CA2610077C - Lithium manganese compounds and methods of making the same - Google Patents

Lithium manganese compounds and methods of making the same Download PDF

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CA2610077C
CA2610077C CA2610077A CA2610077A CA2610077C CA 2610077 C CA2610077 C CA 2610077C CA 2610077 A CA2610077 A CA 2610077A CA 2610077 A CA2610077 A CA 2610077A CA 2610077 C CA2610077 C CA 2610077C
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lithium metal
lithium
compound
manganese dioxide
electrolytic manganese
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CA2610077A1 (en
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Yuan Gao
Marina Yakovleva
Brian Fitch
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FMC Corp
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    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/12—Manganates manganites or permanganates
    • C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
    • C01G45/1228—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [MnO2]n-, e.g. LiMnO2, Li[MxMn1-x]O2
    • 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
    • H01M4/48—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
    • 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
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C01P2002/54—Solid solutions containing elements as dopants one element only
    • 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
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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
    • 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

Abstract

Electrode materials such as LixMnO2 where 0.2 < x <= 2 compounds for use with rechargeable lithium ion batteries can be formed by mixing LiMn2O4 compounds or manganese dioxide compounds with lithium metal or stabilized and non-stabilized lithium metal powders.

Description

LITHIUM MANGANESE COMPOUNDS
AND METHODS OF MAKING THE SAME
FIELD OF THE INVENTION
[0002] This invention generally relates to methods for forming lithium compounds, and the compounds formed by such methods. More particularly, this invention relates to methods for forming lithium manganese compounds and doped lithium manganese compounds by lithiation techniques.
BACKGROUND OF THE INVENTION
[0003] Attractive materials for use as cathode materials for lithium ion secondary batteries include LiCo02, LiNi02, and LiMn204. Unlike LiCo02 and LiNi02, the LiMn204 spinel compounds are believed to be overcharge safer and are desirable cathode materials for that reason. Nevertheless, although cycling over the full capacity range for pure LiMn204 can be done safely, the specific capacity of LiMn204 is low. Specifically, the theoretical capacity of LiMn204 is only 148 mA-hr/g and typically no more than about 115-120 mAshr/g can be obtained with good cycleability. LiMn204 can contain excess lithium on the 16d manganese sites and can be written as Li1+xMn2,04 (0 x .5 0.33). Use of the formula LiMn204 herein is understood to denote Li1+xMn2,(04 as well.
[0004] The orthorhombic LiMn02 and the tetragonally distorted spinel Li2Mn204 have the potential for larger capacities than those obtained with the LiMn204 spinel. However, cycling over the full capacity range for LiMn02 and Li2Mn204 results in a rapid capacity fade. Layered LiMn02 quickly converts to a spinel form upon cycling which also results in a capacity fade.
[0005] Various attempts have been made to either improve the specific capacity or safety of the lithium metal oxides used in secondary lithium batteries by doping these lithium metal oxides with other cations. For example, U.S.
Patent No. 6,214,493 to Bruce et al.

relates to stabilized layered LiMn02 using cobalt (Co) as a dopant material.
Stabilization has been recorded with as little as 15 percent cobalt substitution. In another example, U.S. Patent No. 5,370,949 to Davidson et al. proposes that introducing chromium cations into LiMn02 can produce a tetragonally distorted spinel type of structure which is air stable and has good reversibility on cycling in lithium cells.
[0006] Li2Mn02 compounds have also been considered as electrode materials.
U.S. Patent No. 4,980,251 to Thackeray proposes that Li2Mn02 can be formed having a theoretical capacity of 530 mA=hrig by reacting LiMn204 spinel compounds with n-BuLi as follows:
LiMn204 + n-BuLi Li2Mn204 + 2n-BuLi 2 Li2Mn02 The Li2Mn02 has a hexagonal close packed layered structure, similar to the structure of LiCo02, except that the Li+ ions in Li2Mn02 occupy the tetrahedral sites instead of the octahedral sites as in LiCo02. However, the Li2Mn02 compounds formed according to Thackeray's methods are unstable. In particular, Thackeray notes that the layered structure of Li2Mn02 is unstable and that it converts back to the spinel framework upon delithiation.
This is undesirable because repeated conversion between layered and spinel structures decreases capacity retention and results in voltage gaps.
[0007] A doped lithium manganese oxide preferably exhibits a high usable reversible capacity and good cycleability to maintain reversible capacity during cycling.
LiMn204 can generally only be operated at 115-120 mA=hrig with good cycleability.
Furthermore, Li2Mn02 compounds are expensive to make and are unstable when made according to available methods. Therefore, there is a need to produce a lithium metal oxide that exhibits an improved reversible capacity and good cycleability while maintaining thermal stability.
SUMMARY OF THE INVENTION
[0008] Embodiments of the present invention include methods for making lithium manganese oxide compounds and doped lithium manganese oxide compounds. The lithium manganese compounds and doped lithium manganese oxide compounds formed according to embodiments of the present invention can be used to form electrodes and electrode materials for use in batteries, such as rechargeable lithium ion batteries.
[0009] According to some embodiments of the present invention, a doped lithium manganese spinel compound is mixed with lithium metal to produce a doped LixMn02 compound where 0.2 < x 5 2. The mixing of the spinel compound and lithium metal can be performed with or without a solvent. Mixing of the spinel compound and lithium metal can be performed using processes capable of energetically mixing the doped lithium manganese spinel compound and lithium metal, such as by high energy ball milling. The mixing preferably provides as much contact between the spinel compound and the lithium metal as possible. A doped lithium manganese spinel compound can include compounds such as those disclosed by U.S. Patent No. 6,267,943 to Manev et al.. The lithium metal is preferably a stabilized lithium metal powder such as those disclosed by U.S. Patent Nos.
5,567,474 and 5,776,369 to Dover et al.. One of the added advantages of the present invention is that the amount of lithium x in Li,Mn02, where 0.2 < x 5 2, can be easily controlled and varied by varying the amount of the lithium metal used in synthesis, unlike high temperature solid state synthesis where the x value is governed by the high temperature phase diagram and may not be changed at will.
[0010] In other embodiments of the present invention, a manganese dioxide such as a heat treated electrolytic manganese dioxide (EMD) compound can be mixed with a lithium metal to lithiate the manganese dioxide compound.
The lithiated manganese dioxide such as the lithiated EMD material can be used as an electrode material in rechargeable lithium ion batteries. The lithium metal powder is preferably a stabilized lithium metal powder such as those disclosed by U.S. Patent Nos. 5,567,474 and 5,776,369 to Dover et al.
[0011] Electrodes for use in batteries, and particularly for use with rechargeable lithium ion cell batteries, can be formed using the LixMn02 where 0.2 < x .5 2 compounds or lithiated EMD materials formed according to embodiments of the present invention.
[0011-a] The present invention is also directed to a method for forming LixMn02, comprising mixing a LiMn204 compound with lithium metal to form LixMn02 where 0.2 < x 2 wherein the lithium metal is added in increments of 1/4 x or less and the crystalline structure of the LixMn204 compound is maintained.
[0011-13] In accordance with another aspect, the invention also concerns a method for forming LixMn02, comprising mixing an LiMn204 compound with lithium metal to form LixMn02 where 0.5 < x 2 wherein the crystalline structure of the LiMn204 compound is maintained, wherein the lithium metal is added in one quarter increments of x or less.
[0011-c] The present invention also concerns an electrode formed from the LixMn02 compound wherein the crystalline structure of the LiMn204 is maintained, wherein the LixMn02 compound is obtained from a method as defined hereinabove, and wherein 0.5 < x 2.
[0011-d] The present invention also concerns an electrode, comprising an LixMn02 compound where 0.5 <x 2, formed by mixing an LiMn204 compound with lithium metal wherein the crystalline structure of the LiMn204 compound is maintained, wherein the lithium metal is added in one quarter increments of x or less.
[0012] In accordance to still another aspect, the invention concerns a method of forming a lithiated electrode material, comprising mixing an electrolytic manganese dioxide compound with lithium metal to produce a lithiated electrolytic manganese dioxide material wherein the crystalline structure of the electrolytic manganese dioxide compound is maintained without distorting the EMD structure, wherein the lithium metal is added in one quarter increments of the total amount of lithium metal to be added or less.
[0013] The foregoing and other aspects of the present invention are explained in greater detail in the specification set forth below and will be apparent from the description of the invention.

BRIEF DESCRIPTION OF THE DRAWINGS
[0014] Figure 1 is a graphic comparison of x-ray diffraction patterns according to Example 1.
[0015] Figure 2 is a graphic comparison of x-ray diffraction patterns according to Example 2 and Comparative Example 1.
[0016] Figure 3 is a graph of Voltage (V) versus Specific Capacity (mAH/g) relating to Example 2.
[0017] Figure 4 is a graphic comparison of x-ray diffraction patterns according to Examples 3 and 4, and Comparative Example 1.
[0018] Figure 5 is a graph of Voltage (V) versus Specific Capacity (mAH/g) relating to Example 3.
DETAILED DESCRIPTION OF THE INVENTION
[0019] The present invention now will be described more fully hereinafter.
This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein; rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
[0020] The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used in the description of the invention and the appended claims, the singular forms "a", "an" and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
Additionally, as used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
[0021] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
4a [0022] Embodiments of the present invention include methods for making lithium manganese oxide compounds and doped lithium manganese oxide compounds. The lithium manganese compounds and doped lithium manganese oxide compounds formed according to embodiments of the present invention can be used to form electrodes and electrode materials for use in batteries, such as rechargeable lithium ion batteries.
[0023] According to embodiments of the present invention, methods for forming a lithium manganese oxide compound having the formula LixMn02 where 0.2 < x 5 2 are provided. In some embodiments, the lithium manganese oxide compound can be a doped lithium manganese oxide compound. For example, a doped lithium manganese oxide 4b compound having the formula Li2Mni-otAa02 can be formed, wherein A is a dopant and 0 a <O.5.
[0024] A lithium manganese oxide compound having the formula LixMn02 where 0.2 < x 2, often 0.5 < x 2 can be formed according to embodiments of the present invention by mixing an LiMn204spinel compound with lithium metal. As the LiMn204 compound comes in contact with the lithium metal, the compound accepts the lithium and converts to the desired LixMn02 compound. For example, an LiMn204 compound can be mixed with lithium metal in a ball mill to form LixMn02. The lithium metal is preferably a stabilized lithium metal powder. The mixing of the LiMn204 compound can be performed using any mixing techniques, however, mixing that improves the amount of contact between the LiMn204 compound and the lithium metal is preferred.
[0025] The lithium metal in one embodiment, can be added all at once. In another embodiment, the lithium is added in smaller increments, e.g. x/4 or less. Such addition avoids distortion of the x-ray diffraction pattern, and allows the LixMn02 compound to maintain an x-ray diffraction (crystallinity) pattern similar to that of EMD.
[0026] The lithium metal used with embodiments of the present invention can include stabilized lithium metal powder ("SLMP"). For example, FMC Corporation produces a stabilized lithium metal powder under the name Lectro Max Powder that may be used with embodiments of the present invention. Other lithium metal powders may also be used.
For instance, U.S. Patent No. 5,567,474 and U.S. Patent No. 5,776,369, describe stabilized lithium metal powders and processes for making such powders that can be used with the embodiments of the present invention.
[0027] Stabilized lithium metal powders allow the methods of embodiments of the present invention to be performed with increased safety. However, lithium metal powders that are not stabilized can also be used with embodiments of the present invention. In those embodiments where non-stabilized lithium metal or lithium metal powders are used, additional processes can be employed to improve the safety of the reactions.
For example, the mixing of an LiMn204 compound with the non-stabilized lithium metal or lithium metal powder can be performed in an inert atmosphere to inhibit undesired reactions of the lithium metal with the atmosphere.
[0028] In other embodiments of the present invention, a doped LixMn02 compound can be formed by mixing a doped LiMn204 compound with lithium metal.
The doped LiMn204 compounds can include LiMn204 compounds doped with dopants such as cobalt (Co), nickel (Ni), magnesium (Mg), titanium (Ti), zirconium (Zr), chromium (Cr), or other dopants used in the production of electrode materials for use with batteries and rechargeable lithium-ion batteries. The lithium metal is preferably a stabilized lithium metal powder.
[0029] The mixing of lithium metal with LiMn204 or doped LiMn204 spinel compounds can be performed in a ball mill or according to other mixing techniques. In some embodiments, the mixing preferably includes energetic mixing which increases the mixing of the compounds, improving the amount of contact between the LiMn204 compounds and the lithium metal.
[0030] The mixing of lithium metal with LiMn204 can be performed with or without a solvent. If a solvent is used, the solvent is preferably compatible with lithium such that the lithium metal does not react with the solvent during the mixing.
Solvents that can be used with embodiments of the present invention include, but are not limited to, acyclic and cyclic hydrocarbons, including n-hexane, n-heptane, cyclohexane, and the like;
aromatic hydrocarbons such as toluene, xylene, isopropylbenzene (cumene), and the like;
symmetrical, unsymmetrical, and cyclic ethers, including di-n-butyl ether, methyl t-butyl ether, tetrahydrofuran, and the like.
[0031] In some embodiments of the present invention, the LiMn204 compounds can be produced by calcining a mixture of at least one manganese oxide, at least one lithium compound, and optionally at least one dopant in a firing step at a temperature between 400 C
and 900 C. The manganese oxide compounds can include such compounds as Mn203, Mn304, electrolytic manganese dioxide, and13-Mn02, and the firing step can include multiple firing steps.
[0032] In the calcining step, the mixture of source compounds is fired at between about 400 C and about 900 C. Preferably, the mixture is calcined using more than one firing step at firing temperature with this temperature range. During calcinations, agglomeration of the spinel particles is preferably prevented. For example, during a multiple step firing sequence, agglomeration can be prevented by firing the source compounds in a fluid bed furnace or rotary calciner during at least a portion of the firing steps or by grinding the spinel material between steps.
[0033] The manganese oxide compounds produced in this manner can be formed into LiMn204 compounds that can be used with embodiments of the present invention. In addition, other methods for forming lithium manganese oxides may be used with embodiments of the present invention. For instance, the methods and compounds of U.S.
Patent Numbers 6,267,943; 6,423,294; and 6,517,803 may be used with embodiments of the present invention.
[0034] The lithiated EMD materials formed according to embodiments of the present invention exhibit a capacity of about 150 mA=hr/g to about 160 mA=larig when incorporated into an electrode. In addition, the lithiated EMD materials of the present invention can be made cheaply because EMD compounds are readily available and easily produced.
[0035] According to some embodiments of the present invention, the lithiated EMD materials of the present invention can be used as low cost materials for forming electrodes for use with lithium ion batteries.
[0036] Embodiments of the invention also include batteries and electrodes formed from compounds and materials produced according to embodiments of the present invention.
An electrode for use with a lithium ion battery can be formed from the LiõMn02 compounds or doped LixMn02 compounds formed according to embodiments of the present invention. In.
addition, the lithiated EMD materials formed according to embodiments of the present invention can be used to form electrodes for use in lithiurn ion batteries.
The LiõMn02 compounds and lithiated EMD materials formed according to embodiments of the present invention can be used to form anodes or cathodes for use in batteries and especially for use with rechargeable lithium ion batteries.
[0037] Having now described the invention, the same will be illustrated with reference to certain examples, which are included herein for illustration purposes only, and which are not intended to be limiting of the invention.
EXAMPLES
Example 1 Lithium is added into a heat treated electrolytic manganese dioxide ("HEMD").
Electrolytic manganese dioxide available for Erachem-Comilog was ground to reduce the particle size and heat treated at 400oC for 12 hours to obtaind heat treated electrolytic manganese. The lithium is added in small increments of 0.075 moles of Li per one mole of manganese oxide. The addition is done in glove box at room temperature and stainless steel ball mill jar is used as a mixing vessel.
Figure 1 shows the x-ray diffraction patters of HEMD with no lithium and the various total addition amounts (0.30 moles Li to 0.58 moles Li). Comparison of the x-ray diffraction patterns demonstrates that the lithium can be added incrementally without distorting the structure of the HEMD to maintain the HEMD-like structure.
Example 2 and Comparative Example 1 Li0.3Mn02 is prepared by two ways. In Comparative Example 1, all 0.3 moles of lithium to one mole manganese oxide are added at once. In Example 2, the lithium is added in increments of 0.075 moles lithium to one mole manganese oxide.
The x-ray diffraction pattern of Figure 2 shows a well crystalline spinel-like structure for the Lio.3Mn02 of Comparative Example 1. This is contrasted to the x-ray diffraction pattern for Example 2 which shows a pattern similar to that of the HEMD raw material sample and graphically indicates very little distortion therefrom.
Figure 3 shows electrochemical results. The Lio.3Mn02 of Example 2 shows an increase of first charge efficiency from 45 percent to 93 percent as compared to the one-step addition process of Comparative Example 1. The voltage profile was sustained for over 10 cycles which implies no structural changes occurred. Such sustaining of the voltage profile indicates such a material is a good candidate for 3V rechargeable lithium batteries.
Examples 3 and 4 and Comparative Example 2 Li0.6Mn02 is prepared by three ways. In Comparative Example 2, all of the 0.6 moles of lithium to one mole of manganese oxide are added at once. In Example 3, the 0.6 moles of lithium to one mole of manganese oxide are added in increments of 0.15 moles. In Example 4, the lithium is added in increments of 0.075 moles of lithium to one mole of manganese oxide.
The x-ray diffraction pattern for Comparative Example 2 in Figure 4 shows a well-crystalline spinel-like structure for the Lio.6Mn02 but is distorted as compared to the HEMD raw material sample. This is contrasted to Examples 3 4r.
and 4 which show patterns similar to that of the HEMD raw material sample and indicates very little distortion.
Figure 5 shows electrochemical results. The Li0.6Mn02 of Example 3 shows an increase of first charge efficiency from 39 percent to 81 percent as compared to the one-step addition process of Comparative Example 2.
[0038] Having thus described certain embodiments of the present invention, it is to be understood that the invention is not to be limited by particular details set forth in the above description as many apparent variations thereof are possible.
8a

Claims (8)

1. A method of forming a lithiated electrode material, comprising mixing an electrolytic manganese dioxide compound with lithium metal to produce a lithiated electrolytic manganese dioxide material wherein the crystalline structure of the electrolytic manganese dioxide compound is maintained without distorting the EMD structure, wherein the lithium metal is added in one quarter increments of the total amount of lithium metal to be added or less.
2. The method of claim 1, wherein the lithium metal comprises a lithium metal powder.
3. The method of claim 2, wherein the lithium metal powder comprises a stabilized lithium metal powder.
4. The method of claim 1, wherein the electrolytic manganese dioxide compound comprises a heat treated electrolytic manganese dioxide compound.
5. The method of claim 1, wherein mixing the electrolytic manganese dioxide compound with lithium metal comprises ball milling the electrolytic manganese dioxide compound with lithium metal.
6. The method of claim 5, wherein ball milling the electrolytic manganese dioxide compound with lithium metal further comprises ball milling the electrolytic manganese dioxide compound with lithium metal in the presence of a solvent.
7. The method of claim 6, wherein the solvent is selected from the group consisting of acyclic hydrocarbons, cyclic hydrocarbons, aromatic hydrocarbons, symmetrical ethers, unsymmetrical ethers, and cyclic ethers.
8. The method of claim 6, wherein the electrolytic manganese compound is doped with a dopant selected from the group consisting of cobalt, nickel, titanium, zirconium, chromium and any combinations thereof.
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