NZ526971A - Stabilized spinel battery cathode material and methods - Google Patents

Stabilized spinel battery cathode material and methods

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Publication number
NZ526971A
NZ526971A NZ526971A NZ52697102A NZ526971A NZ 526971 A NZ526971 A NZ 526971A NZ 526971 A NZ526971 A NZ 526971A NZ 52697102 A NZ52697102 A NZ 52697102A NZ 526971 A NZ526971 A NZ 526971A
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New Zealand
Prior art keywords
spinel
particles
lithium
metal oxide
particulate
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NZ526971A
Inventor
Wilmont F Howard
Stephen W Sheargold
Phillip M Story
Robert L Peterson
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Kerr Mcgee Chemical Llc
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Publication of NZ526971A publication Critical patent/NZ526971A/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Secondary Cells (AREA)

Abstract

Improved stabilized spinel battery cathode material and methods of treating particles of spinel battery cathode material to produce a protective coating of battery-inactive lithium metal oxide on the particles are provided. The methods basically comprise mixing the spinel particles with a particulate reactant selected from a lithium salt, a lithium metal oxide or a mixture of a lithium salt and a metal oxide and then heating the resultant particulate mixture for a time and temperature to react the particulate reactant with the spinel particles whereby a protective coating of lithium metal oxide is formed on the spinel particles and the lithium content of the spinel adjacent to the coating is increased a limited amount.

Description

06/27/2003 15:58 FAI 405 270 3030 526971 KERR MCGEE INTELLECTUAL PROPERTY OfFSCE OF N.Z. 2 4 DEC 2004 RECEIVED BXPttESS MATL fJVBEL NO. EL 728 721608 EES Case 1076 STABILIZED SPINEL BATTERY CATHODE MATERIAL AND METHODS This invention relates to stabilized lithium manganese oxide spinel battery cathode material, and to improved methods of stabilizing the spinel against add attack and the like.
Recently, there has been increased interest in using lithium manganese oxide having the formula Ui+xMfl2-x04 (0.02 < x < 0.15, unless stated otherwise), referred to 15 in the art as spinel or 1MO, as a cathode material in lithium-ion batteries. The advantages of using spinel instead of the mote commonly used alternatives, that is , LiCoOz or Li(Co, Ni)Q?, are well known. For example, spinel is less expensive, environmentally friendly and considerably safer during operation than the alternative materials. However, the use of spinel as battery cathode material has major 20 drawbacks, that is, the spinel exhibits a rapid loss in capacity when cycled or stored at temperatures above 45°C and mineral acid impurities in batteries degrade the spinel and reduce its performance.
A variety of solutions to the problem of the rapid loss in capacity of spinel above 45 °C have been proposed by those skilled in the ait The solutions include the 25 incorporation of additional lithium into the spinel lattice to form spinel of the formula l4i*xMn2«04 or substituting fluoride for some of the oxygen to yield spinel having die formula lii4.jMn24O4.2Fz (see Amatucci et al., U.S. Patent No* 5,674,645 and Sugiyama et al., U.S. Patent No. 6,087,042). Another solution involves replacing a fraction of the Mn with a stabilizing metal (M) such as Cr, Ni, Co, Al and the like to 30 form Iii+xMyMni.x-y04 (Dahn et al., U.S. Patent No. 5,900,385) wherein x is greater than 0 but less than 1 and y is less than or equal to 1.
Another proposed solution involves the formation of a protective coating on the particles of spinel to prevent corrosion or dissolution of the spinel. The formation of a protective coating on spinel is disclosed in U.S. Patent No. 5,443,929 issued to UT76 hw App fcr Xfiifrdoc fax26052.tif 28/06/03 07:58 06/27/2003 15:58 FAX 405 270 3030 KERR HCGEG @004 2 Yamamoto et al. on August 22,1995 wherein a lithium-deficient spinel (Ui-wMnjO*) encapsulated by lithium manganite (LigMiiCta) is disclosed. In accordance with the teachings of the patent, liOH powder is added to stoichiometric spinel at various ratios from 0.02:1 to 12:1 and the mixture is heated in air at 200°C to lOOCPC, preferably at 375"C, for 20 hours. The final product is a dual phase material that has acid resistance and enhanced stability during high temperature battery operation, but it suffers from the disadvantage that the maximum capacity is substantially reduced.
U-S. Patent No. 5,733,685 issued to Wang on March 31, 1998 and U.S. Patent No. 5,783,328 also issued to Wang on July 21. 1998 disclose that improved spinel cathode material stability is obtained by protecting the spinel particles with a thin layer of lithium carbonate (LfcCQs)- The coating is accomplished by combining a solution of LiOH with spinel having die formula Lii+xMna.,^ wherein x is greater or equal to 0 and less than or equal to 0.1. After the mixture is dried, it is heated to a temperature of from 270°C to 300°C for 20 hours in the presence of carbon dioxide. While the resulting layer of IJ2CO3 on the spinel makes it more robust than unprotected spinels at temperatures above 45°C, the coated spinel tends to out-gas during battery use which causes the batfceiy case to swell or vent, etc.
U.S. Patent No. 5,705,291 issued to Amatucci et al. on January 6, 1998 discloses that a glassy coating of LiOH mixed with B2Q3 and other additives retards spinel capacity loss, and U.S. Patent No. 6,022,641 issued to Endo et al. on February 8,2000 discloses the benefits of mixing L12CO3 or NajGOa with spinel in an amount of from 0.5% to 20% by weight of the spinel to improve cycle performance. Further, Oesten et al. (WO 00/70694 - November 23, 2000) protect all lithium metal oxide cathode materials by coaling the active particles with an organometallic species and then pyrolyzdng to leave a metal oxide outer layer.
It is also possible to coat lithium manganese oxide spinels with other battery-active cathode materials having the general formula LiMO* wherein M is a transition metal (Iguchi et al., Japanese Kbkai HEX 8[1996] - 162114 and Hwang et al., U.S. Patent No. 5,928,622). In this approach, thermally decomposable Li and M salts (or oxides) in the appropriate Li:M ratio are blended with the spinel and reacted at temperatures up to 750°C. This results in particles of the original spinel having an acid resistant LiMO^-rich outer shell. fax26052.tif 28/06/03 07:58 3 The surface treatments of spinel battery cathode material of the types described above inevitably result in a decrease of the maximum reversible discharge capacity of the spinel. In addition to lowered capacity caused by the added mass of electrochemically inert species, Gummow et al. in Solid State Ionics. 69, 59 (1994) 5 showed that the inclusion of non-stoichiometric Li in Lii+xMn2-xC>4 will decrease the discharge capacity of the resulting material by a factor of (l-3x). The advantage of such treatments is that they slow the loss of discharge capacity (referred to in the art as fade) during repeated charge/discharge cycles. The battery industry's measure of useful battery life dictates battery replacement when the battery has lost 20% of its 10 initial discharge capacity. The protective coatings extend the number of useful cycles that the spinel cathode material can provide, but as mentioned, the maximum reversible discharge capacity of the spinel is significantly decreased.
The prior art discloses providing spinel battery cathode material with a coating of an 15 acid resistant or acid-scavenging compound. Mineral acids present as impurities in lithium ion batteries attack Lii+xMn2-x04 spinel cathode material extracting lithium and up to 25% of the manganese leaving the spinel unable to perform satisfactorily. The impurity acids are generated in lithium-ion batteries by the hydrolysis of LiPF6 electrolyte salt, by trace moisture or by the oxidation of organic carbonate electrolyte 20 solvents at the high voltage end of the battery cycle. While the protection afforded by the above described prior art coatings prevent or reduce the problems associated with acid attack at temperatures below 45°C in batteries for mobile devices such as cell phones, laptop computers, photographic equipment and the like, the prior art coatings significantly reduce the maximum reversible discharge capacity of the spinel cathode 25 material.
The above discussion of background art is included to explain the context of the present invention. It is not to be taken as an admission that any of the documents or other material referred to was published, known or part of the common general 30 knowledge at the priority date of any one of the claims of this specification.
The present invention provides improved stabilized particulate Lii+xMn2-x04 spinel battery cathode material and methods of treating particles of Lii+xMn2-x04 spinel to produce a protective coating of a battery inactive, ceramic-like lithium metal oxide on the particles. The coating resists acid attack, substantially improves the capacity fade of the material and reduces the maximum discharge capacity of the material only minimally.
The methods of the invention are basically comprised of the following steps. The spinel particles are mixed with a particulate reactant selected from a lithium salt, 06/27/2003 15:59 FAX 405 270 3030 KERR MCGEE @006 4 a lithium metal oxide or a mixture of a lithium salt and a metal oxide. Tb aeafter, the resulting particulate mixture is heated for a time in the range of from 15 in inutes to 20 hours at a temperature in the range of from 350°C to 850°C, During the 1 eating step, the particulate lithium salt, lithium metal oxide or mixture of the lithium salt and a metal oxide reacts with the spinel particles whereby a protective coating of battery-inactive lithium metal oxide is formed on the spinel particles and the lith um content of the spinel particles adjacent to the coating is increased a limited amount as represented by the formula Ui+xMn2.x04 wherein x is less than 0.2.
The coated spinel particles are preferably cooled to a temperituie below 200°C in a time period in the range of from 10 to 120 minutes. Thereafte r, the spinel particles are cleaned and sized by removing agglomerates and metallic pa tides while passing the particles through a magnetic trap and 150 mesh or smaller sere ins.
The untreated Lii+xMn2.x04 spinel used in the method described a >ove can be of any desired particle size and there are no restrictions on the lithium oi manganese content or crystal lattice size. Preferably, the spinel particles have an aver ige size less than 35 microns and substantially all of the particles pass through a 200 m ssh screen.
Examples of the lithium salts that can be utilized for forming the coating on the spinel include, but are not limited to, lithium carbonate, lithium hydro) ide, lithium nitrate, lithium salts of organic acids such as lithium acetate, lithium brmate and lithium oxalate, and mixtures of such lithium salts. Of these, lithium carbonate is preferred. Examples of lithium metal oxides that can be utilized include, but are not limited to, LiaMnCb, LiSc02, LiYO* Ii2Zr03, IizHfOa, IiAlOa, LiAlsOg, LiGaOz, LiLa02, I^SiOj, LuSi04, Li2Ge03 and mixtures thereof. Examples of metal oxides that can be utilized include, but are not limited to SC2O3, Y2O3, ZrQfe. IffCh, AI2O3, Ga^Oj, IA2O3, SiOfe GeOj and mixtures thereof.
The lithium salt utilized generally has an average particle size of less than 10 microns and substantially all of the lithium salt particles pass through a 150 mesh screen. The lithium metal oxides utilized generally have an average parti cle size less than 5 microns, and preferably less than 1 micron. The lithium salt, lithium metal oxide or mixture of lithium salt and metal oxide utilized is mixed with the spinel particles in an amount which is less than or equal to 2.5 mole percent of the spinel particles in the mixture. To guard against destructive out-gassing, residu al carbonate fax26052.tif 28/06/03 07:58 06/27/2003 15:59 FAX 405 270 3030 KERR HCGEE @007 in the protective coaling should be limited to at least less than 0.05% fay wpight of the spinel product As will be understood by those skilled in the art, other species of liirium salts, lithium metal oxides and metal oxides can be utilized which have diffe ent atomic ratios from those set forth above. Also, two or more metal oxides or lithium metal oxides can be utilized.
The spinel particles and the lithium salt, lithium metal oxide or mixture of lithium salt and metal oxide particulate reactant(s) utilized are preferably mixed in a high intensity, low shear Tnill such as a vibratory ball mill, a vibratory rot mill or the equivalent which does not reduce the size of the spinel particles. It is un desirable to reduce the spinel particle size during the mixing step in the presence of th< ■ particulate reactant(s) used in that the size reduction which takes place cannot be controlled. Preferably, the mixing of the spinel particles and particulate reactant(s) in performed in a high intensity, low shear ball mill charged with cylindrical ceramic media. The spinel particles and particulate reactant(s) utilized are preferably mixe^ for a time period, including discharging the mixture, which does not exceed 75 minui The heating of the mixture of spinel particles and the particulate reactant(s) utilized can be carried out in a batch mode. That is, the particulate mb ture can be placed in an inert container formed of stainless steel, densified ceramic or the like and heated in a box oven, a belt or pusher furnace or the like. Air is flowed through the reaction chamber to remove moisture, CO2 and other gases while ma ntaining an oxidizing atmosphere. Due to the insulating properties of the ieactant 1 owders, the particulate mixture should be heated to above 575°C as shown in Table will be understood, deeper ieactant beds will require higher heating temperatures while shallower beds require lower temperatures. A preferred bed deptt is less than 5 centimeters (2 inches). At depths above about 5 centimeters, there is a risk that the product will be over-reacted (little Qr no protective coating) at the top p< nrtion of the bed and under-reacted (residual lithium salt) at the bottom portion of the led. Such a non-homogenous product may be susceptible to excessive capacity fate and out-gassing during battery operation. Generally, the reaction time is in the n nge of from 15 minutes to 20 hours, preferably less than 2 hours. below. As fax26052.tif 28/06/03 07:58 08/27/2003 16:00 FAX 405 270 3030 KERR MCGEE @008 6 Preferably, the heating of the mixture of spinel particles and the particulate ieactant(s) utilized is carried out in a rotary calciner with a countercum nt air flow passing through the calciner during the healing to remove residual moist are, carbon dioxide gas and the like. As mentioned above, the particulate mixture Is I leated for a 5 time in the range of from IS minutes to 20 hours, preferably for a time of from 30 minutes to 45 minutes, at a temperature in the range of from 350°C to S50°C, preferably in the range of from 5S0°C to 650°C. During the time that thi>mixture is heated at the above-mentioned temperature, the particulate reactant(s) cc mbme with each other and with the spinel particles whereby protective coatings of li hium metal 10 oxide are formed on the spinel particles. Simultaneously, die lithium cc itent of the surface layers of the spinel particles adjacent to the coatings are incre: sed limited amounts as represented by the formula Lii+xMn^sAi wherein x is less thi in 0.2. The bulk of each particle has a lower litfaium content, that is, a lithium contest t wherein x is less than 0.15.
Lithium manganite (I^MnCb) is the most thermodynamically st Lble lithium manganese oxide compound and will withstand being heated to a temperature of 1000°C without decomposition. However, lithium manganite will react with manganese (HI) compounds such as and UMn(UI)Mn(IV)04 at t imperatives above 300°C. Reaction (1) below is an iterative step in the commercial pi eparation of 20 spinel, while reaction (2) describes the fate of the coating of lithium n anganite on spinel. 2U2Mn03+3Mn203+0.502 —*■ 4UM112O4 (1' 1 yLi2MnC>3+LiMn204 —* Lii+zyMnzt-yO^y+^^Oz (21 The product of reaction (2) is equivalent to 01^^^)4+5, or alternately, 25 Lii+JtMn2-x04 if y is less than approximately 0.1. Otherwise, high Li cant int will lead to tetragonally distorted material that will have poor cycling characte istics. The above reaction shows that a lithium manganite (LijMhOs) coating vill at least partially react with spinel above a temperature of 300°C and produc; a lithium-enriched spinel. The longer the treatment time and/or the higher the treatment 30 temperature, the more lithium migration will take place to form particle: of uniform composition, rather than particles with just a surface portion enriched in lj thium. fax26052.tif 28/06/03 07:58 06/27/2003 16:00 FAI 405 270 3030 KERR MCGEE @009 The above is confirmed by an analysis of X-ray diffraction data which allows the quantification of die lithium manganite coating formed on spinel. That is, samples of mixtures of spinel particles with particulate lithium carbonate were calcined at different temperatures and times. The calcining at or below 575°C for 45 minutes did not produce any detectable lithium manganite coating as shown in Table I below. Table I also shows the percent lithium manganite determined by X-ray diffraction Rietveld analysis at various higher temperatures and reaction times.
TABLEI Reaction Reaction Percent LiaMnOj by Temperature, °C Time, minutes X-ray Diffraction Analysis 575 45 0.0 600 45 0.74 €00 60 0.77 600 75 0.73 625 1.20 625 45 0,92 625 60 0.97 625 75 0.82 As shown in Table I, when the coating treatment was performed at 600°C, approximately 0.75% lithium manganite was formed on the spinel independent of whether the spinel was heated for 45 minutes or 75 minutes. At 625°C, 1.2% lithium manganite was formed after heating for only 30 minutes. That percentage was reduced upon continued heating and the spinel diffraction pattern shifted to greater 15 scattering angle (26), indicating a decrease in the lattice constant as a result of lithium manganite reacting to form a lithium-rich spinel. The spinel lattice constant of li1.ff7Mn1.93O4 typically shrinks from approximately 8.227 Angstroms to 8.218-8223 Angstroms during the treatment The above described treatments were carried out in a static oven. Similar results from treatments carried out in a rotary kiln were 20 obtained at temperatures 20°C to 50°C lower.
Referring to HG. 1, a graph is presented showing the decrease in lattice constant of the treated spinel as a function of reaction time and temperature. As the lithium manganite reacts with the spinel and lithium diffuses through the spinel particles, the lattice constant of the particles shrinks. The rate of lattice gKrinlragy* is a 25 function of the temperature since lithium will diffuse more rapidly as the temperature fax26052.tif 28/06/03 07:58 06/27/2003 16:01 FAX 405 270 3030 KERR MCGEE @010 increases. If lithium manganite and spinel were mixed at the molecular level, there would be no time factor in the lattice contraction. Further, the lithium diffusion kinetics allows a temperature and a time period to be selected that will optimize the economics of the treatment As illustrated in FIG. 1, it is possible to perform the 5 treatment at 300°C, but the preparation time required for a viable product would be very expensive. Alternately, if the temperature exceeds 625°C, lithium diffusion can proceed too rapidly to control and the product as a consequence can be less than optimuin- The above discussion concerning lithium manganite protective coatings holds 10 true for any other lithium metal oxide that is battery-inactive, that is, the metal cannot be further oxidized at a voltage below 4.5 volts. If a coating is placed on the spinel particles that is battery-active, lithium will be extracted and reinserted during normal battery operation and the resulting contraction and expansion will cause the coating to loosen and crack, thereby negating its effectiveness as an acid barrier. The battery-15 inactive lithium metal oxide coatings formed on the spinel particles in accordance with this invention are typically ceramic in character and resist dissolution by acid under normal conditions. Thus, the protective coatings of this invention remain on the spinel particles during battery operation and storage even at elevated temperatures.
Thus, a potential drawback of the treatment method of this invention is that 20 there can be a significant loss in maximum capacity when excessive lithium is added to the spinel, specifically when x in the formula Lil+xMn2^04 is greater than 0.2. Accordingly, it is of great importance in accordance with the present invention that an encapsulating protective layer of battery-inactive lithium metal oxide is added to the spinel particles. Too much lithium added to the spinel will cause excessive formation 23 of ceramic-like lithium metal oxide resulting in poor lithium mobility and unacceptable battery performance. If the lithium metal oxide and spinel are allowed to react for an overly-long period of time, the spinel structure will distort and cathodic stability and performance will be diminished.
Even when an appropriate amount of lithium is added to the spinel, the 30 reaction period may be too lengthy or too hot, allowing lithium to diffuse into the interior of the spinel particles thereby losing the coating effect. Spinel treated in a manner where the coating effect is lost will have lattice constants reduced by 0.01 to fax26052.tif 28/06/03 07:58 M/27/2003 16:01 FAX 405 270 3030 KERR MCGEE Don 0-02 Angstroms, and will exhibit a redaction of 10 to 25 percent in reversible discharge capacity. While the capacity fade will be approximately 0.05% per cycle which is a vety desirable value, (be initial capacity will be less than optimum. Further, if the treatment temperature exceeds approximately 920°C, there will be an 5 irreversible phase change to the unacceptable tetragonal structure which exhibits very poor cathode performance. Lastly, if the temperature reduction after beating is too abrupt, the spinel oxygen deficiency caused by the treatment will not be reversed. Oxygen-deficient spinel species are inferior cathode materials to spinels with correct oxygen stoichiometry. In addition to managing the heating of the particulate mixture 10 of spinel and lithium salt, the cooling of the heated and reacted particulate mixture to a temperature below 200°C should be carried out in a time period in the range of from 10 to 60 minutes, preferably in less than 25 minutes.
After the treated spinel particles are cooled, the particles are cleaned and sized. That is, because the lithium salt utilized may cause flaking (spoiling) of the iron 15 containing alloy that forms the calciner, iron-containing metallic particles will generally be present in the product. In addition, the lithium salts may cause minor agglomeration of the particulate product In order to remove the particles containing iron and oversized particles from the treated product, the treated product particles are subjected to magnetic separation such as by causing the product particles to flow 20 through a column containing multiple magnets which remove the particles containing iron from the particulate producL In addition, the particulate product is caused to pass through a 150 mesh or smaller screen.
A preferred method of this invention of treating particles of spinel having the formula Li i+xMn2.x04(0.02 < x < 0.15) to produce a protective coating of battery-25 inactive lithium metal oxide on the particles is comprised of the following steps: (a) mixing the spinel particles with a particulate ieactant selected from a lithium salt, a lithium metal oxide or a mixture of a lithium salt and a metal oxide; and (b) heating the resulting particulate mixture for a time in the range of 30 from 15 minutes to 20 hours at a temperature in the range of from 350°C to 850°C to thereby react the spinel particles with the ieactant whereby protective coatings of battery-inactive lithium metal oxide axe formed on die spinel particles and the lithium fax26052.tif 28/06/03 07:58 contents of fee spinel particles adjacent to die coatings are increased limited to amounts as represented by flue formula Lii+xMn^CU wherein x is less than 0.2.
Another preferred method of this invention of treating particles of spinel having the fonniila lii+xMit-xOa (0.02 < x < 0.15) to produce a protective coating of batteiy-iti active lithium metal oxide on die particles is comprised of the following steps: (a) mixing the spinel particles with a particulate ieactant selected from a lithium salt, a lithium, metal oxide or a mixture of a lithium salt and a metal oxide in a high intensity, low shear mixer; (b) heating die resulting particulate mixture for a time in the range of from 15 minutes to 20 hours at a temperature in the range of from 350°C to 850°C to thereby react the spinel particles with the reactant whereby protective coatings of battery-inactive lithium metal oxide are formed on the spinel particles and the lithium contents of the spinel particles adjacent to the coatings are increased limited to amounts as represented by the formula Iii+xMnj.xO* wherein x is less than 0.2; (c) cooling the resulting heated and reacted particulate mixture to a temperature below 200°C in a time period in the range of from 10 to 120 minutes; and (d) cleaning and sizing the resulting reacted and cooled particulate mixture by removing metallic particles from said mixture and removing oversize particles by passing said mixture through a 150 mesh or smaller screen.
In order to further illustrate the stabilized spinel battery cathode material and methods of this invention, the following examples are given.
Example 1 Electrolytic manganese dioxide (EMD) of two different particle sizes were converted to lithium manganite (IJaMnOs) by reacting equimolar amounts of lithium carbonate and the EMD at 650°C. The two resultant lithium manganite lots had 0.9 micron and 3.8 microns mean panicle sizes, respectively, designated as fine and super-fine Li2MhOj, respectively. Each lot was separately mixed with spinel having the formula Li1.07Mn1.93O4 from a commercial lot at two addition levels of 1.5% by weight of the mixture and 2.37% by weight of the mixture, respectively. Hie mixtures were each incorporated into a battery cathode and cycle tested in a laboratory coin cell battery. The results of these tests are set forth in Table n below 86/27/2003 16:02 FAX 405 270 3030 KERR HC6EE @013 11 as Tests Nos. 3 and 4. As shown, no improvement ova the starting spinel material (Test No. 1 in Table H) was noted.
Example 2 Test portions of the mixtures from Example 1 woe heated to 575°C for 30 5 minutes. X-ray diffraction analysis of the spinel products revealed a modest decrease in the spinel crystal lattice constant, indicating a migration of lithium from the lithium manganite into the spinel. The resulting products comprised of spinel particles coated with lithium manganite are listed in Tests Nos. 5 - 8 set forth in Table n below. The lithium manganite content was determined by Rietveld analysis of XRD diffraction 10 scans.
TABLE II Test LiiMnOj Maximum Fade Rate, No.
Description of Cathode Material Content, % Discharge %/cycle by XRD 1 Precursor spinel liunMni,9}04 0 123.8 -0.147 2 Spinel treated with L5% JU2CO3 1.2 114.8 -0.11 a Spinel mixed with 1-5% super-fine Li^MnOj 2.4 122-6 •0.16 4 Spinel mixed with 2.37% super-fine Li2MnQj 7A 123.3 -0,175 Spinel treated with 1-5% super-fine Li^MnOj OSi 115.9 -0.08 6 Spinel treated with 2.37% super-fine LijMnQi 23 - 114.2 -0.12 7 Spinel treated with 1-5% fine Li2MnQ3 2.0 121.7 -0.12 8 Spinel treated with 237% fine liaMnOj 2.6 118.3 -0.12 The electrochemical test results given in Table II above were obtained by incorporating the test materials given in Table H into battery cathodes and cycle 15 testing the cathodes in laboratory coin cell batteries at 55°C. The maximum discharge capacities of the cathodes and fade rates during charge/discharge cycling axe given in Table IL As shown in Table U, when lithium manganite (LfcMnCb) having an average particle size of 0.9 microns was the lithium source (Tests Nos. 5 and 6), the maximum discbarge capacity was 8% to 10% less than that of the precursor spinel 20 having the formula li1.07Mn1.93O4 (Test No. 1), while fade rates improved 15% to 40%. When the lithium manganite having a particle size of 3.8 microns was used (Tests Nos. 7 and 8), approximately 5% capacity loss and 15% fade rate improvement were observed. This particle size effect is consistent with the poor mobility of lithium manganite, even at elevated temperatures. The physical mixtures of spinel and fax26052.tif 28/06/03 07:58 06/27/2003 16:02 FAX 405 270 3030 KPIRP MCGEE 12 lithium manganite (Tests Nos. 3 and 4) showed no measurable improvement over die precursor spinel alone (Test No. 1).
Example 3 27.52 grams of L12CO3,100 grams of Mr^Oj and 7.04 grams of AI2O3 were 5 mixed together and calcined at 750°C for 16.7 hours. The resulting calcined mixture was cooled, re-mixed in a blender and re-calcined at 750°C for 16.7 hours. X-ray diffraction analysis revealed a LiMn204 spinel pattern with a lattice constant of 8.207 A and with small peaks from LiAl5Og spinel. Hie produced cathode material calculated as lii.owAlaissMni/rsgO* was cycle tested in a laboratory coin cell battery 10 at 55°C. The maximum discharge capacity of the cathode material was 109 mAh/g and the fade rate was 0.058% per cycle. It is believed that the immobile LiAlsOg is a surface species on the LMO spinel particles. Similarly prepared LiAJo^Mni gOj cathode material exhibited a lattice constant of 8.227 A and an unacceptable capacity of only 55 mAh/g, Extensive AI2O3 was detected in the sample. fax26052.tif 28/06/03 07:58

Claims (14)

13 The claims defining the invention are as follows:
1. A method of treating particles of spinel having the formula Lii+xMn2-x04 (0.02 < x< 0.15) to produce a protective coating of battery-inactive 5 lithium metal oxide on the particles, including the steps of: (a) mixing said spinel particles with a particulate reactant selected from the group consisting of a lithium salt, a lithium metal oxide and a mixture of a lithium salt and a metal oxide; and (b) heating the resulting particulate mixture for a time in the range of 10 from 15 minutes to 20 hours at a temperature in the range from 350°C to 850°C to thereby react said spinel particles with said reactant to form treated spinel particles whereby protective coatings of battery-inactive lithium metal oxide are formed on said spinel particles and the lithium contents of said spinel particles adjacent to said coatings are increased limited to amounts as represented by the formula Lii+xMn2-x04 15 wherein x is less than 0.2.
2. The method of claim 1 wherein a particulate lithium salt reactant is employed and is selected from the group consisting of lithium carbonate, lithium hydroxide, lithium nitrate, lithium salts of organic acids and mixtures thereof. 20 25
3. The method of claim 1 wherein a particulate lithium metal oxide reactant is used and is selected from the group consisting of Li2Mn03, LiScCh, LiYC>2, Li2ZrC>3, Li2Hf£)3, UAIO2, LiAlsOg, LiGaC>2, LiLaC>2, Li2Si03, Li4Si04, Li2GeC>3 and mixtures thereof.
4. The method of claim 1 wherein a particulate metal oxide reactant is used and is selected from the group consisting of SC2O3, Y2O3, ZrC>2, Hf02, AhC^, Ga2C>3, La2C>3, SiC>2, GeC>3 and mixtures thereof. 30
5. The method of any of claims 1 through 4, wherein said particulate reactant is mixed with said spinel particles in an amount which is less than or equal to 2.5 mole percent of said spinel particles in said mixture. 14
6. The method of claim 2 wherein said particulate lithium salt reactant has an average particle size less than 10 microns and substantially all of the particles pass through a 150 mesh screen. 5
7. The method of claim 3 or claim 4 wherein said lithium metal oxide or said metal oxide reactant, respectively, have an average particle size of less than 5 microns.
8. The method of any of claims 1 through 7 wherein said spinel 10 particles have an average size of less than 35 microns and substantially all of said particles pass through a 200 mesh screen.
9. The method of any of claims 1 through 8, wherein said spinal particles and said particulate reactant are mixed in accordance with step (a) in a high 15 intensity, low shear vibratory ball mill or the equivalent which does not reduce the size of said spinel particles.
10. The method of claim 9 wherein said spinel particles and particulate reactant are mixed for a time period including discharging the mixture which does 20 not exceed 75 minutes.
11. The method of any of claims 1 through 10 which further includes the step of cooling said treated spinel particles to a temperature below 200°C in a time period in the range of from 10 to 120 minutes. 25 30
12. The method of claim 11 which further includes the steps of cleaning and sizing said treated spinel particles which have been cooled by removing metallic particles from said mixture and removing oversize particles by passing said mixture through a 150 mesh or smaller screen.
13. A method of treating particles of spinel having the formula Lii+xMn2-x04 (0.02 < x < 0.15) to produce a protective coating of battery- inactive lithium metal oxide on the particles, which method is substantially as herein 15 described with reference to Example 2.
14. A particulate stabilized spinel battery cathode material having a protective coating of lithium metal oxide thereon produced in accordance with the 5 method of any of claims 1 through 13. DATED: 9 November, 2004 PHILLIPS ORMONDE & FITZPATRICK 10 Attorneys for: Kerr-McGee Chemical LLC INTELLECTUAL PROPERTY OFFICE OF N.Z. 2 * OEC 2004 RECEIVED 06/27/2003 16:04 FAX 405 270 3030 KERR MCGEE @018 16 Case 1076 10 Abstract jof the Disclosure Improved stabilized spinel bateiy cathode material and methods of treating particles of spinel battery cathode material to produce a protective coating of battery-inactive lithium metal oxide on the particles arc provided. The methods comprise mixing the spinel particles with a par iculate reactant selected from a lithium salt, a litfaium metal oxide or a mixture of a ithium salt and a metal oxide and then heating die resultant particulate mixture for s time and temperature to react the particulate reactant with flie spinel particles wher iby a protective coating of lithium metal oxide is formed on the spinel particles and the lithium content of the spinel adjacent to the coating is increased a limited amount fax26052.tif 28/06/03 07:58 INTELLECTUAL PROPERTY OFFICE OF N.Z. 2 4 DEC 2004 RECEIVED
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