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WO1999056331A1 - Composes d'intercalaire et electrodes pour batteries - Google Patents

Composes d'intercalaire et electrodes pour batteries Download PDF

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Publication number
WO1999056331A1
WO1999056331A1 PCT/US1999/009384 US9909384W WO9956331A1 WO 1999056331 A1 WO1999056331 A1 WO 1999056331A1 US 9909384 W US9909384 W US 9909384W WO 9956331 A1 WO9956331 A1 WO 9956331A1
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Prior art keywords
oxide
intercalation
compound
particles
lithium
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English (en)
Inventor
Yet-Ming Chiang
Donald R. Sadoway
Young-Il Jang
Biying Huang
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Massachusetts Institute of Technology
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Massachusetts Institute of Technology
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Priority to JP2000546406A priority Critical patent/JP2002513198A/ja
Priority to EP99921547A priority patent/EP1080506A1/fr
Priority to AU38732/99A priority patent/AU3873299A/en
Publication of WO1999056331A1 publication Critical patent/WO1999056331A1/fr
Priority to US09/686,331 priority patent/US6787232B1/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • 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
    • C01G45/1242—Manganates or manganites with trivalent manganese, tetravalent manganese or mixtures thereof of the type (Mn2O4)-, e.g. LiMn2O4 or Li(MxMn2-x)O4
    • 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
    • H01M4/36—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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/77—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by unit-cell parameters, atom positions or structure diagrams
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • 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

Definitions

  • the present invention relates to intercalation compounds for use as electrodes for batteries, and in particular metal ion doped lithium manganese oxide compositions, articles manufactured with such compositions, and batteries including electrodes formed from such compositions.
  • Li x M y N z O 2 wherein M and N are each a metal atom or main group element, and methods for synthesizing such compositions which are demonstrated to have improved electrochemical properties.
  • WO 98/16960 at least insofar as it relates to intercalation compounds, is incorporated herein by reference. The present inventors have continued to investigate lithium intercalation compounds to identify new compounds with further improved properties for use in batteries.
  • composition including particulate metal oxide material including a plurality of particles of multicomponent metal oxide, each including an oxide core of at least first and second metals in a first ratio, and each including a surface coating of metal oxide or hydroxide that does not include the first and second metals in the first ratio formed by segregation of at least one of the first and second - metals from the core.
  • compositions including particulate metal oxide material including particles of a multicomponent metal oxide, each including an oxide core of at least first and second metals in a first ratio, and each including a surface coating of metal oxide or hydroxide that does include the first and second metals in the first ratio formed by application of an auxiliary metal oxide or hydroxide to the particles, and the cores comprise Li x M y N z O 2 , wherein M is a metal atom or a main group element, N is a metal atom or a main group element, each of x, y and z is a number from about 0 to about 1, y and z are such that a formal charge on a M y N z portion of the compound is (4- x), and having a charging voltage of at least about 2.5V.
  • an article including particles as referred to in the previous two paragraphs, wherein the particles are ion intercalation particles at least some of which are in contact with an electrically-conductive material and an ionically-conductive material.
  • a method including allowing a first component of a multicomponent oxide based intercalation compound to segregate from a plurality of particles of the compound disproportionately to the surfaces of the plurality of particles to form protective layers of the first component on the particles; exposing the plurality of the particles to chemically degrading conditions; and allowing the layers to shield the particles from the chemically degrading conditions such that the particles exhibit robustness, under the conditions, greater than identical particles absent the layers.
  • a multicomponent oxide useable as a lithium intercalation material including a multiphase oxide core and a surface layer of one material, which is a component of the multiphase oxide core, that protects the underlying intercalation material from chemical dissolution or reaction.
  • a multicomponent oxide into which lithium can be reversibly intercalated and in which part or all of one constituent of the multicomponent oxide spontaneously forms a surface layer which protects the underlying intercalation compound against chemical dissolution or reaction.
  • an electrode for a primary lithium battery having at least one component, at least one component having a LixAlyMn ! . y O 2 orthorhombic structure, wherein y is non zero.
  • the composite intercalation material comprises at least two compounds. At least one compound has an orthorhombic structure Li x Al y Mn 1-y O 2 , where y is nonzero.
  • a composite intercalation material comprising at least two compounds has at least one compound, which upon electrochemical cycling, has a transformation in the voltage vs. capacity curve from a single plateau at about 4 V to two plateaus at about 4 V and 3 V respectively.
  • a composite intercalation material comprising at least two compounds has at least one compound having a discharge capacity of at least about 100 mAh g over the voltage range 2.0-4.4 V, and an energy density of at least about 400 Wh/kg after 50 cycles.
  • a composite intercalation compound containing at least two individual intercalation compounds where each compound has a different lithium chemical diffusion rate and a voltage vs. capacity profile that varies more continuously than the voltage vs. capacity profile of any noncomposite intercalation compound.
  • a composite intercalation compound containing at least two individual intercalation compounds where each compound has a different particle size and a voltage vs. capacity profile that varies more continuously than the voltage vs. capacity profile of any noncomposite intercalation compound.
  • Figure 1 shows powder X-ray diffraction patterns of LiAl y Mn,. y O 2 prepared according to Example 1 after firing for 2 h at 945 °C in various oxygen partial pressures (filled circles: m-LiMnO 2 with hkl indicated; *: ⁇ -LiMnO 2 ; +: LiMn 2 O 4 ; unfilled circles: Li 2 MnO 3 ; unfilled squares; - LiAlO 2 ).
  • Figure 2 shows simulated X-ray diffraction patterns for (a) -LiMnO 2 (b) m- LiAl 025 Mn 075 O 2 and (c) Li 2 Mn 2 O 4 compared with (d) the experimental pattern for LiAl 025 Mno 75 O 2 prepared according to Example 1.
  • Figure 4 shows a photocopy of a bright-field scanning transmission electron microscopy image of powder particles of w-LiAl 005 Mno 95 O 2 prepared according to Example 1 along with energy dispersive X-ray maps showing Al and Mn distributions.
  • Figures 5 and 6 show a photocopy of a bright field scanning transmission electron microscopy images of powder particles of m-LiAl 025 Mno 75 O 2 prepared according to Example 1 after storage at room temperature for six months, along with energy dispersive X-ray maps showing Al and Mn distributions.
  • Figure 7 compares powder X-ray diffraction patterns of -LiAl 025 Mn 075 O 2 prepared according to Example 1 before and after storage at room temperature for six months.
  • Figure 8 shows the charge-discharge curves for an electrochemical test cell containing m-LiAl 025 Mno 75 O 2 according to Example 1 at 0.4 mA/cm 2 current density (c/5 rate) between 2.0 and 4.4 V, on (a) cycle 1 , and (b) cycle 20.
  • Figure 9 shows the specific capacity vs. cycle number for an electrochemical test cell containing -LiAl 025 Mno 75 O 2 according to Example 1, at 0.4 mA/cm 2 current density (c/5 rate) between 2.0 and 4.4 V.
  • Figure 10 shows discharge curves at C/5 and C/15 rates for an electrochemical test cell containing m-Li Al 025 Mno 75 O 2 cycled as described in Example 1.
  • Figure 11 shows voltage vs. time results for an electrochemical test cell containing m- LiAl 025 Mn 075 O 2 cycled at 60 °C and then 70 °C as described in Example 1.
  • Figure 12 shows the specific capacity vs. cycle number for an electrochemical test cell containing m-LiAl 025 Mno 75 O 2 according to example 1, at room temperature (23 °C) and 55 °C.
  • Figure 13 shows the first charge-discharge curve at 55 °C for an electrochemical test cell containing w-LiAl 005 Mno 95 O 2 according to Example 1.
  • Figure 14 shows the charge-discharge curve at 55 °C, cycle 6, for an electrochemical test cell containing -LiAl 0 osMno 95 O 2 according to Example 1.
  • Figure 15 shows the charge-discharge curve at 55 °C, cycle 17, for an electrochemical test cell containing w-LiAl 0 osMrio 95 O 2 according to example 1.
  • Figure 16 shows the charge-discharge curve at 55° C, cycle 34, for an electrochemical test cell containing -LiAl 0 osMno 95 O 2 according to Example 1.
  • Figure 17 shows the specific capacity vs. cycle number for electrochemical test cells containing m-LiAl 025 Mno 75 O 2 and m-LiAl 005 Mno 95 O 2 cycled at 55 °C according to Example 1.
  • Figure 19 shows the powder X-ray diffraction pattern of a composition m-
  • LiAl 005 Mno 95 O 2 fired 2 h at 900 °C and P 02 10 "10 atm, according to Example 2.
  • Figure 20 shows the specific capacity vs. cycle number for an electrochemical test cell containing m-LiAl 005 Mno 95 O 2 cycled at 55 °C according to Example 2.
  • Figure 21 shows the first charge-discharge curve at 55 °C for an electrochemical test cell containing r ⁇ -LiAl 0 Q 5 M ⁇ Q 95 O 2 according to Example 2.
  • Figure 22 shows the charge-discharge curve at 55 °C, cycle 6, for an electrochemical test cell containing m-LiAl 005 Mno 95 O 2 according to Example 2.
  • Figure 23 shows the charge-discharge curve at 55 °C, cycle 8, for an electrochemical test cell containing m-LiAl 005 Mno 95 O 2 according to Example 2.
  • Figure 24 shows the powder X-ray diffraction pattern of -LiAl 005 Mno 95 O 2 prepared according to Example 1.
  • One embodiment of the invention provides a family of intercalation compounds having the composition Li x Al y Mn,. y O 2 where y is less than about 0.5. These compounds can be used as electrodes in lithium batteries and preferably have an x value of about 1 as synthesized by methods described herein. These compounds crystallize in the monoclinic LiMnO 2 , the orthorhombic LiMnO 2 or the tetragonal spinel Li 2 Mn 2 O 4 structure types, and have other structural characteristics, and performance characteristics associated with those structural characteristics, described herein. In one compound, ions predominantly occupy sites that are octahedrally coordinated by oxygen.
  • the compounds Upon cyclic electrochemical intercalation and de-intercalation in a lithium rechargeable battery, the compounds exhibit a charge in local cation order where the Li ions thereafter occupy sites of both octahedral and tetrahedral oxygen coordination, the extent of change depending on the concentration of Li in the compound.
  • the structure of the compound attained after electrochemical cycling can be, but is not limited to, that of the cubic spinel LiMn 2 O 4 or the tetragonal spinel Li 2 Mn 2 O 4
  • the compounds of this invention exhibit a combination of useful characteristics not found in intercalation compounds typically used previously in rechargeable lithium batteries such as LiCoO 2 , LiMn 2 O 4 (cubic spinel structure), and LiNiO 2 including low materials cost, high reversible charge capacity and energy density at room temperature, high reversible charge capacity and energy density at elevated temperatures (40-70 °C), long life upon storage at elevated temperatures (40-70 °C), and safety, as manifested by the absence of highly exothermic reactions upon heating of a rechargeable lithium battery containing the compound.
  • Another embodiment of the invention also comprises any lithium battery, of primary or secondary (rechargeable) type, including those described herein, that utilizes the compounds of the invention.
  • Another embodiment of the invention comprises any mixture of the aforementioned individual Li x Al y Mn]. y O 2 compounds, and any mixtures of compounds with composition Li x Al y Mn,. y O 2 with other known intercalation compounds such as LiCoO 2 , LiAl y C ⁇ ]. y O 2 , LiNiO 2 . LiCo y Ni]. y O 2 , or LiMn 2 O 4 .
  • Such a mixture can have particular utility because of a voltage that varies more smoothly with charge capacity than is attained for certain individual compounds.
  • the value of x can approach 0 (e.g., during charging of a battery utilizing the compound as the active cathode material).
  • v has a value of between about 0.01 and about 0.5.
  • orthorhombic LiMnO 2 or " -LiMnO 2” refers to Li x MnO 2 of the orthorhombic ordered rocksalt structure described by R. Hoppe, G. Brachtel, and M. Jansen (Z. Anorg. Allg. Chemie, 471, 1 (1975)). Monoclinic Li-.ALMnj _ y O 2
  • One embodiment of this invention reflects the discovery that addition of Al to form an intercalation compound LiAl y M 1-y O 2 allows the stabilization of the ⁇ -NaFeO 2 structure type for a compound which as pure LiMO 2 is not easily formed in this structure.
  • M can be but is not limited to Mn, Fe, and Ti.
  • LiMnO 2 can be crystallized in the orthorhombic symmetry phase as a pure compound, or as the tetragonal spinel Li 2 Mn 2 O 4 by electrochemical or chemical insertion of Li into the spinel LiMn 2 O 4 , but has only been formed in the ⁇ -NaFeO 2 structure type (which in this composition has monoclinic symmetry, space group C2/m) by the ionic exchange of Li + for Na + in NaMnO 2 (A. R. Armstrong and P.G. Bruce, Nature, Vol. 381, p. 499, 1996).
  • a solid solution Li(Al, Mn)O 2 can be readily crystallized in the monoclinic variant of the ⁇ -NaFeO 2 structure type by heating in a reducing gas environment.
  • the intercalation compound LiAl y M,. y O 2 which is crystallized in the monoclinic variant of the ⁇ -NaFeO 2 structure type, forms upon electrochemical cycling an intercalation compound with two characteristic voltages of intercalation, a high energy density, and excellent cycling performance.
  • this intercalation compound can be cycled over voltage and capacity ranges which include plateaus at both about 4V and about 3 V (against a Li metal anode), similar to that of spinels based on Li-Mn-O, but without the loss of capacity upon cycling that is characteristic of previous spinels. This allows practical utilization of both voltage regimes, and consequently results in a higher practical energy density.
  • the energy density can be higher at elevated temperatures than that exhibited by the same compound at room temperature.
  • the elevated temperature stability of the compound is markedly superior to that of typical lithium manganese oxides.
  • the invention encompasses methods of making such compounds as well.
  • Example 1 Synthesis of monoclinic LiA 05 Mno 9? O 2 and LiAl 0. ⁇ M ⁇ , ⁇ ? O 2 by hydroxide precipitation and freeze-drying. and firing in a reducing gas atmosphere, structural characterization of same, and electrochemical testing of same at room temperature and elevated temperature
  • the precipitate was allowed to digest for 12 h, was settled by centrifugation, and then residual nitrate ions were removed by dispersing the precipitate in aqueous LiOH-H 2 O solution, settling the precipitate by centrifugation, and decanting of the supernatant liquid. This rinsing process was carried out five times.
  • the rinsed precipitate was dispersed a final time in an aqueous solution containing dissolved LiOH ⁇ 2 O at a concentration which yielded an overall composition with a Li to Al+Mn ratio of 1.05, and freeze-dried by spraying the suspension into liquid nitrogen, removing the frozen droplets, and freeze-drying in a commercial freeze drier (VirTis Consol 12LL, Gardiner, NY).
  • the precursor powders were fired for 2 h at 945 °C in various partial pressures of oxygen and furnace-cooled to room temperature.
  • argon, argon oxygen, or a buffered CO/CO 2 mixture By firing in argon, argon oxygen, or a buffered CO/CO 2 mixture, a high Mn 3+ fraction was obtained, and a crystal structure isomorphous with monoclinic LiMnO 2 was obtained in the Li x Al y Mn,. y O 2 .
  • Fig. 1 The structure of m-Li x Al y Mn,. y O 2 was confirmed through X-ray powder diffraction and structure simulation using commercial software. X-ray diffraction scans of the oxide powders obtained by firing the aluminum-doped precursors at 945 °C in various oxygen partial pressures are shown in Fig. 1. Considering first the composition LiAl 025 Mn 075 O 2 , at the higher oxygen partial pressures of 10 "2 and 10 "3 atm, the resulting phases are LiMn 2 O 4 , Li 2 MnO 3 and ⁇ -LiAlO 2 (tetragonal phase).
  • the simulated results are shown in Fig. 2 in comparison with the experimental XRD pattern for Li Al 0.25 Mno 75 O 2 . Differences between the three simulated patterns can be seen in the positions and relative intensities of peaks in the 60-68° range, expanded in the inset for each pattern.
  • the monoclinic phases, w-LiMnO 2 and -LiAl 025 Mno 75 ⁇ 2 exhibit (202) and (020) peaks at 65.1 ° and 66.6° respectively, with the latter being of higher intensity.
  • Li 2 Mn 2 O 4 has (400) and (323) peaks at 66.1 ° and 67.0° respectively, with the former being of higher intensity.
  • the experimental pattern in Fig. 2(d) exhibits peak positions (65.1 ° and 66.6°) as well as relative intensities that correspond to the monoclinic phase.
  • Fig. 3 shows the XRD pattern of an undoped LiMnO sample obtained by firing a precursor prepared identically but without Al additive at 945 °C in 10 "6 atm oxygen partial pressure. o-LiMnO 2 is indeed seen to be the predominant phase.
  • the lattice parameters of the »j-LiAl 025 Mno 75 O 2 sample have been calculated from the XRD data using Cohen's least-squares method, and are compared with those for pure ⁇ n-LiMnO 2 obtained by the ion-exchange method in Table 1. No significant differences are found in the values of b and ⁇ , while a and c are slightly decreased.
  • X-ray photoelectron spectroscopy was used to analyze the surface composition of this powder, before and after ion-sputtering to remove the surface layer.
  • the XPS results showed no significant difference in the Al/Mn ratio before and after sputtering, showing that there is not initially a surface atomic layer of a different composition.
  • the excellent intercalation properties of this compound discussed later, may be the resulting formation of a true solid solution m- LiAl y Mnj. y O;,.
  • a maximum amount of Al which is soluble in the structure of -LiAl y Mn,. y 0 2 may be limited.
  • FIG. 5 and 6 show STEM images and X-ray composition maps of a Li Al 025 Mn 075 O 2 powder after storage at room temperature in a sealed container for 6 months. Separation of the powder into distinct Al-rich and Mn-rich regions is observed. Analysis of the energy-dispersive X-ray spectrum showed that approximately 5 atom % of the Al remains in the mixed solid solution /w-LiAl y Mn,. y O 2 . Fig. 7 shows X-ray diffraction results from this powder before and after storage. A broad background, which can indicate the presence of an amorphous phase, has appeared after storage. The peak intensities and peak positions for the monoclinic ⁇ -NaFeO 2 phase have also changed. These results show that an -Li x Al y Mn ! . y O 2 solid solution has a tendency towards phase separation into Al-rich and Mn-rich oxides, even at room temperature.
  • Such a separation will also tend to occur during electrochemical cycling, leading to a structure in which the Al-rich oxide possibly protects the Mn-rich oxide from exposure to surrounding media including the electrolyte in a rechargeable lithium battery.
  • the spontaneous separation of the aluminum component in the form of a surface layer can then protect and stabilize the underlying intercalation compound against dissolution and chemical attack in the environment of a lithium ion battery, thereby contributing to increased charge capacity, less capacity fade upon cycling, and increased stability against capacity loss at elevated temperatures.
  • components of a multicomponent oxide intercalation compound that spontaneously separate can also serve the protective role that aluminum oxide/hydroxide does in this instance.
  • Other such components include boron oxide, phosphorus oxide, silicon oxide, and oxides of the 3d metals.
  • the intercalation compounds were tested in electrochemical test cells including two stainless steel electrodes with a Teflon holder.
  • Cathodes were prepared by mixing together the oxide powders, carbon black (Cabot), graphite (TIMCAL America) and poly(vinylidene fluoride) (PVDF) (Aldrich) in the weight ratio of 78:6:6:10. PVDF was pre-dissolved in ⁇ -butyrolactone (Aldrich) before mixing with the other components. After the ⁇ -butyrolactone was evaporated at 150°C in air, the components were compacted at about 4 t/cm 2 pressure to form pellets 10-25 mg in weight and 0.5 cm 2 in cross-sectional area.
  • the pellets were then dried at 140°C under primary vacuum for 24 h and transferred into an argon-filled glove box.
  • Lithium ribbon of 0.75 mm thickness (Aldrich) was used as the anode.
  • the separator was a film of Celgard 2400TM (Hoechst-Celanese, Charlotte, NC), and the electrolyte consisted of a 1 M solution of LiPF 6 in ethylene carbonate (EC) and diethylene carbonate (DEC). The ratio of EC to DEC was 1 :1 by volume. All cell handling was performed in an argon-filled glove box. Charge-discharge studies were performed with a MACCOR automated test equipment (Series 4000). The cells were charged and discharged between the voltage limits of 2.0 and 4.4 V.
  • Fig. 9 shows the evolution of the charge and discharge capacities of m-LiAl 025 Mn 075 O 2 during cycling between 2.0 and 4.4 V at C/5 rate.
  • LiMn 2 O 4 spinel loses capacity rapidly upon cycling at and upon storage at such temperatures. For use in applications where heat is generated, such as laptop computers or high discharge-rate applications, this is a great limitation to the application of conventional LiMn 2 O 4 spinel.
  • a charging current of 1.6 mA/cm 2 corresponding approximately to a C/2 rate (where C is the capacity and C/2 refers to fully charging or discharging in 2 hours) and a discharge current density of 0.4 mA/cm2 corresponding approximately to a C/8 rate were used.
  • Fig. 11 shows cycling tests for an m-LiAl 025 Mno 75 O 2 cell at 60 °C and 70 °C.
  • Fig. 12 shows test results at room temperature (23 °C) and 55 °C for an m-LiAlo 25 Mno 75 O 2 cell. Remarkably, the capacity is higher at 55 °C than at room temperature. This result is surprising based on the prior art.
  • Figs. 13-16 show the charge-discharge curves for the 1st, 6th, 17th, and 34th cycles respectively in -LiAl 005 Mno 95 O 2 at 55°C. They, like the room temperature tests, show the rapid evolution to a voltage profile with two voltage plateaus. Fig.
  • the compounds of this invention have electrochemical properties superior to those in conventional lithium manganese oxide spinels.
  • the properties are also superior to those in monoclinic LiMnO 2 prepared by ion exchange of Li with NaMnO 2 (G. Vitins and K. West, J. Electrochem. Soc, Vol. 144, No. 8, pp. 2587-2592, 1997), which loses capacity rapidly when cycled over both voltage plateaus.
  • the stability of the present intercalation compounds when cycled over both voltage plateaus increases the practical capacity and energy density of the compound compared to other Li-Mn-O compounds that can only be repeatedly cycled over one voltage plateau without incurring significant capacity loss.
  • a further embodiment of the invention involves the synthesis of an orthorhombic Li x Al y Mn,_ y O 2 having elevated temperature stability in a lithium battery utilizing organic liquid electrolyte as well as very high capacity and energy density.
  • Example 2 shows that such a compound can be synthesized.
  • a starting composition Lij 05 A1 0 osMrio 95 O 2 was prepared by the methods of Example 1, and fired at 900 °C for 2 hours in a CO/CO 2 mixture giving an oxygen partial pressure of 10 "6 atm.
  • Fig. 19 shows that the composition contains three phases: monoclinic Li x Al y Mn].
  • y O 2 orthorhombic Li x Al y Mn,. y O 2 , and Li 2 MnO 3 . This result shows that an orthorhombic compound is achievable.
  • a precursor of overall composition Li t 05 A1 005 Mn 095 O 2 was prepared by the methods of Example 1. This composition previously gave m- Li x Al y Mn,. y O 2 when fired at 945 °C in reducing atmosphere, as we described in previous examples.
  • We fired the precursor at 900 °C in a CO/CO 2 gas atmosphere giving an oxygen partial pressure of PO 2 : 10 "10 atmospheres, for 2 hours.
  • An X-ray diffractogram of the resulting material appears in Fig. 19. This figure shows that the majority phase in the orthorhombic phase, with only a small amount of the monoclinic phase and very minor amount of Mn 3 O 4 being detectable.
  • the sample contains a total of about 5% of Al on a cation basis. From the intensity of the X-ray diffraction peaks, it is determined that there is at most 15% by mole of the monoclinic phase and 5% by mole of the Mn 3 O 4 . Our previous experiments have shown that the solid solubility of Al in the monoclinic phase at 945 °C is approximately 5%. At the present firing temperature of 900°C it is even lower.
  • the orthorhombic phase may be Al-doped, and that o- Li x Al y Mn,. y O 2 has most likely been synthesized.
  • a preferred embodiment of this compound has an aluminum content of y less than about 0.25.
  • Fig. 20 shows the discharge capacity for this cell as a function of cycle number at a test temperature of 55 °C, in a cycling test where the charging current was 183 mA/g, and the discharging current was 91 mA/g.
  • This is a high current density, corresponding approximately to a C/0.8 charging rate and C/1.6 discharging rate at the 10 th cycle.
  • the discharge capacity increases rapidly over the first few cycles, reaching a value of approximately 150 mAh/g at the 10 th cycle.
  • the corresponding energy density is about 450 Wh/kg.
  • Another aspect of the invention involves formation of a shielding layer on the exterior of particulate metal oxide material that can be ion intercalation particles such as lithium intercalation particles Li x M y N z O 2 as described herein.
  • the particles are of multicomponent metal oxide, and each include an oxide core of at least first and second metals in a first ratio, and a surface coating of metal oxide or hydroxide that does not include the first and second metals in the first ratio.
  • the surface coating can be formed by segregation of at least one of the first and second metals from the core.
  • the particles can be used in battery arrangements as described herein.
  • the surface-layer shielded particles can be made, according to one embodiment, by allowing a first component of a multicomponent oxide based intercalation compound to segregate from a plurality of particles of the compound disproportionately to the surfaces of the plurality of particles to form protective layers of the first component on the particles.
  • the particles can be exposed to chemically degrading conditions, and the layers can be allowed to shield the particles from the chemically degrading conditions such that the particles exhibit robustness, under the conditions, greater than identical particles absent the layers.
  • the intercalation compound is an Al/Mn compound in which the aluminum component is allowed to segregate from the manganese rich oxide, resulting in a microstructure in which amorphous aluminum oxides or hydroxides spontaneously form as a layer on the crystalline intercalation compound.
  • This surface layer protects and stabilizes the underlying intercalation compound against dissolution and chemical attack in the environment of a lithium ion battery, thereby contributing to increased charge capacity, less capacity fade upon cycling, and increased stability against capacity loss at elevated temperatures.
  • This aspect of the invention encompasses any component of a multicomponent oxide intercalation compound which tends to spontaneously separate, which will tend to do so as a surface layer, and that this surface layer can serve the protective role that aluminum oxide/hydroxide does in this example.
  • Other such components include boron oxide, phosphorous oxide, silicon oxide, and oxides of the 3d metals.
  • a powder of composition LiAl 025 Mno 75 O 2 , prepared according to Example 1 was stored at room temperature in air for 4 months, then examined by transmission electron microscopy (TEM) and scanning transmission electron microscopy (STEM).
  • This powder exhibited, by powder x-ray diffraction, the monoclinic derivative of the ⁇ -NaFeO 2 structure type as the majority crystalline phase, and exhibited a microstructure in which crystalline oxide particles rich in Mn were surrounded by amorphous or nanocrystalline layers of a phase that is rich in- Al.
  • This layer is an aluminum oxide, possibly hydrated to some degree. It tends to spontaneously form from the overall composition of the material Li x Al y Mn,. y O 2 .
  • the stabilizing effect of aluminum addition in Li x Al y Mn,. y O 2 was demonstrated to apply to a range of compositions by carrying out studies with LiAl 005 Mno 95 O 2 , is stabilized in the ⁇ - NaFeO 2 structure type.
  • the composition LiAl 0 osMiio 95 O 2 was prepared using a procedure as described in Example 1. The sample was fired in reducing atmosphere at 945 °C. X-ray diffraction, Fig. 24, showed that the resulting powder has the monoclinic derivative of the ⁇ - NaFeO 2 structure type, as previously found in the composition LiAl 025 Mno 75 ⁇ 2 .
  • the as- prepared LiAl 0 o 5 Mno 95 O 2 powder was examined in a Vacuum Generators HB 603 STEM, and bright-field imaging and energy dispersive X-ray mapping for Al and Mn were conducted.
  • Fig. 4 shows a bright-field image of the powder particles, along with the X-ray maps showing Al and Mn distribution.
  • the presence of Mn appears to be accompanied by the presence of Al with a constant relative Al/Mn x-ray intensity ratio throughout the powder particles.
  • the composition is most likely uniform, and that there is not initially a distinguishable surface layer or separation of the Al and Mn into separate regions.
  • Figs. 5 and 6 show STEM results for LiAl 025 Mno 75 O 2 powder after storage at room temperature in a sealed container for 6 months. Separation of the powder into distinct Al-rich and Mn-rich regions is observed.
  • Fig. 7 shows X-ray diffraction results from this powder before and after storage. A broad background , typically indicating the presence of an amorphous phase, has appeared after storage. The peak intensities and peak positions for the monoclinic ⁇ -NaFeO 2 phase have also changed. These results may show that the Li x Al y Mn,. y O 2 solid solution prepared according to the present invention has a strong tendency towards phase separation into Al-rich and Mn-rich oxides, even at room temperature.
  • any one of the above compounds can also be realized in a mixture of any two or more. That is, it is not necessary to realize a single-phase compound in order to realize the advantages of high energy density, long cycle life, and elevated temperature stability discussed earlier.
  • Such mixtures can be achieved by physical mixing of separately prepared powders, or by a single material prepared so as to achieve more than one- phase, as exemplified by Example 2.
  • the mixture is a composite intercalation material comprising at least two compounds.
  • a composite defined by the mixture comprises at least two different compounds where each of the at least two different compounds is present in an amount of at least about 1%, preferably at least about 5%>, more preferably at least about 10%.
  • Each of the at least two compounds can be present in greater amounts, for example at least about 25% or 35%), in some embodiments.
  • the composite intercalation material comprising at least two compounds comprises at least one compound having an orthorhombic structure Li x Al y Mn,_ y O 2 , where y is nonzero.
  • the composite intercalation material comprises a mixture of orthorhombic and monoclinic Li x Al y Mn,. y O 2 .
  • the composite comprises monoclinic Li x Al y Mn,. y O 2 and orthorhombic Li x MnO 2 or Li x Al y Mn,_
  • a particular embodiment results in a voltage-vs.-capacity curve, hereafter referred to as the "voltage profile,” which is advantageous.
  • the above results have shown that monoclinic Li x Al y Mn,. y O 2 and orthorhombic Li x MnO 2 or Li x Al y Mn].
  • y O 2 have different rates of lithium intercalation and de-intercalation, the latter two compounds being typically slower.
  • both compounds exhibit a two-step voltage profile with plateaus at about 4 V and about 3 V. When both compounds are present in one electrode, they will intercalate and de-intercalate lithium at different rates. This has the effect of "voltage averaging" such that the voltage profile of the resulting compound exhibits less sharply defined plateaus.
  • a more gradually varying voltage profile is advantageous in many battery applications.
  • a composite electrode giving voltage profile smoothing as described above can be achieved with a mixture of different compounds with disparate lithium chemical diffusion rates, or with a mixture of compounds of similar or identical lithium chemical diffusion rate but varying particle size.
  • the rate-limiting transport step in the electrode is most likely diffusion in one or more of the intercalation compounds.
  • Such a composite cathode can be realized not only with the compounds of Examples 1-3, but also with any combination of individual intercalation compounds satisfying the requirement of disparate lithium chemical diffusion rates or widely varying particle size, in an electrode construction whereby lithium diffusion in the compounds is rate-limiting.
  • One aspect of the present invention provides a composite intercalation compound containing at least two individual intercalation compounds, each compound having a different lithium chemical diffusion rate and a voltage vs. capacity profile that varies more continuously than the voltage vs. capacity profile of any noncomposite intercalation compound.
  • Another aspect of the present invention provides a composite intercalation compound containing at least two individual intercalation compounds, each compound having a different particle size and having a voltage vs. capacity profile that varies more continuously than the voltage vs. capacity profile of any noncomposite intercalation compound.
  • an electrode for a lithium battery contains a compound having a different particle size and a voltage vs. capacity profile as described above where the compound has a particle size sufficient to cause the slowest lithium transport step in the electrode to be the diffusion of lithium in the compound.
  • a composite intercalation material comprises at least two compounds having at least one compound, which upon electrochemical cycling, has a transformation in the voltage vs. capacity curve from a single plateau at about 4 V to two plateaus at about 4 V and 3 V respectively.
  • a composite intercalation material comprises at least two compounds having at least one compound with a discharge capacity of at least about

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Abstract

Des composés d'intercalaire et en particulier des composés d'intercalaire au lithium présentent des caractéristiques améliorées et conviennent pour des batteries. Les compositions décrites comprennent un matériau oxyde métallique particulaire comprenant des particules d'oxyde métallique à plusieurs constituants, chaque particule comprenant un noyau d'oxyde composé au moins d'un premier et d'un second métal dans une première proportion, et une couche superficielle d'oxyde ou d'hydroxyde métallique ne présentant pas cette première proportion de premier et second métaux formant le noyau, formée par une ségrégation d'au moins un des premier et second métaux du noyau. Le noyau comprend de préférence le composé LixMyNzO2, dans lequel M et N sont des atomes métalliques ou des éléments du groupe principal, x, y et z sont des nombres compris entre 0 et 1 environ, et y et z sont tels qu'une charge formelle sur la partie MyNz du composé est de (4-x), et présentent une tension de charge d'au moins 2,5 V environ. Cette invention peut également se définir comme une microstructure d'oxyde à plusieurs constituants pouvant être utilisée comme matériau d'intercalaire au lithium, et comprenant un noyau d'oxyde à plusieurs phases et une couche superficielle composée d'un matériau qui est un constituant du noyau d'oxyde à plusieurs phases, cette couche superficielle protégeant le matériau d'intercalaire sous-jacent contre une dissolution ou une réaction chimique. Dans un exemple préféré, cet oxyde à plusieurs constituants est une composition d'oxyde de lithium-manganèse dopée à l'aluminium. L'invention concerne en outre de telles compositions oxyde de lithium-manganèse dopées à l'aluminium présentant une structure orthorhombique, ainsi que des articles, en particulier des électrodes pour batteries formées avec les compositions décrites, et des batteries comprenant de telles électrodes. L'invention concerne de plus un matériau composite d'intercalaire comprenant au moins deux composés dont un au moins comprend une structure orthorhombique LixAlyMn1-yO2 dans laquelle y est différent de zéro, ou un mélange de LixAlyMn1-yO2 orthorhombique et monoclinique.
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US7338734B2 (en) 2001-12-21 2008-03-04 Massachusetts Institute Of Technology Conductive lithium storage electrode
US7387851B2 (en) 2001-07-27 2008-06-17 A123 Systems, Inc. Self-organizing battery structure with electrode particles that exert a repelling force on the opposite electrode
US7553584B2 (en) 2000-10-20 2009-06-30 Massachusetts Institute Of Technology Reticulated and controlled porosity battery structures
US7579112B2 (en) 2001-07-27 2009-08-25 A123 Systems, Inc. Battery structures, self-organizing structures and related methods
US8999571B2 (en) 2007-05-25 2015-04-07 Massachusetts Institute Of Technology Batteries and electrodes for use thereof
US9065093B2 (en) 2011-04-07 2015-06-23 Massachusetts Institute Of Technology Controlled porosity in electrodes
US10569480B2 (en) 2014-10-03 2020-02-25 Massachusetts Institute Of Technology Pore orientation using magnetic fields
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JP2001325947A (ja) * 2000-05-16 2001-11-22 Toyota Central Res & Dev Lab Inc リチウム二次電池用正極、その製造方法およびそれを用いて構成されたリチウム二次電池
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US8586238B2 (en) 2000-10-20 2013-11-19 Massachusetts Institute Of Technology Battery structures, self-organizing structures, and related methods
US8580430B2 (en) 2000-10-20 2013-11-12 Massachusetts Institute Of Technology Battery structures, self-organizing structures, and related methods
US8241789B2 (en) 2000-10-20 2012-08-14 Massachusetts Institute Of Technology Battery structures, self-organizing structures and related methods
US7553584B2 (en) 2000-10-20 2009-06-30 Massachusetts Institute Of Technology Reticulated and controlled porosity battery structures
US8206468B2 (en) 2000-10-20 2012-06-26 Massachusetts Institute Of Technology Battery structures, self-organizing structures and related methods
US7781098B2 (en) 2000-10-20 2010-08-24 Massachusetts Institute Of Technology Reticulated and controlled porosity battery structures
US7387851B2 (en) 2001-07-27 2008-06-17 A123 Systems, Inc. Self-organizing battery structure with electrode particles that exert a repelling force on the opposite electrode
US7579112B2 (en) 2001-07-27 2009-08-25 A123 Systems, Inc. Battery structures, self-organizing structures and related methods
US7338734B2 (en) 2001-12-21 2008-03-04 Massachusetts Institute Of Technology Conductive lithium storage electrode
US8852807B2 (en) 2001-12-21 2014-10-07 Massachusetts Institute Of Technology Conductive lithium storage electrode
US7087348B2 (en) 2002-07-26 2006-08-08 A123 Systems, Inc. Coated electrode particles for composite electrodes and electrochemical cells
US7318982B2 (en) 2003-06-23 2008-01-15 A123 Systems, Inc. Polymer composition for encapsulation of electrode particles
US8999571B2 (en) 2007-05-25 2015-04-07 Massachusetts Institute Of Technology Batteries and electrodes for use thereof
US9065093B2 (en) 2011-04-07 2015-06-23 Massachusetts Institute Of Technology Controlled porosity in electrodes
US10164242B2 (en) 2011-04-07 2018-12-25 Massachusetts Institute Of Technology Controlled porosity in electrodes
US10569480B2 (en) 2014-10-03 2020-02-25 Massachusetts Institute Of Technology Pore orientation using magnetic fields
US10675819B2 (en) 2014-10-03 2020-06-09 Massachusetts Institute Of Technology Magnetic field alignment of emulsions to produce porous articles

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