WO2000063923A1 - Layered lithium manganese compounds - Google Patents

Layered lithium manganese compounds Download PDF

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WO2000063923A1
WO2000063923A1 PCT/US2000/010209 US0010209W WO0063923A1 WO 2000063923 A1 WO2000063923 A1 WO 2000063923A1 US 0010209 W US0010209 W US 0010209W WO 0063923 A1 WO0063923 A1 WO 0063923A1
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group
lithium manganese
manganese oxide
layered
combinations
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PCT/US2000/010209
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WO2000063923A9 (en
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Gerbrand Ceder
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Massachusetts Institute Of Technology
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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
    • H01M4/36—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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/0018—Mixed oxides or hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/0018—Mixed oxides or hydroxides
    • C01G49/0072—Mixed oxides or hydroxides containing manganese
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G55/00—Compounds of ruthenium, rhodium, palladium, osmium, iridium, or platinum
    • C01G55/002—Compounds containing, besides ruthenium, rhodium, palladium, osmium, iridium, or platinum, two or more other elements, with the exception of oxygen or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/20—Two-dimensional structures
    • C01P2002/22—Two-dimensional structures layered hydroxide-type, e.g. of the hydrotalcite-type
    • 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
    • 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

Definitions

  • the present invention relates to lithium manganese oxide insertion compounds.
  • the invention relates to lithium manganese oxide compounds in the layered R3m structure.
  • it pertains to rechargeable batteries and the use of these insertion compounds as cathode materials.
  • Insertion compounds are those which are capable of reversibly introducing an element, molecule or other species ("intercalant") into a host structure. While the compound may distort somewhat upon introduction of the intercalant into the host lattice structure, the compound regains its original structure upon deintercalation. This process has been exploited in the battery industry to provide rechargeable lithium batteries.
  • Lithium ion secondary batteries are known to give high voltages and to have high discharge capacities.
  • a popular rechargeable lithium battery produced by Sony Corporation and others, consists of a carbon-based negative electrode and a layered LiCo0 2 material as the positive electrode in a non- aqueous electrolyte. While providing a high electrical capacity, LiCo0 2 suffers from the disadvantages of toxicity and expense.
  • LiMn0 2 is of interest as an alternative insertion electrode material in lithium secondary cells because of its high theoretical capacity of 286 mAh/g and because of its relatively lower cost and non-toxicity as compared to LiCo0 2
  • LiMn0 2 Lithium manganese dioxide
  • LiMn0 2 Lithium manganese dioxide
  • LiMn0 2 can also be prepared as a monoclinic phase through metastable synthesis routes.
  • the phase has an ⁇ - NaFe0 2 -type structure in which Li + ions are located between Mn0 6 sheets, giving the phase a layered arrangement which is particularly advantageous in the reversible insertion of lithium into the compound. Due to Jahn-Teller distortion around Mn 3+ , the symmetry is monoclinic.
  • a layered Li x M y Mn, .y 0 2 compound in which M is selected from the group selected from B, Ga, In, Ru, Os, Rh, Ir, Pd, Pt, Na, K, Rb, Group 2a, Group 3a, Group 4a, Group 5a, Group 6a, Group lb, Group 2b, Group 4b and Group 5b and combinations thereof, x is in the range of 0.6 to 1.1, and 0.05 ⁇ y ⁇ 0.5.
  • Li x M y Mn,. y 0 2 has an ⁇ -NaMn0 2 -type structure or distorted variant thereof.
  • M is a metal selected from the group consisting of B, Ga, In, Ru, Os, Rh, Ir, Pd, Pt, Na, K, Rb, Group 2a, Group 3a, Group 4a, Group 5a, Group 6a, Group lb, Group 2b, Group 4b and Group 5b and combinations thereof, x is in the range of 0.6 to 1.1, and 0.05 ⁇ y ⁇ 0.5.
  • M is selected from the group consisting of Ga, In, Na, Rb, Si, Group 2a, Group 2b, Group 4a and combinations thereof.
  • M is selected from the group consisting of Ti, Zn and Si.
  • M is a non-magnetic element selected from the group consisting of Na, K, Rb, Ga, In, Group 2a, Group 3a, Group 4a, Group 5a, Group 4b and Group 5b, and combinations thereof.
  • M is a cation having a valance of greater than +3 selected from the group consisting of Group 4a, Group 5 a, Group 6a, and Group 4b elements, and combinations thereof.
  • M is a cation having a valance of greater than +3 selected from the group consisting of Ge, Sn, V, Ti, and Si.
  • M may be a cation having a valance of less than +3 selected from the group consisting of Na, K, Rb, Group 2a, Group lb, Group 2b, and combinations thereof.
  • M may be a cation having a valance of less than +3 selected from the group consisting of Zn, Cu, and Mg and combinations thereof.
  • LiMn0 2 is distorted due to Jahn-Teller effects into monoclinic C2/m symmetry.
  • reference to a "layered structure" encompasses both the rhombohedral and monoclinic layered structures and other distorted variants thereof.
  • non-magnetic element and “non-magnetic ions” as those terms are used herein it is meant elements and the ions derived therefrom which possess no unpaired electrons.
  • manganese in the compound Li-A y Mn, 0 2 is generally present in the +3 valent state, which has four unpaired electrons.
  • Mn 3+ is not encompassed by this definition, and indeed Mn 3+ is recognized as an ion with strong magnetic interactions, usually leading to an antiferromagnetic state.
  • Non-magnetic ions also may be identified by the tendency of the metal ion to form non-magnetic metal oxides.
  • Figure 3 is a schematic illustration of a secondary cell incorporating the lithium manganese oxide compound of the invention.
  • the present invention identifies previously unknown Li(M, Mn)0 2 compositions which favor the layered structure.
  • the compound has the formula Li x (M y Mn 1 . y )0 2 , where x is 0.6 ⁇ x ⁇ 1.1 and 0.05 ⁇ y ⁇ 0.5, and where M is selected from the group selected from B, Ga, In, Ru, Os, Rh, Ir, Pd, Pt, Na, K, Rb, Group 2a, Group 3a, Group 4a, Group 5a, Group 6a, Group lb,
  • dopant levels for M are in the range of 0.05 ⁇ y ⁇ 0.15.
  • M is chosen from the group of Ga, In, Na, K, Rb, Si, Group 2a, Group 4a, and Group 2b.
  • the present invention demonstrates that, contrary to current belief, the size of the metal ion dopant is not an important factor in determining the stability of the layered lithium manganese oxides structure. It is observed that for layered LiCo0 2 and LiNi0 2 , the radii of Co 3+ and Ni 3+ are 0.545A and 0.560A, respectively (R.D. Shannon, Ada Crystall. Sec.
  • the present invention has identified the ability of the dopant, M, to disrupt the antiferromagnetic state of the Mn 3+ ion of LiMn0 2 as one of the defining characteristics in determining a stable layered Li(M, Mn)0 2 .
  • Figure 2 shows the calculated energy difference between orthorhombic (ortho) and layered (LA) LiMn0 2 structures in which the Mn 3+ is primarily non-magnetic 12, primarily ferromagnetically (FM) aligned 14 and primarily anti ferromagnetically (AF) aligned 16.
  • antiferromagnetism in itself may not be responsible for the stability of the orthorhombic structure, but rather the electron localization caused by antiferromagnetic alignment.
  • Antiferromagnetism promotes ordered arrangement of the magnetic moments of the ions such that the vector sum of the moments is zero. This order restricts the movement of electrons and prevents electron hopping or other modes of electron delocalization.
  • the layered LiMn0 2 may be stabilized by incorporating dopants into the solid state structure that perturb the antiferromagnetic ordering of the Mn 3+ ions and/or increase electron hopping or delocalization.
  • the present invention provides compositions in which the antiferromagnetic cation-cation interaction is perturbed leading to the stabilization of the layered crystal structure.
  • antiferromagnetic cation-cation interaction may be perturbed in a variety of ways.
  • non-magnetic ions may be substituted for Mn in the LiMn0 2 lattice.
  • Non-magnetic ions introduce disorder between the magnetic moments of the Mn ions and thereby lower the degree of antiferromagnetic ordering.
  • the strength of the antiferromagnetic ordering can be deduced from magnetic susceptibility measurements, as in Greeden et al, Solid State Chem. 128:209 (1997), the contents of which are hereby incorporated by reference.
  • the Neel temperature, ⁇ p can be measured. Neel temperatures greater than -1056 K are indicative of perturbation of the antiferromagnetic ordering of the Mn 3+ cations.
  • Suitable non-magnetic ions may be selected from elements of the Na, K, Rb, Ga, In, Group 2a, Group 3a, Group 4a, Group 5a, Group 4b or Group 5b elements of the periodic table.
  • elements that themselves form magnetic oxide but which are expected to perturb the Mn-Mn antiferromagnetic interactions may be used.
  • Cr 3+ while having a small magnetic moment is expected to be effective in stabilizing the layered phase.
  • ions having a valence highter than +3 may be substituted for Mn in the LiMn0 2 lattice of compounds of the formula Li x M y Mn,. y 0 2 or Li x M y Mn 2 0 2 .
  • ions having a valence of lower than +3 may be substituted for Mn 3+ in the LiMn0 2 lattice structure of compounds of the formula Li x M y Mn 2 0 2 or Li x M y Mn 2 0 2 .
  • Suitable elements expected to have ions with valences of lower than +3 include, but are not limited to those of Na, K, Rb, Ru, Rh, Os, Ir, Pt, Pd, Group 2a, Group lb and Group 2b of the periodic table.
  • lithium ion it is possible for lithium ion to additionally substitute for Mn 3+ in combination with M, e.g., Li j -M ⁇ -i-Mn, 0 2 .
  • Li 1+ contributes no more than 50% of the total ion substitution of the Mn-lattice sites, and preferably no more than 35%, and more preferably about 10-35% of the total ion substitution at the Mn-lattice sites.
  • Substitution by lithium at the manganese lattice site in no way alters the value of x in the formula, Li-.M y Mn. O 2 _ Stated differently, the degree of lithium ion substitution on the manganese sites does not affect the level of lithium substitution in the layers of the layered structure.
  • the substituting cation should have sufficient solubility in LiMn0 2 so that it can modify the stability of LiMn0 2 towards the layered structure.
  • solubility should be at least 5 %.
  • the ionic radius of the cation substitution should be close to that of Mn 3+ , and preferably iii the range of 0.5 to 0.75 A. Among possible choices for substitution, it is preferred — all else being equal — a smaller radius ion is preferred.
  • perturbation of the antiferromagnetic interactions between the Mn ions can be achieved by substituting different anions for oxygen. This will favor the layered structure since the antiferromagnetic coupling between Mn ions has contributions from the so-called superexchange type, which is mediated by the anion.
  • Suitable elements expected to have ions with valences of more negative than 0 include, but are not limited to those of Group la, Group 5b, Group 6b, and Group 7b of the periodic table.
  • the compound may have the formula Li x Mn(O x ,Z y ) 2 where 0.05 ⁇ y ⁇ 0.5 and x + y approximately equals one.
  • the compounds of the invention may prepared by any conventional means used to prepared solid solutions of mixed metal oxides.
  • the compound may be prepared by mixing or coprecipitation of mixed metal salts, followed by sintering at elevated temperatures.
  • the lithium manganese oxide is in the layered or ⁇ -NaFe0 2 -type form or phase and other phases are desirably excluded. This may be accomplished during the formation of the layered phase by using proper stoichiometry in the reaction materials used in forming the layered phase and in controlling the reaction temperature and oxygen partial pressure during the reaction.
  • the crystal structure of the resultant metal oxide is readily determined using conventional solid state investigation techniques, such as X-ray diffraction analysis.
  • a cathode for use in a electrochemical cell, such as a battery
  • the active cathode material comprises the layered doped lithium manganese oxide of the invention, having in its simplest form the formula Li x M y Mn_ .y 0 2 , wherein M is selected from the group selected from Ga, In, Mo, W, Ru, Os, Rh, Ir, Pd, Pt, Na, K, Rb, Group 2a, Group 4a, Group 5a, Group lb, Group 2b, Group 4b and Group 5b and combinations thereof, x is in the range of 0.6 to 1.1, and 0.05 ⁇ y ⁇ 0.5.
  • the amount of lithium in the cathode material will change as the state of charge is varied during use.
  • the cathode may also include a solid electrolyte and/or binder.
  • the layered lithium manganese oxide cathode may be used in a secondary cell such as illustrated in Figure 2.
  • the cell includes a casing 20 which may be an insulating material or a metal. When the casing is a metal, it may include a current collector 22 for either the anode or cathode of the cell. In addition, the casing may include an insulating layer 24 to electrically isolate the casing from the interior of the cell.
  • the cell further includes an lithium metal or other anode 26 which is separated from the lithium manganese oxide cathode 28 of the invention by a separator 30.
  • Example 1 Doping with a +3 valent cation.
  • Li(V 025 Mn 075 )0 2 may be synthesized by reacting the stoichiometric amounts of Li 2 C0 3 with Mn 3 0 4 and V0 2 at 900 °C and P 02 less than 10 "5 atm. Reducing conditions are required to obtain the Mn 3+ oxidation state. The difference in the energies of formation between the layered and orthorhombic Li(V 025 Mn 075 )0 2 structures is -35 meV, indicating that formation of the layered structure is favored.
  • Example 2 Doping with a 2+ valent cation.
  • Li(Zn 025 Mn 075 )0 2 may be synthesized by reacting the stoichiometric amounts of Li 2 C0 3 with Mn 3 0 4 and ZnO.
  • the difference in the energies of formation between the layered and orthorhombic Li(Zn 025 Mn 075 )0 2 structures is -47 meV, indicating that formation of the layered structure is favored. This example further illustrates that large ions can be used to stabilize the layered structure.
  • Example 3 Doping with a 4+ valent cation.
  • Li(Ti 025 Mn 075 )0 2 may be synthesized by reacting the stoichiometric amounts of Li 2 C0 3 with Mn 3 0 4 and Ti0 2 .
  • the difference in the energies of formation between the layered and orthorhombic Li(Ti 025 Mn 075 )0 2 structures is -67 meV, indicating that formation of the layered structure is favored.
  • Fe 3+ being an antiferromagnetic ion, is not expected to perturb the energy state of Mn 3+ . Indeed, the differences in energies of formation between the iron-doped and the undoped structure are negligible.

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Abstract

A layered LixMyMn1-yO2 compound wherein M is selected from the group selected from B, Ga, In, Ru, Os, Rh, Ir, Pd, Pt, Na, K, Rb, Group 2a, Group 3a, Group 4a, Group 5a, Group 6a, Group 1b, Group 2b, Group 4b and Group 5b and combinations thereof, x is in the range of 0.6 to 1.1, and 0.05 ≤ y ≤ 0.5.

Description

LAYERED LITHIUM MANGANESE COMPOUNDS
Background of the Invention
The present invention relates to lithium manganese oxide insertion compounds. In particular, the invention relates to lithium manganese oxide compounds in the layered R3m structure. In addition, it pertains to rechargeable batteries and the use of these insertion compounds as cathode materials.
Insertion compounds are those which are capable of reversibly introducing an element, molecule or other species ("intercalant") into a host structure. While the compound may distort somewhat upon introduction of the intercalant into the host lattice structure, the compound regains its original structure upon deintercalation. This process has been exploited in the battery industry to provide rechargeable lithium batteries.
Lithium ion secondary batteries are known to give high voltages and to have high discharge capacities. A popular rechargeable lithium battery, produced by Sony Corporation and others, consists of a carbon-based negative electrode and a layered LiCo02 material as the positive electrode in a non- aqueous electrolyte. While providing a high electrical capacity, LiCo02 suffers from the disadvantages of toxicity and expense. LiMn02 is of interest as an alternative insertion electrode material in lithium secondary cells because of its high theoretical capacity of 286 mAh/g and because of its relatively lower cost and non-toxicity as compared to LiCo02
Lithium manganese dioxide (LiMn02) exists in several solid state structures. When heated at elevated temperature so equilibrium conditions are achieved, LiMn02 exists in an orthorhombic Pmmm structure having an ordered rock salt lattice. However, the orthorhombic phase is unstable and undergoes irreversible phase transformation to a material with spinel-like ordering upon electrochemical cycling. LiMn02 can also be prepared as a monoclinic phase through metastable synthesis routes. The phase has an α- NaFe02-type structure in which Li+ ions are located between Mn06 sheets, giving the phase a layered arrangement which is particularly advantageous in the reversible insertion of lithium into the compound. Due to Jahn-Teller distortion around Mn3+, the symmetry is monoclinic.
Many attempts have been made to prepare layered LiMn02 from aqueous solution, however, the product tends to have stoichiόmetries which differ from LiMn02, which are of poor crystallinity or which are unstable during electrochemical cycling. United States Patent No. 5,558,961 describes an orthorhombic MxZyMn1_y02, where M is an alkali metal and Z is a metal capable of substituting for Mn in the orthorhombic structure; however, there is no discussion of layered LiMn02 compounds. Similarly, United States Patent No. 5,561,006 also describes an orthorhombic LiMn02 compound.
Armstrong and Bruce report preparation of the layered LiMn02 compound by lithium ion-exchange from the sodium manganese oxide (NaMn02) (Nature, 381:499 (June, 1996)); however, the compound is metastable and only a fraction of the theoretical capacity is realized upon repeated electrochemical cycling. Compositions for which the layered phase is metastable are not attractive, since they can not be prepared using conventional methods.
Jang et al. report the formation of LiAlxMn1.x02 solid solutions which crystallize in the α-NaFe02 structure (Electrochem. Solid State Lett. 1(1): 13 (May, 1998)). The use of aluminum as an addition to LiMn02 to stabilize the layered structure can easily be understood since LiA102 is layered. Hence, when added to LiMn02 it enhances the tendency to form a layered structure. Unfortunately, Li(AlxMn1.x)02 does not retain the layered structure, but rather transforms to spinel upon cycling. While this example of LiMn02 doping is of interest, it fails to provide the robust and high capacity materials sought by the battery industry. Thus, there is a need for other layered LiMn02-based compounds which are stable and suitable for use in lithium batteries.
Summary of the Invention In one aspect of the invention, a layered LixMyMn,.y02 compound is provided in which M is selected from the group selected from B, Ga, In, Ru, Os, Rh, Ir, Pd, Pt, Na, K, Rb, Group 2a, Group 3a, Group 4a, Group 5a, Group 6a, Group lb, Group 2b, Group 4b and Group 5b and combinations thereof, x is in the range of 0.6 to 1.1, and 0.05 < y < 0.5.
In another aspect of the invention, a lithium manganese oxide of the formula,
LixMyMn,.y02 has an α-NaMn02-type structure or distorted variant thereof. M is a metal selected from the group consisting of B, Ga, In, Ru, Os, Rh, Ir, Pd, Pt, Na, K, Rb, Group 2a, Group 3a, Group 4a, Group 5a, Group 6a, Group lb, Group 2b, Group 4b and Group 5b and combinations thereof, x is in the range of 0.6 to 1.1, and 0.05 < y < 0.5. In preferred embodiments, M is selected from the group consisting of Ga, In, Na, Rb, Si, Group 2a, Group 2b, Group 4a and combinations thereof. In more preferred embodiments, M is selected from the group consisting of Ti, Zn and Si.
In one embodiment, M is a non-magnetic element selected from the group consisting of Na, K, Rb, Ga, In, Group 2a, Group 3a, Group 4a, Group 5a, Group 4b and Group 5b, and combinations thereof.
In still another embodiments, M is a cation having a valance of greater than +3 selected from the group consisting of Group 4a, Group 5 a, Group 6a, and Group 4b elements, and combinations thereof. In a preferred embodiment, M is a cation having a valance of greater than +3 selected from the group consisting of Ge, Sn, V, Ti, and Si.
In another embodiment, M may be a cation having a valance of less than +3 selected from the group consisting of Na, K, Rb, Group 2a, Group lb, Group 2b, and combinations thereof. M may be a cation having a valance of less than +3 selected from the group consisting of Zn, Cu, and Mg and combinations thereof.
Reference to groups of elements throughout the specification are made with reference to the Periodic Table of the Elements found in Figure 1.
Unlike LiCo02 and NaFe02, which are rhombohedral (R3m), LiMn02 is distorted due to Jahn-Teller effects into monoclinic C2/m symmetry. Hereinafter, reference to a "layered structure" encompasses both the rhombohedral and monoclinic layered structures and other distorted variants thereof.
By "non-magnetic element" and "non-magnetic ions" as those terms are used herein it is meant elements and the ions derived therefrom which possess no unpaired electrons. For example, manganese in the compound Li-A yMn, 02 is generally present in the +3 valent state, which has four unpaired electrons. Thus, Mn3+ is not encompassed by this definition, and indeed Mn3+ is recognized as an ion with strong magnetic interactions, usually leading to an antiferromagnetic state. Non-magnetic ions also may be identified by the tendency of the metal ion to form non-magnetic metal oxides. Thus, titanium is considered a non-magnetic element, in any valence state, as titanium oxides are never found to be magnetic. In contrast, iron, chromium and nickel which form strongly magnetic metal oxides are not considered "nonmagnetic" elements within the scope of the present invention. Brief Description of the Drawing The invention is described with reference to the Figures which are presented for illustration purposes only and in which: Figure 1 is a Periodic Table of the Elements; Figure 2 is a plot of calculated formation energies for LiMn02 having Mn3+ ions which are non-magnetic, ferromagnetically aligned and antiferromagnetically aligned; and
Figure 3 is a schematic illustration of a secondary cell incorporating the lithium manganese oxide compound of the invention.
Description of the Preferred Embodiments
The present invention identifies previously unknown Li(M, Mn)02 compositions which favor the layered structure. The compound has the formula Lix(MyMn1.y)02, where x is 0.6 < x < 1.1 and 0.05 < y < 0.5, and where M is selected from the group selected from B, Ga, In, Ru, Os, Rh, Ir, Pd, Pt, Na, K, Rb, Group 2a, Group 3a, Group 4a, Group 5a, Group 6a, Group lb,
Group 2b, Group 4b and Group 5b. In preferred embodiments dopant levels for M are in the range of 0.05 < y < 0.15. In other preferred embodiments, M is chosen from the group of Ga, In, Na, K, Rb, Si, Group 2a, Group 4a, and Group 2b. The present invention demonstrates that, contrary to current belief, the size of the metal ion dopant is not an important factor in determining the stability of the layered lithium manganese oxides structure. It is observed that for layered LiCo02 and LiNi02, the radii of Co3+ and Ni3+ are 0.545A and 0.560A, respectively (R.D. Shannon, Ada Crystall. Sec. A, A32:751 (1976)), which are significantly smaller than that of Li+ ion (0.76A). One could deduce that any M3+ion forming an ionic solid with lithium ion which is the same as or larger than Li+ would not help in the stabilization of the layer structure. Indeed, a state of the art review of the structure of lithium metal oxides advocates such belief. See, Hewston and Chamberland, J. Phys. Chem. Solids 48:97 (1987). The present invention has surprisingly discovered that M3+ ionic size is not an important factor in predicting the stability of resultant layered structures. The present invention has identified the ability of the dopant, M, to disrupt the antiferromagnetic state of the Mn3+ ion of LiMn02 as one of the defining characteristics in determining a stable layered Li(M, Mn)02. Figure 2 shows the calculated energy difference between orthorhombic (ortho) and layered (LA) LiMn02 structures in which the Mn3+ is primarily non-magnetic 12, primarily ferromagnetically (FM) aligned 14 and primarily anti ferromagnetically (AF) aligned 16. The calculations used to generate the data shown in Figure 2 were performed with first-principles quantum mechanical methods in soft-pseudopotential approximations as implemented in the program VASP (Kresse and Furthmϋller, Comput. Mat. Sci. 6:15 (1996)), the accuracy of which has been well-established. The energy differences for the various constructs are shown. As is confirmed in nature, the antiferromagnetic Mn3+ ions favor the orthorhombic structure (data points 16). Surprisingly, the order of stability between the orthorhombic and layered structures is reversed for non-magnetic and ferromagnetic Mn ions, leading to a stabilized layered LiMn02 structure.
It is recognized that antiferromagnetism in itself may not be responsible for the stability of the orthorhombic structure, but rather the electron localization caused by antiferromagnetic alignment. Antiferromagnetism promotes ordered arrangement of the magnetic moments of the ions such that the vector sum of the moments is zero. This order restricts the movement of electrons and prevents electron hopping or other modes of electron delocalization. Thus, the layered LiMn02 may be stabilized by incorporating dopants into the solid state structure that perturb the antiferromagnetic ordering of the Mn3+ ions and/or increase electron hopping or delocalization.
The present invention provides compositions in which the antiferromagnetic cation-cation interaction is perturbed leading to the stabilization of the layered crystal structure. According to the invention, antiferromagnetic cation-cation interaction may be perturbed in a variety of ways.
In one aspect of the invention, non-magnetic ions may be substituted for Mn in the LiMn02 lattice. Non-magnetic ions introduce disorder between the magnetic moments of the Mn ions and thereby lower the degree of antiferromagnetic ordering. The strength of the antiferromagnetic ordering can be deduced from magnetic susceptibility measurements, as in Greeden et al, Solid State Chem. 128:209 (1997), the contents of which are hereby incorporated by reference. For example, the Neel temperature, θp, can be measured. Neel temperatures greater than -1056 K are indicative of perturbation of the antiferromagnetic ordering of the Mn3+ cations. Suitable non-magnetic ions may be selected from elements of the Na, K, Rb, Ga, In, Group 2a, Group 3a, Group 4a, Group 5a, Group 4b or Group 5b elements of the periodic table. In addition to non-magnetic elements, elements that themselves form magnetic oxide but which are expected to perturb the Mn-Mn antiferromagnetic interactions may be used. For example, Cr3+ while having a small magnetic moment is expected to be effective in stabilizing the layered phase.
In another aspect of the invention, the compound may have the formula LixMyMnz02, where x + ay + bz = 4 (total valence of Li and Mn sites) is approximately equal to one and where a and b are the valence states of M and Mn, respectively. In one embodiment, ions having a valence highter than +3 may be substituted for Mn in the LiMn02 lattice of compounds of the formula LixMyMn,.y02 or LixMyMn202. Valanced difference form may be used in order to satisfy the equation x + ay + bz = 4. These ions create extra electrons in the material which will tend to make the electronic state more itinerant, rather than localized. More itinerant electrons tend to lower the magnetic moments on the ions. Suitable elements expected to have ions with valences of greater than +3 include, but are not limited to those of Group 4a, Group 5a, Group 6a and Group 4b of the periodic table. Particulary interesting compositions include but are not limited to Ge4+= (r=0.53 A), Sn4+ (r=0.69A), V4+ (r=0.53 A) and Si4+ (r=0.4A).
In another embodiment of the invention, ions having a valence of lower than +3 may be substituted for Mn3+ in the LiMn02 lattice structure of compounds of the formula LixMyMn202 or LixMyMn202. Such valances difference for m may be used in order to satisfy the equation x + ay + bz = 4. These ions create extra holes in the material which also tend to make the electronic state more itinerant, rather than localized. More itinerant holes tend to lower the magnetic moments on the ions. Suitable elements expected to have ions with valences of lower than +3 include, but are not limited to those of Na, K, Rb, Ru, Rh, Os, Ir, Pt, Pd, Group 2a, Group lb and Group 2b of the periodic table. Particularly interesting compositions include but are not limited to Zn2+ (r=0.74A), Cu2+ (ι=0.73A), Mg2+ (r=0.72A). Note that these compositions are predicted to form layered structures although the ionic radii of the cations are of a size comparable to Li+. In all of the above embodiments, it is possible for lithium ion to additionally substitute for Mn3+ in combination with M, e.g., Lij-M^-i-Mn, 02. In those instances in which Li ion substitutes for Mn3+, Li1+ contributes no more than 50% of the total ion substitution of the Mn-lattice sites, and preferably no more than 35%, and more preferably about 10-35% of the total ion substitution at the Mn-lattice sites. Substitution by lithium at the manganese lattice site in no way alters the value of x in the formula, Li-.MyMn. O2_ Stated differently, the degree of lithium ion substitution on the manganese sites does not affect the level of lithium substitution in the layers of the layered structure.
In all of the above embodiments, the substituting cation should have sufficient solubility in LiMn02 so that it can modify the stability of LiMn02 towards the layered structure. In preferred embodiments, solubility should be at least 5 %. In preferred embodiments, therefore, the ionic radius of the cation substitution should be close to that of Mn3+, and preferably iii the range of 0.5 to 0.75 A. Among possible choices for substitution, it is preferred — all else being equal — a smaller radius ion is preferred.
In yet another aspect of the invention, perturbation of the antiferromagnetic interactions between the Mn ions can be achieved by substituting different anions for oxygen. This will favor the layered structure since the antiferromagnetic coupling between Mn ions has contributions from the so-called superexchange type, which is mediated by the anion. Suitable elements expected to have ions with valences of more negative than 0 include, but are not limited to those of Group la, Group 5b, Group 6b, and Group 7b of the periodic table. In particular, the compound may have the formula LixMn(Ox,Zy)2 where 0.05 < y < 0.5 and x + y approximately equals one.
The compounds of the invention may prepared by any conventional means used to prepared solid solutions of mixed metal oxides. For example, the compound may be prepared by mixing or coprecipitation of mixed metal salts, followed by sintering at elevated temperatures. According to the invention, the lithium manganese oxide is in the layered or α-NaFe02-type form or phase and other phases are desirably excluded. This may be accomplished during the formation of the layered phase by using proper stoichiometry in the reaction materials used in forming the layered phase and in controlling the reaction temperature and oxygen partial pressure during the reaction. The crystal structure of the resultant metal oxide is readily determined using conventional solid state investigation techniques, such as X-ray diffraction analysis.
In another aspect of the invention, a cathode for use in a electrochemical cell, such as a battery, is provided. The active cathode material comprises the layered doped lithium manganese oxide of the invention, having in its simplest form the formula LixMyMn_.y02, wherein M is selected from the group selected from Ga, In, Mo, W, Ru, Os, Rh, Ir, Pd, Pt, Na, K, Rb, Group 2a, Group 4a, Group 5a, Group lb, Group 2b, Group 4b and Group 5b and combinations thereof, x is in the range of 0.6 to 1.1, and 0.05 < y < 0.5. The amount of lithium in the cathode material will change as the state of charge is varied during use. The cathode may also include a solid electrolyte and/or binder.
The layered lithium manganese oxide cathode may be used in a secondary cell such as illustrated in Figure 2. The cell includes a casing 20 which may be an insulating material or a metal. When the casing is a metal, it may include a current collector 22 for either the anode or cathode of the cell. In addition, the casing may include an insulating layer 24 to electrically isolate the casing from the interior of the cell. The cell further includes an lithium metal or other anode 26 which is separated from the lithium manganese oxide cathode 28 of the invention by a separator 30.
The invention is described in the following examples which are illustrative of the invention only and in no way limiting of the invention.
Example 1. Doping with a +3 valent cation.
Li(V025Mn075)02 may be synthesized by reacting the stoichiometric amounts of Li2C03 with Mn304 and V02 at 900 °C and P02 less than 10"5 atm. Reducing conditions are required to obtain the Mn3+ oxidation state. The difference in the energies of formation between the layered and orthorhombic Li(V025Mn075)02 structures is -35 meV, indicating that formation of the layered structure is favored. Example 2. Doping with a 2+ valent cation.
Li(Zn025Mn075)02 may be synthesized by reacting the stoichiometric amounts of Li2C03 with Mn304 and ZnO. The difference in the energies of formation between the layered and orthorhombic Li(Zn025Mn075)02 structures is -47 meV, indicating that formation of the layered structure is favored. This example further illustrates that large ions can be used to stabilize the layered structure.
Example 3. Doping with a 4+ valent cation.
Li(Ti025Mn075)02 may be synthesized by reacting the stoichiometric amounts of Li2C03 with Mn304 and Ti02. The difference in the energies of formation between the layered and orthorhombic Li(Ti025Mn075)02 structures is -67 meV, indicating that formation of the layered structure is favored.
Example 4-10.
Additional calculations were performed to determine the relative energies of formation for the layered and orthorhombic forms for a variety of other dopant elements. The results are found in the Table.
Figure imgf000014_0001
These results are consistent with observed behavior of these dopant ions. Fe3+, being an antiferromagnetic ion, is not expected to perturb the energy state of Mn3+. Indeed, the differences in energies of formation between the iron-doped and the undoped structure are negligible.
What is claimed is:

Claims

1. A layered Li_.MyMn._yO2 compound wherein M is selected from the group selected from B, Ga, In, Ru, Os, Rh, Ir, Pd, Pt, Na, K, Rb, Group 2a, Group 3a, Group 4a, Group 5a, Group 6a, Group lb, Group 2b, Group 4b and Group 5b and combinations thereof, x is in the range of 0.6 to 1.1, and 0.05 < y < 0.5.
2. A lithium manganese oxide of the formula,
LixMyMn_.y02 wherein said oxide has an α-NaMn02-type structure or distorted variant thereof and wherein M is a metal selected from the group consisting of B, Ga, In, Ru, Os, Rh, Ir, Pd, Pt, Na, K, Rb, Group 2a, Group 3a, Group 4a, Group 5a, Group 6a, Group lb, Group 2b, Group 4b and Group 5b and combinations thereof, x is in the range of 0.6 to 1.1, and 0.05 < y < 0.5.
3. The lithium manganese oxide of claim 1 or 2, wherein Li may additionally substitute for Mn in combination with M.
4. The lithium manganese oxide of claim 3, wherein Li contributes no more than 50% of the total ion substitution for Mn.
5. The lithium manganese oxide of claim 3, wherein Li contributes in the range of 10-35% of the total ion substitution for Mn.
6. The lithium manganese oxide of claim 1 or 2, wherein M is selected to perturb the antiferromagnetic ordering of the Mn ions.
7. The lithium manganese oxide of claim 1 or 2, wherein M is a non-magnetic element selected from the group consisting of Na, K, Rb, Ga, In, Group 2a, Group 3a, Group 4a, Group 5a, Group 4b and Group 5b, and combinations thereof.
8. The lithium manganese oxide of claim 1 or 2, wherein M is selected from the group consisting of Ga, In, Na, Rb, Si, Group Si, Group 2a, Group 2b, and Group 4a, and combinations thereof.
9. A layered lithium manganese oxide of the formula,
LixMyMnz02 wherein M is selected from the group selected from B, Ga, In, Ru, Os, Rh, Ir, Pd, Pt, Na, K, Rb, Group 2a, Group 3a, Group 4a, Group 5a, Group 6a, Group lb, Group 2b, Group 4b and Group 5b and combinations thereof, where x is in the range of 0.6 to 1.1, and 0.05 ≤ y ≤ 0.5, where a and b are valence for M and Mn, respectively, and where x + ay + bz is about 4.
10. The lithium manganese oxide of claim 1, 2 or 9, wherein M is a cation having a valence of greater than +3 selected from the group consisting of Group 4a, Group 5a, Group 6a, and Group 4b elements, and combinations thereof.
11. The lithium manganese oxide of claim 1 , 2 or 9, wherein M is a cation having a valence of greater than +3 selected from the group consisting of Ge, Sn, V, Ti, and Si.
12. The lithium manganese oxide of claim 1, 2 or 9 wherein M is a cation having a valence of less than +3 selected from the group consisting of Na, K, Rb, Group 2a, Gourp lb, Group 2b, and combinations thereof.
13. The lithium manganese oxide compound of claim 1, 2 or 9 wherein M is a cation having a valence of less than +3 selected from the group consisting of Zn, Cu, and Mg and combinations thereof.
14. The lithium manganese oxide compound of claim 1 or 2, wherein
M is selected from the group consisting of Ti, Zn and Si.
15. The lithium manganese oxide of claim 1 or 2, wherein M comprises titanium.
16. The lithium manganese oxide of claim 1 or 2, wherein 0.05 < y
<0.15.
17. The lithium manganese oxide compound of claim 1, 2, or 9, wherein the layered compound further includes substitution for oxygen by an element Z, wherein Z is selected from the group consisting of elements of Group 5b, Group 6b and Group 7b, and combinations thereof.
18. The lithium manganese oxide compound of claim 7, wherein the layered compound further includes substitution for oxygen by an element Z, wherein Z is selected from the group consisting of elements of Group 5b, Group 6b and Group 7b, and combinations thereof.
19. The lithium manganese oxide compound of claim 17, wherein Z substitutes for oxygen in the range of 5 to 50 percent.
20. The lithium manganese oxide compound of claim 18, wherein Z substitutes for oxygen in the range of 5 to 50 percent.
21. An electrochemical cell having a positive electrode, a negativeelectrode separated by an electrolyte, wherein the positive electrode is comprised of the layered lithium manganese oxide compound of claim 1 , 2 or 9.
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