NZ554078A - Process for producing lithium transition metal oxides - Google Patents

Process for producing lithium transition metal oxides

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Publication number
NZ554078A
NZ554078A NZ554078A NZ55407805A NZ554078A NZ 554078 A NZ554078 A NZ 554078A NZ 554078 A NZ554078 A NZ 554078A NZ 55407805 A NZ55407805 A NZ 55407805A NZ 554078 A NZ554078 A NZ 554078A
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New Zealand
Prior art keywords
process according
aqueous solution
transition metal
metal oxide
lithium transition
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NZ554078A
Inventor
Feng Zou
Mohammad Jahangir Hossain
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Cvrd Inco Ltd
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Publication of NZ554078A publication Critical patent/NZ554078A/en

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/04—Carbonyls
    • 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
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C01D15/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/12—Complex oxides containing manganese and at least one other metal element
    • C01G45/1221—Manganates or manganites with trivalent manganese, tetravalent manganese or mixtures thereof
    • C01G45/1228—Manganates or manganites with trivalent manganese, tetravalent manganese or mixtures thereof of the type (MnO2)-, e.g. LiMnO2 or Li(MxMn1-x)O2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/04—Oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/40—Complex oxides containing cobalt and at least one other metal element
    • C01G51/42—Complex oxides containing cobalt and at least one other metal element containing alkali metals, e.g. LiCoO2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/40—Complex oxides containing cobalt and at least one other metal element
    • C01G51/42—Complex oxides containing cobalt and at least one other metal element containing alkali metals, e.g. LiCoO2
    • C01G51/44—Complex oxides containing cobalt and at least one other metal element containing alkali metals, e.g. LiCoO2 containing manganese
    • C01G51/50—Complex oxides containing cobalt and at least one other metal element containing alkali metals, e.g. LiCoO2 containing manganese of the type (MnO2)n-, e.g. Li(CoxMn1-x)O2 or Li(MyCoxMn1-x-y)O2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/04—Oxides
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Compounds Of Iron (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

A direct low temperature process for lithiating hydroxides and forming lithiated transition metal oxides of suitable crystallinity is disclosed, wherein, elemental transition metal powders are combined with an aqueous solution of lithium hydroxide, the aqueous slurry solution is subject to oxidation and agitation, the resultant lithium transition metal oxide is crystallized in-situ and subsequently removed from the reactor. By utilizing a relatively low processing temperature below about 150 Deg. C a desirable lithiated product is sufficiently formed. Therefore the problems associated with diffusion and atmospheric controls for heat treatment are reduced, as such a continuous rotary furnace may be employed for heat treatment rather than a batch static furnace.

Description

554078 PROCESS FOR PRODUCING LITHIUM TRANSITION METAL OXIDES TECHNICAL FIELD id="p-1" id="p-1" id="p-1" id="p-1" id="p-1" id="p-1" id="p-1" id="p-1" id="p-1"
[001] The present invention relates to the production of lithium transition metal oxides in general and to the direct conversion of transition elemental metal powders to lithium metal oxide particles in particular.
BACKGROUND OF THF. INVENTION id="p-2" id="p-2" id="p-2" id="p-2" id="p-2" id="p-2" id="p-2" id="p-2" id="p-2"
[002] With the continuing remarkable development of electronic apparatus such as portable computers, cell phones, cameras, personal digital assistants (PDA's) electric vehicles, etc. there has been a strong demand for the enhancement of the performance of the batteries used to supply power for these devices. Lithium battery systems are becoming the battery system of choice because of their superior energy density and power density over other rechargeable battery technologies. id="p-3" id="p-3" id="p-3" id="p-3" id="p-3" id="p-3" id="p-3" id="p-3" id="p-3"
[003] Lithium cobalt dioxide (LiCo02) is the major active cathodic material currently used in lithium batteries. id="p-4" id="p-4" id="p-4" id="p-4" id="p-4" id="p-4" id="p-4" id="p-4" id="p-4"
[004] Typically, most commercial lithium cobalt oxide is made by a solid-state reaction between a lithium compound and a cobalt compound occurring at high temperatures (900-950 C) for many hours. This process requires several steps involving lengthy heat treatments combined with good mixing steps such as ball milling or other fine grinding methods. Variations include aqueous solutions, extensive pre-mixing, mechanical alloying, sol-gel, spray drying, solution combustion, catalysts, co-precipitation, hydro thermal 554078 methods, etc. Often, these processes are complex or produce pollutants that must be treated. id="p-5" id="p-5" id="p-5" id="p-5" id="p-5" id="p-5" id="p-5" id="p-5" id="p-5"
[005] In addition, other lithium metal oxides have been extensively studied as alternatives to LiCo02. Among them, Ni/Mn or Ni/Mn/Co based mixed lithium oxides with layered structures are considered promising substitute cathode materials for lithium batteries with better performance including large scale automotive applications than the currently used IJC0O2. Again, complex, cumbersome, high temperature solid-state reactions are 10 generally used to produce these materials. id="p-6" id="p-6" id="p-6" id="p-6" id="p-6" id="p-6" id="p-6" id="p-6" id="p-6"
[006] Accordingly, there is a need for a simple, low temperature process for producing crystallized mixed lithiated metal oxides.
SUMMARY OF THE INVENTION id="p-7" id="p-7" id="p-7" id="p-7" id="p-7" id="p-7" id="p-7" id="p-7" id="p-7"
[007] There is provided a low temperature, environmentally friendly process for producing lithium transition-metal oxide with spherical or elliptic particle shapes directly from the metallic form of the transition metal in an 20 aqueous solution containing lithium ion with a pH more than about 13. The transition metal could be a single element or combination of them suitable for lithium energy cells including cobalt, manganese, nickel, etc. An oxidizing environment, for example an oxidant, such as oxygen, or an oxygen containing gas such as air, hydrogen peroxide, ozone, hypochloride, or persulfate, is 25 introduced into the solution and the mixture is heated to above 30°C.
BRIEF DESCRIPTION OF THE DRAWINGS id="p-8" id="p-8" id="p-8" id="p-8" id="p-8" id="p-8" id="p-8" id="p-8" id="p-8"
[008] Figure 1 is an x-ray diffraction spectrum pattern of various timed samples made in accordance with an embodiment of the invention. 2 554078 id="p-9" id="p-9" id="p-9" id="p-9" id="p-9" id="p-9" id="p-9" id="p-9" id="p-9"
[009] Figure 2 is photomicrograph of a sample made in accordance with an embodiment of the invention. id="p-10" id="p-10" id="p-10" id="p-10" id="p-10" id="p-10" id="p-10" id="p-10" id="p-10"
[0010] Figure 3 is a photomicrograph of a sample made in accordance with an embodiment of the invention. id="p-11" id="p-11" id="p-11" id="p-11" id="p-11" id="p-11" id="p-11" id="p-11"
[0011] Figure 4 is an x-ray diffraction pattern of a sample made in accordance with an embodiment of the invention. 10012] Figure 5 is a charge/discharge graph of a cell made in accordance with an embodiment of the invention. id="p-13" id="p-13" id="p-13" id="p-13" id="p-13" id="p-13" id="p-13" id="p-13" id="p-13"
[0013] Figure 6 is an x-ray diffraction pattern of samples made in 10 accordance with an embodiment of the invention. id="p-14" id="p-14" id="p-14" id="p-14" id="p-14" id="p-14" id="p-14" id="p-14" id="p-14"
[0014] Figure 7 is an x-ray diffraction pattern of samples made in accordance with an embodiment of the invention.
PREFERRED EMBODIMENTS OF THE INVENTION id="p-15" id="p-15" id="p-15" id="p-15" id="p-15" id="p-15" id="p-15" id="p-15" id="p-15"
[0015] The adverb "about" before a series of values will be construed as being applicable to each value in the series unless noted to the contrary. id="p-16" id="p-16" id="p-16" id="p-16" id="p-16" id="p-16" id="p-16" id="p-16" id="p-16"
[0016] As noted above, LiCoOi is currently used as a cathodic material in lithium batteiy systems. Other single or mixed LiM02 (M = Ni, Mn, Co, Fe, etc.) compounds are also under development. id="p-17" id="p-17" id="p-17" id="p-17" id="p-17" id="p-17" id="p-17" id="p-17" id="p-17"
[0017] The present low temperature process for making a lithiated oxide is relatively simple and more efficient when compared to current commercial techniques. id="p-18" id="p-18" id="p-18" id="p-18" id="p-18" id="p-18" id="p-18" id="p-18" id="p-18"
[0018] In the present process, metallic transition metals such as Co, Mn, Fe and Ni may be used directly to make lithium metal oxide. The aforementioned elements are specifically identified as components of lithium cells. However, the process is applicable to any transition metal. According to potential-pH equilibrium diagrams transition metals are not stable under high 3 554078 alkaline (pH>13) and oxidizing (slightly high potential) conditions. As a result, soluble species such as HMO2" (M=Co, Ni, Mn, Fe, etc.) may be formed. The oxidizing conditions can be created chemically, e.g. introducing an oxidant into the system, or electrochemically, e.g. applying anodic current to the metals. id="p-19" id="p-19" id="p-19" id="p-19" id="p-19" id="p-19" id="p-19" id="p-19" id="p-19"
[0019] By combining the transition metal, lithium hydroxide and source of oxidation, a reaction occurs causing lithium metal oxide to precipitate immediately after the metallic metal dissolves in solution. id="p-20" id="p-20" id="p-20" id="p-20" id="p-20" id="p-20" id="p-20" id="p-20"
[0020] The overall reaction is believed to be represented by the following equation for the case of using oxygen as the oxidant: 4M + 4LiOH + 302 4LiM02 + 2H2O (M=Co, Mn, Ni, or mixtures thereof) id="p-21" id="p-21" id="p-21" id="p-21" id="p-21" id="p-21" id="p-21" id="p-21" id="p-21"
[0021] The above referenced reaction may be carried out at atmospheric 15 pressure, at temperatures equal to and above ambient temperature, and with a pH equal to and above about 13. However, in order to accelerate the kinetics of the reactions, the operating temperature and pH preferably should be increased, e.g. temperature at 100°C and pH at 14.5. Operating at levels greater than about atmospheric pressure may also increase the kinetics of the process although 20 higher pressures inevitably raise cost issues. Even though other alkaline materials such as NaOH and KOH may be used to adjust pH, it is preferable to use LiOH for pH adjustment to eliminate any potential contamination. In the following examples, metallic metal powders were used as starting materials. However, the process is not so limited thereto. In principle, any metallic metal 25 form can be used in this process. id="p-22" id="p-22" id="p-22" id="p-22" id="p-22" id="p-22" id="p-22" id="p-22" id="p-22"
[0022] The benefits using the present invention over current commercial processes include: id="p-23" id="p-23" id="p-23" id="p-23" id="p-23" id="p-23" id="p-23" id="p-23"
[0023] 1) The avoidance or substantial shortening of the subsequent high temperature crystallization heat treatment as compared to the conventional solid 4 554078 reaction route. If desired, an optional heat treatment at about 850°C for about 0.5-4 hours appears to provide additional results, as opposed to conventional 12-30 hour multiple-stage heat treatment regimens. id="p-24" id="p-24" id="p-24" id="p-24" id="p-24" id="p-24" id="p-24" id="p-24"
[0024] The present process generates lithiated layered cobalt oxide (space group: R-3m) with (003)FWHM (Full Width at Half Maximum) and (104)FWHM of about 0.5° without the need for a subsequent heat treatment. If higher crystallinity levels are desired, a subsequent heat treatment step may be utilized. However, in contrast to the prior art since the lithiated oxide 10 compound is already sufficiently crystallized, the time for the optional heat treatment step to raise crystallinity higher is significantly shorter by an order of about one magnitude. id="p-25" id="p-25" id="p-25" id="p-25" id="p-25" id="p-25" id="p-25" id="p-25" id="p-25"
[0025] In light of the enhanced initial crystallinity levels, if needed, the 15 heat treatment may be carried out from about 300°C to 1100°C. id="p-26" id="p-26" id="p-26" id="p-26" id="p-26" id="p-26" id="p-26" id="p-26" id="p-26"
[0026] 2) Spherical particles with high tap density can be obtained. Because the present process can be considered as a type of co-precipitation process, the particles generally grow with the time of the reaction and reaction conditions such as agitation and slurry density. This results in better control of both powder size and morphology. Moreover, the entire prior art ball milling process or other mixing process is eliminated. id="p-27" id="p-27" id="p-27" id="p-27" id="p-27" id="p-27" id="p-27" id="p-27" id="p-27"
[0027] 3) By utilizing a relatively low processing temperature below 25 about 150 C a desirable lithiated product is sufficiently formed. Therefore the problems associated with diffusion and atmospheric controls for heat treatment are reduced. id="p-28" id="p-28" id="p-28" id="p-28" id="p-28" id="p-28" id="p-28" id="p-28" id="p-28"
[0028] As a result of the improved morphologies and less critical control 30 demands brought by lower temperature processing, production efficiencies may 554078 be realized since a continuous rotary furnace may be employed for heat treatment rather than a batch static furnace. id="p-29" id="p-29" id="p-29" id="p-29" id="p-29" id="p-29" id="p-29" id="p-29" id="p-29"
[0029] 4) There will be no effluent generation with present process because the liquid can be totally reused after standard liquid/solid separation. id="p-30" id="p-30" id="p-30" id="p-30" id="p-30" id="p-30" id="p-30" id="p-30" id="p-30"
[0030] It is believed that at least one molar solution of lithium hydroxide is required for the process to operate at ambient temperatures. However, a higher concentration of lithium hydroxide is more favorable to complete the reaction mentioned above. As the temperature of the reaction is increased, the solubility of the lithium hydroxide increases as well. It is believed that an about 8 molar lithium hydroxide aqueous solution can be obtained at a temperature around 100C°. id="p-31" id="p-31" id="p-31" id="p-31" id="p-31" id="p-31" id="p-31" id="p-31"
[0031] In order to ensure the success of the examples below, the metallic powder is introduced along with solid lithium hydroxide (LiOH H2O) into the aqueous lithium hydroxide solution so as to have sufficient lithium hydroxide in the solution. In commercial practice, the most expeditious way of supplying lithium hydroxide should be utilized. id="p-32" id="p-32" id="p-32" id="p-32" id="p-32" id="p-32" id="p-32" id="p-32" id="p-32"
[0032] If desired doping elements such as aluminum and magnesium may be added to the aqueous solution. id="p-33" id="p-33" id="p-33" id="p-33" id="p-33" id="p-33" id="p-33" id="p-33" id="p-33"
[0033] A number of experiments were run to demonstrate the efficacy of 25 the present invention. id="p-34" id="p-34" id="p-34" id="p-34" id="p-34" id="p-34" id="p-34" id="p-34" id="p-34"
[0034] Example 1 id="p-35" id="p-35" id="p-35" id="p-35" id="p-35" id="p-35" id="p-35" id="p-35" id="p-35"
[0035] 250g metallic cobalt powder together with 250g LiOH H2O was introduced into a 3000mL vessel having a 1500mL LiOH aqueous solution with a concentration about 3M at atmospheric pressure. The temperature of the slurry was maintained between about 80-120°C. The slurry was agitated with an 6 554078 impeller at 700 revolutions per minute. 40g of LiCo02 (lithium cobalt oxide) with averaged particle size of 2|iin was also introduced into the vessel as seeds. To start the reaction, oxygen gas was continuously introduced into the vessel at a flow rate of about 150-200 mL per minute. The reaction lasted 104 hours.
About 50g LiCoC>2 samples were taken out respectively at 10 hour, 34 hour, 58 hour, 82 hour and 104 hour of reaction time with magnetic separations from the unreacted cobalt and water wash. After each sampling, 220g cobalt powder and 150g LiOH^O were added into the reacting system. id="p-36" id="p-36" id="p-36" id="p-36" id="p-36" id="p-36" id="p-36" id="p-36"
[0036] Table 1 shows the results of lithium to cobalt molar ratio with inductively coupled plasma (ICP) analysis and the particle size measured using a Microtrac® particle size analyzer for each sample. Continuously increasing in particle size indicates that newly formed product could precipitate on the surface of existing particles. However, the Li/Co molar ratios for all the samples 15 were about 1.00 as expected for a completed reaction to produce LiCoC>2, which implies that LiCo02 was produced instantly under the reaction. The XRD (x-ray diffraction) spectra for each sample show a single layered LiCoCh phase as seen in representation sample curves in Figure 1, which supports above conclusion of LiCo02 formation. For comparison purposes, Figure 1 also shows a standard 20 LiCoC>2 XRD pattern just above the X-axis.
Table 1 Reaction time (hours) Li/Co molar ratio Particle size D5o (jum) 1.01±0.02 3.76 34 1.01±0.02 4.82 58 1.00±0,02 6.08 82 0.99±0.02 7.06 104 1.01±0.02 y 99 7 554078 id="p-37" id="p-37" id="p-37" id="p-37" id="p-37" id="p-37" id="p-37" id="p-37" id="p-37"
[0037] A SEM (scanning electron microscope) image of the sample taken at 104 hour of reaction time is shown in Figure 2. It can be seen that the particles are quite spherical with smooth surfaces. In order to increase the 5 crystallinity, a one-hour heat treatment was performed at 880°C. There was no change in the particle shape after the heat treatment as seen in figure 3. The XRD spectrum for the sample with the heat treatment showed that crystal structure was still a layered LiCo02 structure but the crystallinity was changed as seen in figure 4. The FWHM of (003) and (104) was 0.55° and 0.47° respectively for the sample before heat treatment but was 0.10° and 0.12° for the sample after heat treatment. The tap density of the sample after heat treatment was about 2.6g/cm3, and the surface area measured by the Brunauer-Emmett-Teller (BET) method was about 0.78m2/g. id="p-38" id="p-38" id="p-38" id="p-38" id="p-38" id="p-38" id="p-38" id="p-38"
[0038] In order to test the electrochemical performance of the above LiCo02 material, a Swagelok® type cell with three-electrode system was used in which Li metal was used for both counter and reference electrodes. The electrolyte solution is 1 M LiPFg in ethylene carbonate/dimethyl carbonate (EC/DMC, 1:1). Figure 5 shows the test results with C/5 charge/discharge rate.
The charge/discharge voltage window was 3.0V to 4.3V for the first twenty cycles and 3.7V to 4.3V for the remaining cycles. The discharge capacity of the material was stabilized at about 140mAh/g for 3.0-4.3V window and about 130mAh/g for 3.7-4.3V window. id="p-39" id="p-39" id="p-39" id="p-39" id="p-39" id="p-39" id="p-39" id="p-39"
[0039] Example 2 id="p-40" id="p-40" id="p-40" id="p-40" id="p-40" id="p-40" id="p-40" id="p-40" id="p-40"
[0040] 250g metallic cobalt powder together with 400g LiOH H20 was introduced into a 3000mL vessel having a 1500mL LiOH aqueous solution with a concentration of 3M at atmospheric pressure. The temperature of the slurry was maintained between about 80-120°C. The slurry was agitated with an impeller at 720 revolutions per minute. In contrast to example 1, there was no 8 554078 LiCoC>2 introduced into the vessel as seeds. To start the reaction, oxygen gas was continuously introduced into the vessel at a flow rate of about 100 mL per minute. 385g of product was obtained after 45 hours reaction with magnetic separations from the unreacted cobalt and water wash. By ICP analysis and 5 XRD examination, the product was pure LiCo02 as expected. The conversion of the reaction was about 92%. id="p-41" id="p-41" id="p-41" id="p-41" id="p-41" id="p-41" id="p-41" id="p-41" id="p-41"
[0041] Example 3 id="p-42" id="p-42" id="p-42" id="p-42" id="p-42" id="p-42" id="p-42" id="p-42"
[0042] 250g metallic cobalt powder together with 400g LiOH H20 was introduced into a 3000mL vessel having a 1400mL LiOH aqueous solution with a concentration of 3M at atmospheric pressure. The temperature of the slurry was maintained between about 90-110°C. The slurry was agitated with an impeller at 700 revolutions per minute. About 40g of LiCo02 was also 15 introduced into the vessel as seeds. Instead of using oxygen as in example 1, air was continuously introduced into the vessel at a flow rate of about 320 mL per minute. 190g of product was obtained after 48 hours reaction with magnetic separations from the unreacted cobalt and a water wash. By ICP analysis and XRD examination, the product was pure LiCo02 as expected. The conversion 20 of the reaction was about 46%. id="p-43" id="p-43" id="p-43" id="p-43" id="p-43" id="p-43" id="p-43" id="p-43" id="p-43"
[0043] Example 4 id="p-44" id="p-44" id="p-44" id="p-44" id="p-44" id="p-44" id="p-44" id="p-44" id="p-44"
[0044] 250g metallic cobalt powder together with about 400g LiOH H20 25 was introduced into a 3000mL vessel having a 1400mL LiOH aqueous solution with a concentration of 3M at atmospheric pressure. The temperature of the slurry was maintained at room temperature, i.e. about 25-30°C. The slurry was agitated with an impeller at 700 revolutions per minute. 40g of LiCo02 was also introduced into the vessel as seeds. Oxygen was continuously introduced into 30 the vessel at a flow rate of 100 mL per minute. 405g of product was obtained after 67 hours reaction time with magnetic separations from the unreacted cobalt 9 554078 and water wash. By XRD examination, the product was a mixture of LiCo02 and CoOOH as seen in Figure 6. ICP analysis result showed that the Li to Co molar ratio was only 0.34, which implied that only 34% of Co was LiCo02 and the rest was CoOOH, even through about 98% Co powder was reacted. For 5 comparison purposes, standard LiCo02 and CoOOH are shown above the X-axis, id="p-45" id="p-45" id="p-45" id="p-45" id="p-45" id="p-45" id="p-45" id="p-45" id="p-45"
[0045] Example 5 id="p-46" id="p-46" id="p-46" id="p-46" id="p-46" id="p-46" id="p-46" id="p-46"
[0046] 250g metallic cobalt powder together with 400g LiOH H20 was introduced into a 3000mL vessel having a 1400mL LiOH aqueous solution with a concentration of 3M at atmospheric pressure. The temperature of the slurry was maintained at about 90-100°C. The slurry was agitated with an impeller at 700 revolutions per minute. 30g of L1C0O2 was also introduced into the vessel 15 as seeds. Instead of using oxygen, H2O2 (30% solution) was continuously introduced into the vessel at an averaged flow rate of about 1.0 mL per minute. About 420g of product was obtained after about 45 hours reaction with magnetic separations from the unreacted cobalt and water wash. By XRD examination, the product was LiCo02. ICP analysis result showed that the Li to 20 Co molar ratio was about 1.0. The Co conversion was almost 100%. id="p-47" id="p-47" id="p-47" id="p-47" id="p-47" id="p-47" id="p-47" id="p-47" id="p-47"
[0047] Example 6 id="p-48" id="p-48" id="p-48" id="p-48" id="p-48" id="p-48" id="p-48" id="p-48" id="p-48"
[0048] 250g metallic manganese powder together with 400g LiOH H20 25 was introduced into a 3000mL vessel having a 1500mL LiOH aqueous solution with a concentration of 3M at atmospheric pressure. The temperature of the slurry was maintained about 90-100°C. The slurry was agitated with an impeller at 700 revolutions per minute. 30g of fresh prepared Mn(OH)2 was also introduced into the vessel as seeds. Oxygen was continuously introduced into 3 0 the vessel at a flow rate of 100 mL per minute. 415g of product was obtained after about 31 hours reaction with the water wash. By XRD examination, the 554078 product was LiMnC>2 (lithium manganate) as seen in Figure 7. ICP analysis result showed that Li to Mn molar ratio was about 1.03. For comparison purposes, standard LiMnCh is shown in Figure 7. id="p-49" id="p-49" id="p-49" id="p-49" id="p-49" id="p-49" id="p-49" id="p-49"
[0049] Example 7 id="p-50" id="p-50" id="p-50" id="p-50" id="p-50" id="p-50" id="p-50" id="p-50" id="p-50"
[0050] 208g metallic cobalt powder was introduced into a 3000mL vessel having a 1400mL LiOH aqueous solution with a concentration 8M at atmospheric pressure. The temperature of the slurry was maintained at 100°C.
The slurry was agitated with an impeller at 700 revolutions per minute. Oxygen was continuously introduced into the vessel at a flow rate of about 150 mL per minute. After 30 minutes of introducing oxygen, 2g of manganese powder was added into the reacting system every one hour for 14 hours, i.e. total 28g Mn powder added into the reactor. After one hour from the last Mn powder addition, the reaction was terminated and about 140g product was collected with magnetic separations from the unreacted cobalt and water wash. ICP analysis result showed that Mn/Co molar ratio was 0.5 and Li to (Co+Mn) molar ratio was 1.04. XRD spectrum of the product showed a similar structure as layered LiCo02- The expected peak shifting slightly toward lower degree direction, which was due to the larger Mn ion replacing Co in the lattice was also observed. All these results suggest that a mixed Li(Mni/3Co2/3)02 was formed. id="p-51" id="p-51" id="p-51" id="p-51" id="p-51" id="p-51" id="p-51" id="p-51" id="p-51"
[0051] In principle, any size of the initial elemental metal powder may be used in present process. By judicious adjustment and timing of the reaction the resultant lithium transition metal oxides may range from about 0.1 (am to 30^m. id="p-52" id="p-52" id="p-52" id="p-52" id="p-52" id="p-52" id="p-52" id="p-52" id="p-52"
[0052] The present process is an exquisite simplification of current somewhat cumbersome processes to produce ever finer and purer lithium transition metal oxides. Taking basic elemental pure metal powders and 11 554078 transforming them into the finished product in an economically and environmentally friendly is a decided advance over the current state of the art. id="p-53" id="p-53" id="p-53" id="p-53" id="p-53" id="p-53" id="p-53" id="p-53" id="p-53"
[0053] While in accordance with the provisions of the statute, there is illustrated and described herein specific embodiments of the invention. Those skilled in the art will understand that changes may be made in the form of the invention covered by the claims and that certain features of the invention may sometimes be used to advantage without a corresponding use of the other features. 12 554078

Claims (25)

CLAIMS:
1. A process for producing lithium transition metal oxide, the process 5 comprising: a) providing an aqueous solution of LiOH, b) introducing M elemental metal into the aqueous solution wherein M elemental metal is selected from a group consisting of at least one transition metal; 10 c) creating an oxidizing environment in the aqueous solution, d) agitating the aqueous solution; e) causing the resultant lithium transition metal oxide to crystallize in-situ; and f) collecting the resultant lithium transition metal oxide from the 15 aqueous solution.
2. The process according to claim 1 wherein the transition metals are selected from at least one of a group consisting of nickel, cobalt, manganese, and iron. 20
3. The process according to claim 1 wherein the pH of the aqueous solution is at least about 13.
4. The process according to claim 1 wherein the temperature of the 25 aqueous solution is at least about 30°C.
5. The process according to claim 1 wherein M elemental metal is a powder. 30
6. The process according to claim 1 wherein the oxidizing environment is created by an oxidant. 13 WO 2006/037205 554078 PCT/CA2005/000879
7. ' The process according to claim 6 wherein the oxidant is selected from at least one of the group consisting of oxygen, air, hydrogen peroxide, ozone, hypochloride, and persulfate. 5
8. The process according to claim 1 wherein the pH of the aqueous solution is modulated by the addition of an alkaline selected from at least one of a group consisting of LiOH, NaOH and KOH. 10
9. The process according to claim 1 wherein the resultant lithium transition metal oxide is subjected to a crystallization heat treatment.
10. The process according to claim 9 wherein the crystallization heat treatment is conducted for about 300°C to 1100°C, 15
11. The process according to claim 8 wherein the crystallization heat treatment is conducted for about 0.5 to 4 hours.
12. The process according to claim 1 wherein additional resultant lithium 20 transition metal oxide is introduced into the aqueous solution as seed.
13. The process according to claim 1 wherein Li0HH20 is co-introduced with M elemental metal into the aqueous solution of LiOH to create at least a one molar aqueous solution of lithium hydroxide. 25
14. The process according to claim 1 wherein the temperature of the aqueous solution ranges from about 25°C to 150°C.
15. The process according to claim 1 wherein the process is conducted at 30 about atmospheric pressure. 14 554078
16. The process according to claim 1 wherein the resultant lithium transition metal oxide is at least essentially spherical.
17. The process according to claim 1 wherein the resultant lithium transition metal oxide is at least essentially elliptical.
18. The process according to claim 1 including adding additional M elemental metal and of LiOH to the aqueous solution.
19. The process according to claim 1 wherein the size of the M elemental metal ranges from about 1 ,um to 500pm.
20. The process according to claim 1 wherein the size of the resultant lithium transition metal oxide ranges from about lprn to 30p.m.
21. The process according to claim 1 wherein a dopant is introduced into the aqueous solution.
22. The process according to claim 1 wherein the oxidizing environment is created by an electrochemical reaction.
23. The process according to claim 1 wherein the aqueous solution is about one to eight molar lithium hydroxide.
24. A lithium transition metal oxide produced by a method according to any one of claims 1 to 23.
25. A process according to claim 1, substantially as herein described with reference to any one of Examples 1 to 7 and/or Figures 1 to 7 thereof. 15 INTELLECTUAL PROPERTY OFFICF OF M 7. - 8 JUL 2009 RECEIVED
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