraction patterns (Fig. 13) were taken of the dried powder and the fired powder.
[00147] The slurry after mixing the reactants was placed on a glass surface to dry in air. The air-dried powder was analyzed by field emission SEM and the micrograph is shown in Figure 10. It is shown that there is some nanostructure already formed from the CPF methodology. The particles appear to align as staggered layers.
Primary particles are in the nanometer range as shown by several individual particles interspersed within.
[00148] In Figure 11A (10000 x) and 11B (25000x), the same nanostructure can be seen after spray drying the slurry mixture from the mixing step. The layering structure is very clearly shown in Figure 11B. That the nanostructure still remains after drying indicates that this formation is an advantage of the CPF process.
[00149] After the calcination step for 5h at 900 C, the layered nanostructure observed in Figures 10 and 11 still remains intact in the calcined powder as shown in the SEM micrograph in Figure 12 at 10000 x which consists of loosely bound layers of the particles allowing ease of Li migration within the structure during battery cycling.
Such flaky structure resembles a "nanocroissant" and has already been formed from the precursor feed to the spray dryer and thereon to the calciner.
[00150] Coin cells were prepared as described in the preparation of coin cells. The capacity of this lithium cobalt oxide prepared by the CPF methodology is shown in Fig.
14 plotted with the commercial sample in Example 1 for 500 cycles at C/20.
From the data, the commercial sample of Example 1 performed lower, as shown by the lower discharge capacity. Both powders decreased in capacity with increase in the number of cycles. However, the powder prepared by the CPF process exhibited higher capacity up to 400 cycles compared to the commercial sample of Example 1. At 300 cycles, thecapacity of the CPF powder of Example 2 was 110 mAh/g compared against the capacity of the commercial sample at 300 cycles which was 80 mAh/g. EXAMPLE 3 [00151] The powders in Examples 1 and 2 were refired at 900 C for another 5h. Coin cells were prepared as described. A comparison of the battery cycling tests is given in Figure 15 at 1C for 500 cycles.
[00152] In the battery cycling tests at a higher C rate of 1C, the lithium cobalt oxide powder from Example 2 that was refired again performed significantly better than the commercial powder that was also refired at the same temperature and for the same time period. The capacity of the commercial sample dropped from 120 mAh/g to 20 mAh/g after 200 cycles. The CPF sample had a capacity of 100 mAh/g after 300 cycles and 80 mAh/g at 400 cycles.
[00153] The scanning electron micrographs of the refired samples are shown in Figures 16 and 17 at the same magnification of 10000 x for comparison. While recalcination for another 5h has caused more fusion in both samples, it is noted that the commercial sample of lithium cobalt oxide has larger fused particles and the layers were also more fused together. The lithium cobalt sample prepared by this invention still retained much of the layered structure and the additional firing has not diminished battery performance significantly compared to the commercial sample.

[00154] The same procedure described in Example 2 was used in this example but with the added nickel and manganese compounds to illustrate the synthesis of multicomponent lithium oxides by the CPF methodology. The formulation made is Li1.2oNio.1sMno.5oCoo.1202 which is a high energy lithium nickel manganese cobalt oxide material for lithium ion batteries that would meet the electric vehicle performance standards.
[00155] Nickel hydroxide (16.8 grams, 99%) and cobalt carbonate (14.4 grams, 99.5%) were weighed out and placed in a reactor vessel described in Figure 4 equipped with a tube bubbler and an agitator as shown in Figure 5 already containing one liter of deionized water and 140 ml of acetic acid (99.7%). The solids were mixed at ambient temperature to obtain a solution of both metals. Manganese acetate (123.3 grams) was then weighed out and added to the same reaCtor. A similar reactor was also set-up to contain one liter of deionized water and lithium carbonate (44.7 grams, 99%). Carbon dioxide was bubbled through the gas bubbler. Ammonia, 100 ml,was added to the Li- containing reactor. The Co, Ni, Mn solution was then pumped into the Li-containing reactor at about 3.5 Llh at ambient temperature. Additional ammonia, 155 ml,was then added to the mixture to maintain pH of at least 9Ø The resulting mixture was then dried in a spray dryer. Inlet temperature was at 115 C. The Li-Co-Ni-Mn spray dried powder was then placed in a sagger and calcined at 900 C for 5h. The fired powder was very soft and was just crushed. No classification was done.
[00156] Scanning electron micrographs (Figs.18-20) and X-ray powder diffraction patterns (Fig. 21) were taken of the dried powder and the fired powder. Note that the SEM data in Figures 18A (2000 x) and 188 (10000 x) before spray drying and Figures 19A (5000 x) and 198 (10000 X) after spray drying show a "nanorose" or a "nanohydrangea" structure as the nanostructures formed by the layering of the particles look similar to these flowers. The particles form nanostructure layers at the mixing stage where the complexcelle nucleation begins and this same nanostructure is retained even after spray-drying. The calcined powder has discrete nanoparticles about 200-300 nm and some very loose agglomerates as shown in the SEM micrographs in Figures 20A (10000 x) and 20B (25000 x).
[00157] A crystalline lithium nickel manganese cobalt oxide was obtained in the X-ray powder diffraction pattern in Figure 21.
[00158] Coin cells were prepared as described in Example 1. The capacity of this lithium nickel cobalt manganese oxide prepared by the CPF methodology is shown in Figs. 22-24.
[00159] In Figure 22, the capacity of this lithium nickel manganese oxide was relatively constant at an average of 125 mAh/g for 500 cycles at a high C rate of 1C.
This is indicative of potential high performance in lithium ion batteries for electric vehicle applications. Capacity retention for as much as 500 cycles at 1C is excellent performance.
[00160] In Figure 23A, the battery performance for the same material was done in a temperature controlled chamber at 30 C and plotted showing different cycling rates from C/20 to 1C. As shown, the capacity decreases as the C rate increases. At C/20, the capacity was about 250 mAh/g and at 1C, about 150 mAh/g.
[00161] In Figure 23B, the Crates shown are C/10, C/3 and 1C for 5 cycles each.
Capacities were 240 mAh/g, 180 mAh/g and 150 mAh/g, respectively. The battery cycling tests were done at 30 C in a temperature controlled chamber.
[00162] In Figure 24A, the battery coin cells were placed in the temperature controlled chamber at 25 C. Cycling rates were taken from C/20 to 1C. The capacity at C/20 was almost 300 mAh/g. At 1 C, the capacity was at 180 mAh/g. This is attributed to a better controlled environment. The cycling data at 1C for 500 cycles is shown in Figure 24B.
Capacity was constant for 500 cycles at 1C rate at 25 C.

[00163] A cathode material, LMPas, such as LiFePO4, which is also preferably coated with an organic coating such as carbon to promote conductivity and may be doped or not, can be made by this CPF methodology. The iron source can be selected from divalent salts of iron.
The phosphate source can be H3PO4, ammonium phosphates, ammonium dihydrogen phosphates and the like. Iron is either a +2 or a +3 ion. The Fe+2 salt is preferred over the Fe#3 salt. The reactions must be done under inert atmosphere to prevent the oxidation of Fe+2 to Fe+3. A reducing atmosphere can also be used to reduce the Fe+3to Fe+2.
[00164] To illustrate the preparation of LiFePO4, an iron salt soluble in aqueous solvents like water is prepared in one reactor. Such salts can be iron oxalate, iron nitrate and others. Carbon dioxide gas can be introduced in the solution.
Phosphoric acid is also added to the solution. In a second reactor, a lithium salt such as lithium carbonate, lithium hydroxide and the like is dissolved in water under carbon dioxide gas. The iron phosphate solution in reactor 1 is then slowly transferred into the lithium solution in the second reactor. Ammonia solution may be introduced simultaneously as the iron solution or at the end of the transfer of the iron solution. The slurry solution is then dried using a spray dryer and the spray dried powder is calcined under inert atmosphere to obtain LiFePO4. If a dopant is added from selected metals, this dopant solution must be dissolved in any reactor. The carbon coating can be attained by adding a carbon material to obtain not more than a 10 wt.% carbon in the product.
[00165] Other types of phosphate compounds such as calcium phosphate may be made in a similar way to obtain a calcium phosphate nanopowder that can be used for bone implants and other medical applications as well as dental applications.
[00166] The invention has been described with reference to the preferred embodiments without limit thereto. One of skill in the art would realize additional embodiments and improvements which are not specifically set forth herein but which are within the scope-of the invention as more specifically set forth in the claims appended hereto.

Claims (35)

Claimed is:

1. A method of forming a powder MjXp wherein Mj is a positive ion or several positive ions selected from the group consisting of alkali metal, alkaline earth metal and transition metal; and Xp is a monoatomic or a polyatomic anion selected from Groups consisting of IIIA, IVA, VA, VIA
and VIIA; called complexometric precursor formulation or CPF, comprising:
providing a first reactor vessel with a first gas diffuser and an first agitator; providing a second reactor vessel with a second gas diffuser and a second agitator;
charging said first reactor vessel with a first solution comprising first salt of Mj; introducing gas into said first solution through said first gas diffuser, charging said second reactor vessel with a second solution comprising a salt of Xp;
adding said second solution and said first solution to form a complexcelle; drying said complexcelle, to obtain a dry powder; and calcining said dried powder of said MjXp.

2. The method of forming a powder of claim 1 wherein at least one of said first diffusor or said second diffuser is selected from the group consisting of a porous ceramic, a tube, a membrane and a dome diffuser.

3. The method of forming a powder of claim 1 further comprising adjusting a final pH of at least one of said first solution, said second solution or said complexcelle.

4. The method of forming a powder of claim 1 wherein said gas is introduced into said first solution at a rate sufficient to increases a volume of said first solution by at least 5%.

5. The method of forming a powder of claim 1 wherein said gas is introduced into said first solution at a rate of at least one liter of said gas per liter of said first solution per minute.

6. The method of forming a powder of claim 1 wherein at least one of said first agitator or said second agitator comprises concentric wires.

7. The method of forming a powder of claim 1 wherein at least one of said first agitator or said second agitator comprises at least one blade.

8. The method of forming a powder of claim 7 wherein at least one said blade rotates on a shaft and on a blade axis.

9. The method of forming a powder of claim 1 wherein at least one of said first agitator or said second agitator has a mixing speed of at least 100 rpm.

10. The method of forming a powder of claim 1 wherein said gas comprises a gas selected from the group consisting of air, carbon dioxide, methane, SF6, HF, HCI, NH3, propane, 02 and inert gas.

11. The method of forming a powder of claim 1 comprising a salt of said Mj wherein said salt is selected from the group consisting of chlorides, hydroxides, nitrates, phosphates, oxalates, carbonates, acetates, sulfates, hydroxycarbonates, hydroxyl phosphates, hydroxysilicates, and silicates.

12. The method of forming a powder of claim 1 wherein said first solution comprises up to 30 wt.% of said first salt of Mj.

13. The method of forming a powder of claim 1 wherein said second solution comprises up to 30 wt.% of said second salt of Xp.

14. The method of forming a powder of claim 1 wherein said powder of said MjXP is selected from the group consisting of lithium metal oxides, calcium phosphates, lithium aluminosilicates, lithium aluminates and lithium metal phosphates.

15. The method of forming a powder of claim 1 wherein said powder further comprises a dopant.

16. The method of forming a powder of claim 15 wherein said dopant is selected from the group consisting of alkali or alkaline earth metals, Group III A
elements, Group IV A elements and transition metals.

17. The method of forming a powder of claim 15 wherein said dopant is selected from the group consisting of cobalt, aluminum and gadolinium.

18. The method of forming a powder of claim 15 wherein said dopant is present in an amount of up to 10 weight % of said lithium metal oxide.

19. The method of forming a powder of claim 1 further comprising applying a coating to said powder.

20. The method of forming a powder of claim 19 wherein said coating is an organic compound.

21. The method of forming a powder of claim 19 wherein said coating comprises carbon.

22. The method of forming a powder of claim 1 wherein said powder of said MjXp is selected from the group consisting of lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, and lithium mixed oxides of cobalt, nickel and manganese.

23. The method of forming a powder of claim 1 wherein said forming said complexcelle is at a temperature of no more than 100°C.

24. The method of forming a powder of claim 1 wherein said drying is at a temperature of no more than 350°C.

25. The method of forming a powder of claim 1 wherein said drying is done by a method selected from the group consisting of spray drying, freeze drying, tray drying and evaporation drying.

26. The method of forming a powder of claim 1 wherein said calcining is in an apparatus selected from the group consisting of a box furnace, a rotary calciner, a fluidized bed calciner and a spray pyrolyzer.

27. The method of forming a powder of claim 1 wherein said calcining is at a temperature of from 350-3000°C.

28. The method of forming a powder of claim 1 wherein said powder has a particle size of less than 1 micron.

29. The method of forming a powder of claim 1 wherein said powder has a surface area of more than 1 m2/gm.

30. The method of forming a powder of claim 1 wherein said adding said second solution to said first solution is through a tube.

31. The method of forming a powder of claim 30 wherein said tube has an inner diameter of at least 2 mm.

32. The method of forming a powder of claim 30 wherein said tube further comprises at least one of an atomizer, sprinkler or nozzle.

33. The method of forming a powder in Claim 1, wherein said powder has a microstructure or a nanostructure.

34. The method of Claim 33, wherein the nanostructure is a nanocroissant, nanorose or a nanohydrangea.

35. A method of forming a powder MjXp wherein Mj is a positive ion or several positive ions selected from the group consisting of an alkali metal, an alkaline earth metal and a transition metal;

-and Xp is a monoatomic or a polyatomic anion selected from the Groups consisting of IIIA, IVA, VA, VIA or VIIA; called complexometric precursor formulation or CPF, comprising:
providing a first reactor vessel with a first gas diffuser and a first agitator;
providing a second reactor vessel with a second gas diffuser and a second agitator;
charging said first reactor vessel with a first solution comprising first salt of Xp;
introducing gas into said first solution through said first gas diffuser, charging said second reactor vessel with a second solution comprising a salt of Mj;
adding said second solution and said first solution to form a complexcelle;
drying said complexcelle, to obtain a dry powder; and calcining said dried powder of said MjXp.