WO1999000860A1 - Cathodes en oxyde de manganese de transition - Google Patents

Cathodes en oxyde de manganese de transition Download PDF

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Publication number
WO1999000860A1
WO1999000860A1 PCT/US1998/013226 US9813226W WO9900860A1 WO 1999000860 A1 WO1999000860 A1 WO 1999000860A1 US 9813226 W US9813226 W US 9813226W WO 9900860 A1 WO9900860 A1 WO 9900860A1
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WO
WIPO (PCT)
Prior art keywords
cell
cathode
lithium
primary
electrochemical
Prior art date
Application number
PCT/US1998/013226
Other languages
English (en)
Inventor
David L. Chua
Hsiu-Ping Lin
Hung-Chieh Shiao
Original Assignee
Maxpower, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Maxpower, Inc. filed Critical Maxpower, Inc.
Publication of WO1999000860A1 publication Critical patent/WO1999000860A1/fr

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Classifications

    • 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
    • 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
    • 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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
    • 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 generally to primary or secondary non-aqueous electrochemical cells or batteries utilizing a lithium ion containing anode in combination with a liquid-based or polymer-based electrolyte and chargeable metal oxide cathode materials. More particularly, the invention relates to novel transition metal oxide, namely, transition manganese oxide cathode materials for use in both secondary (rechargeable) and primary batteries.
  • One approach to reducing or eliminating dendrite formation in rechargeable lithium-based batteries involves the use of a carbonaceous material susceptible of being intercalated and de-intercalated, i.e., that reversibly intercalates, in combination with lithium containing metal complex oxide cathodes.
  • This lithiated cathode material provides a source of lithium during the first charging of this type of battery and the intercalation and de- intercalation of lithium in the carbonaceous material during the charge and discharge half cycles greatly reduces dendrite formation.
  • the problem of dendrite formation has been addressed, for example, in U.S.
  • Patent 5 292 601 to Sugeno et al in which dendrite formation is inhibited by the use of lithium in the form of a carbon-lithium intercalation compound for the negative electrode.
  • a system using a carbonaceous anode and a rechargeable lithium system is also described in European Patent Application 0 634 805 Al, published June 23, 1994.
  • Such materials include certain transition metal oxides, notably manganese oxides.
  • the present invention enables the cycling of Li x Mn 4 O z where 8 ⁇ z ⁇ 9 in a manner which yields an energy density (discharge capacity) > 250 mAh/g.
  • Another object of the invention is to provide a new cathode material of higher energy density useful for implantable lithium-based primary Pacer batteries and secondary VAD batteries.
  • a further object of the invention is to increase the energy density by using Li x Mn 4 0 2 where 1.8 ⁇ x ⁇ 2.2 and 8 ⁇ z ⁇ 9 and more specifically, 1.9 ⁇ x ⁇ 2.1 and 8.3 ⁇ z ⁇ 8.7 cathodes in combination with either lithium-based or lithium-ion-based anodes by increasing the available electron exchange between the charged and discharged material.
  • Yet still another object of the present invention is to provide Li x Mn 4 O z 0.5 ⁇ x ⁇ 4.5 , 8 ⁇ z ⁇ 9 cathodes for use in combination with either lithium-based or lithium-ion- based anodes in a higher energy density, non-aqueous electrochemical battery.
  • an improved lithium, manganese oxide cathode material is provided for use in combination with either lithium-based or lithium- ion-based anode materials in both primary and secondary non-aqueous cells and batteries.
  • the combinations of the invention enable the realization of very high energy densities which may exceed 250 mAh/g.
  • the present invention involves the use of Li x Mn 4 O z as the cathode material. In the fully charged state for the material of the invention x is generally in the range of 0.5 to 1; and in the fully discharged state, x is in the range of 4 to 4.5.
  • the material Li x Mn 4 O z , 1.8 ⁇ x ⁇ 2.2 and 8 ⁇ z ⁇ 9 and more specifically, 1.9 ⁇ x ⁇ 2.1 and 8.3 ⁇ z ⁇ 8.7 is prepared by a solid-state reaction process.
  • lithium- manganese oxide materials can be synthesized from any decomposable, i.e., calcinable, Li and Mn salts, including carbonates, hydroxides, oxides, nitrates and acetates.
  • the solid state reaction is a diffusion controlled process. In order to obtain a completely reacted and uniform product, both intimate contact between reacting species and uniform distribution of each species are needed.
  • the intimately mixing of the two different powders has been achieved by first dissolving the LiOH » H 2 0 in de-ionzed (D.I.) water, then, mixing the MnC0 3 powder into the slurry and homogenizing the slurry at 4,000 - 6,000 rpm for 5 - 30 minutes. After evaporation of the D.I. water at 100°C, the soft powder cake is blended as by using a Waring high speed blender for 1 to
  • Li x Mn 4 0 z can be synthesized at 350 to 450°C by reaction of stoichiometric amounts (for example, in a mole ratio of 1 to 2) of thoroughly mixed
  • LiOH H 2 0 and MnC0 3 powders in an oxygen-rich environment.
  • reaction conditions including calcination temperature (from 350 to 500°C) , dwell time (20 to 60 hours) , and reaction environments (0 2 and/or air) have been evaluated for the solid state reaction process. Some of the reaction condition ranges are listed as follows: Atmosphere air and/or 0 2
  • PVDF polyvinylidene fluoride
  • Electrolyte solution e.g., 1.0 M LiPF 6 /ethylene carbonate (EC) : dimethyl carbonate (DMC) :diethyl carbonate (DEC) at volume ratios, for example, at 50/40/10
  • EC ethylene carbonate
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • This electrochemical cell can then be charged at constant current to the predetermined levels of state-of-charge, or discharged at constant current to the pre-determined levels of state-of- discharge to obtain Li x Mn 4 0 9 (0.5 ⁇ x ⁇ 1) and Li x Mn 4 0 9 (4 ⁇ x ⁇ 4.5), respectively.
  • low discharge current density should be used, typically, 0.5 ma/cm 2 .
  • FIGURE 1 is an exploded schematic view of a cell including a cathode in accordance with the invention
  • FIGURE 2 is a schematic view showing the cell of FIGURE 1 in the assembled configuration
  • FIGURE 3 is a graphical representation of cell charge capacity over several cycles in the cut off potential range vs. Li of 3.75 - 1.5V;
  • FIGURE 4 is a graphical representation showing cell discharge capacity for cathode samples synthesized at various temperatures over the temperature range of 375 to 450°C.
  • FIGURE 5 is a flow chart for an example of the Li x Mn 4 0 z synthesis process.
  • the invention involves using innovative transition manganese oxide cathode technologies for both rechargeable and primary implantable batteries.
  • Specific examples of uses include implantable pacer batteries and in an external charger for a Ventricular Assist Device (VAD) .
  • VAD Ventricular Assist Device
  • the invention extends the operating range of lithium concentrations of Li x Mn 4 0 z from 1.0 ⁇ x - ⁇ 4.0 to 0.5 - ⁇ x - ⁇ 4.5 and possibly to 0 ⁇ x ⁇ 5.
  • the Li 2 Mn 4 O z material is known to have a defect spinel structure with cubic symmetry. This spinel framework provides a three- dimensional interstitial space for Li ion diffusion in and out and is retained during lithiation and delithiation.
  • the optimum cathode candidate is Li 0 Mn 4 O z where O ⁇ x ⁇ 0.5, and the net electrochemical reaction during discharge is :
  • Li x Mn 4 0 2 where 0.5 ⁇ x ⁇ 2.0 and where 8.3 ⁇ z ⁇ 8.7, can be employed as a cathode for a fully charged implantable lithium-based primary pacer battery.
  • the maximum theoretical capacity of Li x Mn 4 O z cathode operating between lithium concentration limits of 0 to 5 is 337 mAh/g, of which 142 mAh/g is delivered at approximately 4.0 volts, and 213 mAh/g is delivered at about 3.0 volts.
  • Li x Mn 4 O z where 0.5 ⁇ x ⁇ 1.0 with a plasticized polymer-based electrolyte (PPE) , or solid polymer-based electrolyte and lithium metal as the anode is contemplated for an advanced pacer battery.
  • Li x Mn 4 0 9 where 4.0 ⁇ x ⁇ 5.0, can be used as a cathode for a fully discharged advanced rechargeable battery that can be used as the external power supply for a VAD device.
  • This cathode in combination with the Li ion anode or lithium metal anode is projected to deliver similar capacity as Li x Mn 4 O z mentioned above with extended cycle life capability.
  • Li ion-based rechargeable system can be used as the external charger for an implanted VAD device.
  • Li 5 Mn 4 0 9 is the optimum cathode material.
  • Li- based rechargeable batteries use carbon or graphite material (Li ion) as an anode to couple with lithiated cathode material. This lithiated cathode material provides the source of lithium during the first charging of the battery. This technology has demonstrated a life greater than 1000 cycles and is a much safer system compared to the Li anode batteries.
  • the equation representing the net electrochemical reaction is shown as follows:
  • Li 2 Mn 4 0 9 is an intermediate compound for the lithium operating range of interest. When this material is used as the starting cathode active material, an initial partial charge or discharge step is required for a full capacity delivery. In a primary system, a partial charging process is needed to form fully charged cathode Li 0 Mn 4 O 9 . This charging process complicates the cell design does require some volume compensation to accommodate for negative electrode expansion due to plated lithium.
  • the rechargeable system embodiment requires an amount of excess lithium metal in the cell if lithium metal is used as the anode and if Li 2 Mn 4 0 9 is coupled with a carbon (Li ion) anode as the host structure does not have enough lithium to supply the full capacity corresponding to the 4.0 volt and 3.0 volt level.
  • Li 2 Mn 4 O z was prepared by first dissolving 44.6 grams of LiOH»H 2 0 in 300 grams de-ionized water as at 10. 244.6 grams of MnC0 3 powder were then mixed into the slurry at 12 and homogenized at 5,000 rpm for 20 minutes at 14 to form a slurry at 16. After drying by evaporation of the D.I. water which may be accomplished by spray drying, freeze drying or oven drying at 100°C to 110°C as at 18 for several hours to dry, the powder was then blended in a Waring high speed blender to micronize the sample cake to form powders at 20.
  • Li x Mn 4 0 z can be synthesized at 21 from the prepared fine homogenous powder of the step at 20 by reaction of stoichiometric amounts 350 to 450°C (for example, in a mole ratio of 1:1.9, 1:2 or 1:2.1) of the thoroughly mixed LiOH»H 2 0 and MnCQ powders in an oxygen-rich environment. Analysis may be made by thermo gravimetric analysis (TGA) as at 22.
  • TGA thermo gravimetric analysis
  • the calcination temperature (preferably from 400 to 450°C) , dwell time (20 to 60 hours and preferably 20 to 40 hours) , and reaction environments (0 2 ) have been evaluated for the solid state reaction process.
  • the composition can be verified as by x-ray diffraction at 24 and used for actual electrochemical evaluation as at 26 and as will be described below.
  • the construction of one experimental cell is shown generally in FIGURES 1 and 2 sandwiched between a pair of glass covers 30 and 32 and including an aluminum cathode grid 34 with electrical lead 36.
  • a thin sheet of cathode composite cathode active material is illustrated at 38 and the layers of a composite separator material such as Cellgard 2300 separator material and noted by a composite representation 40.
  • the anode consists of a thin layer of lithium foil imbedded on a nickel grid current collector as at 42 which, in turn, is connected to an electrical lead 44. As shown in FIGURE 2, the cell components may be fastened together in sandwich fashion as by wire retainers at 46.
  • the electrochemical cell shown in Figures 1 and 2 or similar cells can also be used to assess the electrical characteristics and cycle performance of the Li 2 Mn 4 O z cathode.
  • the electrode design is made cathode limited.
  • KS-44 graphite from Lonza can be used for the Li ion anode, 1.5 M LiPF 6 /EC+DMC electrolyte solution, and teflonated Li 2 Mn 4 O z /C cathode.
  • Li x Mn 4 0 z cathodes were prepared by mixing 83 weight percent Li x Mn 4 O z , prepared as in Example 1, 10 weight percent conductive carbon and 7 weight percent Teflon. The mix was then kneaded and rolled into a thin sheet, 4 to 6 mil thick.
  • a cell was assembled by layering an aluminum grid, a cathode, two layers of Cellgard 2300 separators, a lithium foil and a nickel grid.
  • one cell was cycled for 29 cycles at a current density of 0.025 mA/cm 2 between 1.5 and 3.75 V.
  • the charge capacity initially approached 180 mAh/g and remained above 160 mAh/g throughout the test.
  • Figure 4 depicts performance of solid state cathode samples synthesized at various calcination or synthesis temperatures. As borne out by that figure, the highest discharge capacity (initially above 250 mAh/g) was achieved for synthesis temperatures of about 450°C. In all cases, however, the discharge capacity remains fairly constant throughout the 11 or 12 test cycles depicted in the figure. In accordance with the present invention, it is believed that the feasibility of increasing the net electron exchange of Li x Mn 4 O z can be increased to a range of from about 3.5 net electrons to a value - 5. This should result in a rate increase in the available energy density of both primary and secondary cells utilizing the technology.
  • Cathodes constructed using the cathode active material of the invention are generally constructed using a composition of from about 75% to 85% Li x Mn 4 O z , between about 15% and 10% conductive carbon and between about 10% and 5% of a binder material. Specific examples are meant to be examples only and are by no means intended to limit the scope of the invention.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

L'invention concerne un matériau amélioré pour cathode, utilisé dans des piles non aqueuses primaires et secondaires en métal actif et comprenant une certaine quantité de carbone conducteur combinée à une certaine quantité de LixMn4Oz (0≤x≤5 et 8≤z≤9).
PCT/US1998/013226 1997-06-27 1998-06-25 Cathodes en oxyde de manganese de transition WO1999000860A1 (fr)

Applications Claiming Priority (2)

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US88453897A 1997-06-27 1997-06-27
US08/884,538 1997-06-27

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1317012A2 (fr) * 2001-12-03 2003-06-04 VARTA Microbattery GmbH Procédé de fabrication d'éléments galvaniques à électrolytes organiques liquides

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5240790A (en) * 1993-03-10 1993-08-31 Alliant Techsystems Inc. Lithium-based polymer electrolyte electrochemical cell
US5240794A (en) * 1990-12-20 1993-08-31 Technology Finance Corporation (Proprietary) Limited Electrochemical cell
US5316877A (en) * 1992-08-28 1994-05-31 Technology Finance Corporation (Proprietary) Limited Electrochemical cell
WO1994019836A1 (fr) * 1993-02-17 1994-09-01 Valence Technology, Inc. Electrodes pour piles au lithium rechargeables
US5753202A (en) * 1996-04-08 1998-05-19 Duracell Inc. Method of preparation of lithium manganese oxide spinel

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5240794A (en) * 1990-12-20 1993-08-31 Technology Finance Corporation (Proprietary) Limited Electrochemical cell
US5316877A (en) * 1992-08-28 1994-05-31 Technology Finance Corporation (Proprietary) Limited Electrochemical cell
WO1994019836A1 (fr) * 1993-02-17 1994-09-01 Valence Technology, Inc. Electrodes pour piles au lithium rechargeables
US5240790A (en) * 1993-03-10 1993-08-31 Alliant Techsystems Inc. Lithium-based polymer electrolyte electrochemical cell
US5753202A (en) * 1996-04-08 1998-05-19 Duracell Inc. Method of preparation of lithium manganese oxide spinel

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
LE CRAS F., BLOCH D., STROBEL P.: "LOW-TEMPERATURE LITHIUM-MANGANESE OXIDE CATHODE MATERIALS FOR POLYMER BATTERIES.", JOURNAL OF POWER SOURCES, ELSEVIER SA, CH, vol. 63., no. 01., 1 November 1996 (1996-11-01), CH, pages 71 - 77., XP002913169, ISSN: 0378-7753, DOI: 10.1016/S0378-7753(96)02448-2 *
THACKERAY M. M., ET AL.: "SPINEL ELECTRODES FROM THE LI-MN-O SYSTEM FOR RECHARGEABLE LITHIUM BATTERY APPLICATIONS.", JOURNAL OF THE ELECTROCHEMICAL SOCIETY, ELECTROCHEMICAL SOCIETY, vol. 139., no. 02., 1 February 1992 (1992-02-01), pages 363 - 366., XP002913168, ISSN: 0013-4651 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1317012A2 (fr) * 2001-12-03 2003-06-04 VARTA Microbattery GmbH Procédé de fabrication d'éléments galvaniques à électrolytes organiques liquides
EP1317012A3 (fr) * 2001-12-03 2005-04-13 VARTA Microbattery GmbH Procédé de fabrication d'éléments galvaniques à électrolytes organiques liquides

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