+

WO1998038648A1 - Cathodes dopees a oxydes pour accumulateur electrique au lithium et pour accumulateur aux ions de lithium - Google Patents

Cathodes dopees a oxydes pour accumulateur electrique au lithium et pour accumulateur aux ions de lithium Download PDF

Info

Publication number
WO1998038648A1
WO1998038648A1 PCT/US1998/003847 US9803847W WO9838648A1 WO 1998038648 A1 WO1998038648 A1 WO 1998038648A1 US 9803847 W US9803847 W US 9803847W WO 9838648 A1 WO9838648 A1 WO 9838648A1
Authority
WO
WIPO (PCT)
Prior art keywords
lithium
spinel
metal oxide
cations
manganese
Prior art date
Application number
PCT/US1998/003847
Other languages
English (en)
Inventor
Titus Faulkner
Wayne Barnette
Yuan Gao
Vesselin Manev
Original Assignee
Fmc Corporation
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 Fmc Corporation filed Critical Fmc Corporation
Priority to JP10537881A priority Critical patent/JP2000500280A/ja
Publication of WO1998038648A1 publication Critical patent/WO1998038648A1/fr

Links

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—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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/40—Complex oxides containing cobalt and at least one other metal element
    • C01G51/42—Complex oxides containing cobalt and at least one other metal element containing alkali metals, e.g. LiCoO2
    • C01G51/44—Complex oxides containing cobalt and at least one other metal element containing alkali metals, e.g. LiCoO2 containing manganese
    • C01G51/54—Complex oxides containing cobalt and at least one other metal element containing alkali metals, e.g. LiCoO2 containing manganese of the type (Mn2O4)-, e.g. Li(CoxMn2-x)O4 or Li(MyCoxMn2-x-y)O4
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/30—Three-dimensional structures
    • C01P2002/32—Three-dimensional structures spinel-type (AB2O4)
    • 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
    • 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
    • C01P2002/77—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
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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 composite metal oxide positive electrode materials for secondary lithium and lithium-ion batteries.
  • Lithium-manganese spinels are presently considered useful positive electrode materials for 4 V secondary lithium and lithium- ion batteries.
  • the stoichiometric spinel LiMn 2 0 4 exhibits poor cycling performance in comparison to other positive electrode materials used for 4 V batteries. Therefore, there have been numerous methods proposed in the art for increasing the cycling performance of LiMn 2 0 4 .
  • LiMn 2 0 4 spinel a portion of the manganese in the LiMn 2 0 4 spinel can be replaced with excess lithium as proposed in R-.J. Gummow et al . , Solid State Ionics, 69 (1994), p. 59; and U.S. Patent No. 5,425,932 to Tarascon. Nevertheless, the stabilization of the LiMn 2 0 4 structure by doping the spinel with excess lithium to form Li 1+x Mn 2 _ x 0 4 is accompanied by a significant decrease in its specific capacity.
  • the doping ion replaces a 3 + manganese ion, but cannot itself be transferred to 4 + during the charge process (e.g. Ni 2+ , Co 3+ , Cr 3+ and Al 3+ ) , or it replaces a lithium ion in its tetrahedral site reducing the number of lithium ions which can be reversibly intercalated in the 4 V range (e.g. Fe 3+ , Ga 3+ , Ti 4+ and V 5+ .) .
  • the present invention provides a positive electrode material for secondary lithium and lithium- ion cells which comprises a multiple-doped lithium manganese metal oxide having a spinel structure and described by the general formula:
  • 1 , 2 , ...M k are at least two cations different than lithium or manganese, selected from the group consisting of alkaline earth metals, transition metals,
  • X, Y, m x , m 2 , ....m k are molar parts with numbers between 0 and 0.2; m 1# m 2 and Y are greater than 0; Z is a number between -0.1 and 0.2; and wherein the metals M 1 , M 2 , ...M k and the corresponding molar parts m 1# m 2 , ...m k satisfy the following equation and inequality:
  • V 1 ( V 2 , . . . . V k are the corresponding valence states of the cations M 1 , M 2 , . . . M k . More preferably, the cations M 1 , M 2 , ...M k and the corresponding molar parts m 1# m 2 , ....m k satisfy the following two equations:
  • the codopants in the multiple- doped lithium manganese oxide spinel compounds of the invention preferably do not cause significant contraction or expansion of the spinel structure.
  • the unit cell parameter (a) of the multiple-doped lithium manganese metal oxide of the invention is preferably within about ⁇ 0.0015 A/mol%, more preferably ⁇ 0.0005 A/mol%, of the unit cell parameter (a) of the corresponding unsubstituted Li 1+x Mn 2 _ x 0 4+z spinel.
  • the spinel compound is codoped with equivalent amounts of Co 3+ and Ti 4+ to form a spinel material having a composition described by the formula:
  • Figure 1 is a graph showing the discharge specific capacity versus cycle number for a secondary lithium cell with a positive electrode material prepared in accordance with the present invention, and for secondary lithium cells having alternative positive electrode materials, wherein the excess lithium is the same for all examples.
  • Figure 2 is a graph showing the discharge specific -capacity versus cycle number for a secondary lithium cell with a positive electrode material prepared in accordance with the present invention, and for secondary lithium cells having alternative positive electrode materials, wherein the sum of the molar parts of the excess lithium and the codopants is the same for all examples.
  • the present invention is directed to improvements in the electrochemical performance of the secondary lithium and lithium-ion cells resulting from the use of a multiple-doped lithium manganese spinel as the positive electrode material.
  • the electrical performance of a stoichiometric lithium manganese oxide spinel Li 1+x Mn 2 _ x° 4+z can b e improved by replacing a portion of the manganese with a combination of two or more cations other than lithium or manganese.
  • a portion of the manganese can be replaced with excess lithium ions in the spinel to improve the electrical performance of the Li 1+x Mn 2 _ x 0 4+z spinel.
  • the multiple-doped lithium manganese oxide has a spinel structure and can be described by the general formula:
  • M 1 , M 2 , ...M k are at least two cations different than lithium or manganese, selected from the group consisting of alkaline earth metals, transition metals, B, Al, Si, Ga and Ge;
  • X, Y, m 17 m 2 , ....m k are molar parts with numbers between 0 and 0.2; Z is a number between -0.1 and 0.2; and wherein the metals M 1 , M 2 , ...M k and the corresponding molar parts m 1 ,m 2 ,...m k satisfy the following equation and inequality:
  • m- L and m 2 are greater than 0 and therefore Y is also greater than 0 in accordance with the invention.
  • the mean valency of the codopants satisfies the relationship: 3 . 3 ⁇ m 1 V 1 + m V 2 + - + m V ⁇ 3 . 7 m 1 + m 2 + m 3 + ••• + m k
  • V x , V 2 , . . . . V k are the corresponding valence states of the cations M 1 , M 2 , . . . M k .
  • the mean valency state of the substituted ions are equal or nearly equal to the mean valency state of the manganese ions in the corresponding unsubstituted spinel compound.
  • the Li 1+x Mn 2 _ x 0 4+z spinel compound is codoped with Co 3+ and Ti 4+ to form the spinel material .
  • the molar amounts of Co 3+ and Ti 4+ are equivalent.
  • a portion of the manganese can also be replaced by excess lithium.
  • the composition can be described by the formula: Li 1+x Mn 2 . x _ 2m Co ra 3+ Ti m 4+ 0 4+z wherein X and m are molar parts with numbers between 0 and 0.2 and Z is a number between -0.1 and 0.2.
  • codopant combination of cobalt and titanium is described as a preferred embodiment for use in the invention, various other combinations can be used in accordance with the invention.
  • combinations of aluminum, cobalt, chromium, copper, iron, gallium, magnesium, nickel, germanium, molybdenum, niobium, titanium, vanadium and tungsten such as aluminum/titanium, gallium/titanium, nickel/titanium, iron/titanium, chromium/titanium, cobalt/vanadium, aluminum/vanadium, magnesium/vanadium, gallium/vanadium, nickel/vanadium, iron/vanadium, chromium/vanadium, cobalt/molybdenum, aluminum/molybdenum, gallium/molybdenum, nickel/molybdenum, iron/molybdenum, chromium/molybdenum, cobalt/germanium, aluminum/germanium, magnesium/germanium, gallium, gall
  • the codopants in the multiple- doped lithium manganese oxide spinel compounds of the invention are preferably selected not to cause significant contraction or expansion of the spinel structure. Therefore, the codopants typically have a mean ionic radii size (R which corresponds to the mean ionic radii size of the manganese ions being replaced.
  • the unit cell parameter (a) of the multiple-doped lithium manganese oxide spinel compound is within + 0.0015 A/mol%, more preferably within about + 0.0005 A/mol%, of the unit cell parameter of the corresponding unsubstituted Li 1+x Mn 2 _ x 0 4+z spinel (i.e., wherein m x , m 2 , ...
  • introducing the codopants into the lithium manganese oxide spinel causes an increase or decrease in the unit cell parameter of the spinel of less than or equal to about 0.0015 A/mol%, more preferably, less than or equal to about ⁇ 0.0005 A/mol% .
  • the unit cell parameter (a) of the spinel structure can be readily determined by x-ray diffraction analysis using CuKc ⁇ rays or other rays as would be understood by those skilled in the art.
  • Co 3+ ions have an ionic radii of 0.55 A and replace Mn 3+ ions which have a higher ionic radii size of about 0.62 A. Therefore, the replacement of Mn 3+ ions with Co 3+ ions in the spinel structure causes a corresponding decrease in the unit cell parameter.
  • Ti 4+ ions have an ionic radii size of 0.68 A and replace Mn + ions which have a smaller ionic radii size of about 0.54 A thereby causing an increase in the unit cell parameter.
  • the doped ions used in the spinel of the invention are preferably selected such that not all of the doped ions occupy the same sites (e.g. octahedral and tetrahedral sites) in the spinel structure.
  • the Co 3+ ions generally occupy octahedral sites and the majority of the Ti 4+ ions occupy tetrahedral sites when included in the spinel structure.
  • Other ion combinations e.g., Ni 2+ and V 5+ , can also occupy different positions in the spinel structure as preferred in accordance with the invention.
  • the present invention also includes a method of preparing a multiple-doped lithium manganese oxide spinel compound as described above. Specifically, source compounds (i.e. raw materials) containing lithium, manganese, oxygen, and the dopants (M 1 , M 2 , ... M k ) are mixed to provide the formula:
  • X, Y, m 1 , m 2 , ....m k are molar parts with numbers between 0 and 0.2; l l m 2 and Y are greater than 0; Z is a number between -0.1 and 0.2; and the metals M 1 ,
  • V l r V 2 , ....V k are the corresponding valence states of the cations M 1 , M 2 , ...M k .
  • the cations can be selected to correspond to the ionic radii size of the manganese being replaced as discussed in more detail above.
  • the source compounds for preparing the multiple-doped lithium manganese metal oxides of the invention can be pure elements but are typically compounds containing these elements such as oxides, salts or complexes thereof.
  • the cations for the multiple-doped spinel compound can each be supplied from separate source compounds or two or more of the cations can be supplied from the same source compound. In either case, it is important that the source compounds have high purity to limit the amount of defects in the spinel compound.
  • the source compounds can be mixed in any desirable order to provide the desired elements for the multiple-doped lithium manganese oxide spinels of the invention.
  • the source compounds are mixed using wet chemistry such as sol-gel type reactions, coprecipitation, and other methods.
  • the non- lithium source compounds are mixed together in aqueous solution to evenly distribute the source compounds and the resulting mixture is precipitated out of solution for later mixture with the lithium source compound.
  • MnC0 3 , (CH 3 C0 2 ) 2 Co- 4H 2 0 and [CH 3 CH (O) C0 2 NH 4 ] 2 Ti (OH) _ can be coprecipitated together and then mixed with LiOH to provide the desired elements.
  • the source compounds used in the invention can be mixed using dry methods. As will be understood by those skilled in the art, the selection of mixing methods will vary depending on the source compounds used and the desired end product. In any event, the source compounds are preferably sufficiently mixed to provide an even distribution of the metals in the mixture. It has been discovered in accordance with the invention that the even distribution of the metals produces a more homogenous and structurally stable spinel compound .
  • the mixture once prepared can be reacted by a solid state reaction to form the multiple-doped lithium manganese oxide spinel compounds of the invention.
  • the mixture is reacted by firing the mixture at an elevated temperature between about 400 °C and about 900 °C in the presence of oxygen, e.g., in an atmosphere with a partial pressure of oxygen of at least 20 kPa .
  • the mixture can be fired in one step but is preferably fired in more than one step to produce the spinel compound.
  • the mixture is fired at a temperature between about 400 °C and about 500 °C for 1 to 24 hours, at a temperature between about 500 °C and about 600 °C for 1 to 24 hours, and at a temperature of between about 700°C and about 900°C for 1 to 24 hours. Additional firing steps can also be used in the invention to improve the quality of the resulting spinel as described, e.g., in U.S. Patent No. 5,718,877, which is hereby incorporated in its entirety by reference.
  • this compound is preferably cooled to ambient temperature in a controlled manner, e.g., at a rate of 5°C/min or less, to produce a spinel compound suitable for use as a positive electrode material for secondary lithium and lithium-ion batteries.
  • the multiple-doped lithium manganese oxide spinel compounds can be used in positive electrodes in secondary lithium and lithium-ion cells.
  • the multiple- doped lithium manganese oxide spinel is typically combined with a conductive agent such as graphite or carbon black and a binder material such as polyvinylidene difluoride (PVDF) and dispersed in a solvent such as n-methyl pyrrolidinone (NMP) (e.g. 1- methyl-2-pyrrolidinone) to form a slurry.
  • PVDF polyvinylidene difluoride
  • NMP n-methyl pyrrolidinone
  • the slurry is typically spread on aluminum and then heated to evaporate the solvent to form a dry electrode material.
  • the dry electrode is then compressed by rolling, pressing, or other known methods, and cut into, for example, a disk, to form the positive electrode.
  • the electrode is then placed inside an secondary lithium or lithium- ion cell with a lithium counterelectrode and an electrolyte such as EC :DMC/LiPF 6 .
  • Li- L 01 Ti 0 01 O 4 was then mixed with 10% graphite and a 5% PVDF binder dissolved in n-methyl pyrrolidinone (NMP) solvent to form a slurry.
  • NMP n-methyl pyrrolidinone
  • the slurry was spread on aluminum foil and then heated to evaporate the solvent.
  • the dry electrode was then pressed at 500 kg/cm 2 and cut into a disk test sample electrode having a diameter of about 1 cm and a thickness of about 0.015 cm.
  • the prepared test electrode was placed inside an electrochemical cell with a lithium counter electrode and with an
  • Example 1 750°C for 6 hours, 825°C for 24 hours, and 725°C for 6 hours .
  • the heated mixture was then cooled to ambient temperature at a rate of 100°C/hr.
  • the stoichiometry of the resulting multiple oxide compound was Li L03 M1i L95 COo.oiTio.oiO 4 .
  • a spinel Li 1.03 Mn 1.95 Co 0.01 Ti 0.01 O 4 positive test electrode was prepared and an electrochemical cell assembled in the same manner as in Example 1. The cell charge/discharge characteristics were then measured under the same conditions as Example 1.
  • a spinel Li 1.05 Mn 1.93 Co 0.02 O 4 positive test electrode was prepared and the electrochemical cell assembled in the same manner as in Example 1. The cell charge/discharge characteristics were then measured under the same conditions as Example 1.
  • a spinel Li x .05 Mni .93 Ti o.o2 ⁇ 4 positive test electrode was prepared and an electrochemical cell assembled in the same manner as in Example 1. The cell charge/discharge characteristics were then measured under the same conditions as Example 1.
  • the heated mixture was then cooled to ambient temperature at a rate of 100°C/hr.
  • the stoichiometry of thus obtained multiple oxide compound was Li 1.05 Mn 1.95 O 4 .
  • a spinel Li 1.05 Mn 1-95 O 4 positive test electrode was prepared and an electrochemical cell assembled in the same manner as in Example 1. The cell charge/discharge characteristics were then measured under the same conditions as Example 1.
  • Figure 1 illustrates the specific capacity versus cycle number for the cell prepared according to Example 1 and the cells prepared according to
  • the undoped spinel has a good initial specific capacity but considerable capacity loss or capacity fade.
  • the titanium-doped spinel exhibits a slight improvement in capacity loss compared to the undoped spinel at the expense of a small decrease in specific capacity.
  • the cobalt-doped spinel compound demonstrates a significant improvement in capacity fade over the undoped spinel but also has a significant decrease in initial specific capacity.
  • the spinel produced in accordance with the invention, as shown in Figure 1 exhibits superior capacity fade without significant loss of initial specific capacity. This result would not be expected based on the initial specific capacity and cycling performance of the single-doped compounds as shown in Figure 1.
  • Figure 2 further illustrates the advantages of the multiple-doped lithium manganese oxide spinel compounds of the invention. Specifically, Figure 2 illustrates the specific capacity versus cycle number for the cell prepared according to Example 2 and the cell prepared according to Comparative Example 3. As shown in Figure 2, the substitution of excess lithium in the spinel compound with equivalent amounts of Co 3+ and Ti + cations can cause a substantial increase in the initial specific capacity without negatively affecting the capacity fade or cycleability of the spinel. Therefore, the addition of codopants can be used in combination with excess lithium or in place of excess lithium in the spinel compounds to benefit the electrical performance of the spinel.
  • the multiple-doped lithium manganese oxide spinels of the invention exhibit increased cycleability and reversible capacity over unsubstituted Li 1+x Mn 2 . x 0 4 spinels.
  • the multiple-doped lithium manganese oxide spinels produced in accordance with the invention in order to achieve an increase in cycleability without a corresponding significant decrease in specific capacity it has been found particularly important to have the combination of the valency state of the dopants, the position of the doped ions in the spinel structure, and the ionic radii size of the dopants described above. It is understood that upon reading the above description of the present invention and reviewing the accompanying drawings, one skilled in the art could make changes and variations therefrom. These changes and variations are included in the spirit and scope of the following appended claims.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

La présente invention concerne une électrode positive pour éléments d'accumulateur au lithium et aux ions de lithium, cette électrode présentant une aptitude à la cyclisation, des capacités spécifiques réversibles, et une stabilité structurelle satisfaisantes. Cette électrode positive comprend un oxyde multimétallique de lithium présentant une structure à spinelles, décrit par la formule générale (I) dans laquelle M1, M2, .....Mk sont au moins deux cations différents du lithium ou du manganèse, choisi dans le groupe composé des métaux alcalino-terreux, des métaux de transition, B, Al, Si, Ga, et Ge; X, Y, m¿1?, m2, ...mk sont des parties molaires dont les chiffres se situent entre 0 et 0,2; m1, m2, et Y sont supérieurs à 0; Z est un chiffre situé entre -0,1 et 0,2; et les métaux M?1, M2, ...Mk¿ et les parties molaires correspondantes m¿1?, m2, ...mk satisfont l'équation et l'inégalité suivantes: Y = X + m1 + m2 + ... + mk et (a) dans laquelle V1, V2, ...Vk sont les valences correspondantes des cations M?1, M2, ...Mk¿.
PCT/US1998/003847 1997-02-28 1998-02-27 Cathodes dopees a oxydes pour accumulateur electrique au lithium et pour accumulateur aux ions de lithium WO1998038648A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP10537881A JP2000500280A (ja) 1997-02-28 1998-02-27 リチウム二次電池及びリチウムイオン二次電池用の複数の金属イオンでドープされた酸化物のカソード材料

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US3966697P 1997-02-28 1997-02-28
US60/039,666 1997-02-28

Publications (1)

Publication Number Publication Date
WO1998038648A1 true WO1998038648A1 (fr) 1998-09-03

Family

ID=21906714

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1998/003847 WO1998038648A1 (fr) 1997-02-28 1998-02-27 Cathodes dopees a oxydes pour accumulateur electrique au lithium et pour accumulateur aux ions de lithium

Country Status (2)

Country Link
JP (1) JP2000500280A (fr)
WO (1) WO1998038648A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0973217A3 (fr) * 1998-07-13 2000-06-28 Ngk Insulators, Ltd. Composés de métaux de transition contenant du lithium pour une pile secondaire au lithium
EP1032061A1 (fr) * 1999-02-24 2000-08-30 Sony Corporation Pile à électrolyte non-aqueux
WO2001024293A1 (fr) * 1999-09-29 2001-04-05 Kerr-Mcgee Chemical Llc Compositions d'insertion pour cathodes, procedes de production et piles au lithium rechargeables renfermant ces compositions
US7026071B2 (en) 1996-10-11 2006-04-11 Massachusetts Institute Of Technology Non-crosslinked, amorphous, block copolymer electrolyte for batteries
EP1311013A3 (fr) * 2001-11-08 2006-12-27 Saft Finance S.à.r.l. Composé d'insertion du lithium à haute tension utilisable comme matière active cathodique de générateur électrochimique rechargeable au lithium
US8734998B2 (en) 2010-07-16 2014-05-27 Mitsui Mining & Smelting Co., Ltd. Spinel-type lithium transition metal oxide and positive electrode active material for lithium battery
CN114467200A (zh) * 2019-09-30 2022-05-10 松下知识产权经营株式会社 非水电解质二次电池用正极活性物质、和非水电解质二次电池

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20250013156A (ko) 2022-05-30 2025-01-31 스미또모 가가꾸 가부시키가이샤 알칼리 금속 함유 산화물, 정극 활물질, 전극 및 전지

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04345759A (ja) * 1991-05-21 1992-12-01 Toshiba Battery Co Ltd 非水溶媒二次電池

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04345759A (ja) * 1991-05-21 1992-12-01 Toshiba Battery Co Ltd 非水溶媒二次電池

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
GRYFFROY D. et al., "Cation Distribution, Cluster Structure and Ionic Ordering of the Spinel Series Lithium Nickel Manganese Titanium Oxide", J. PHYS. CHEM. SOLIDS, 1992, 53(6), pp. 777-84. *
GRYFFROY D. et al., "Optical Absorption of Nickel ÄNi2+(d8)Ü and Manganese ÄMn4+(d3)Ü in Some Spinel Oxides", SOLID STATE COMMUN., 1992, 82(7), pp. 497-500. *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7026071B2 (en) 1996-10-11 2006-04-11 Massachusetts Institute Of Technology Non-crosslinked, amorphous, block copolymer electrolyte for batteries
EP0973217A3 (fr) * 1998-07-13 2000-06-28 Ngk Insulators, Ltd. Composés de métaux de transition contenant du lithium pour une pile secondaire au lithium
US6368750B1 (en) 1998-07-13 2002-04-09 Ngk Insulators, Ltd. Lithium secondary battery
EP1032061A1 (fr) * 1999-02-24 2000-08-30 Sony Corporation Pile à électrolyte non-aqueux
US6656638B1 (en) 1999-02-24 2003-12-02 Sony Corporation Non-aqueous electrolyte battery having a lithium manganese oxide electrode
WO2001024293A1 (fr) * 1999-09-29 2001-04-05 Kerr-Mcgee Chemical Llc Compositions d'insertion pour cathodes, procedes de production et piles au lithium rechargeables renfermant ces compositions
US6248477B1 (en) 1999-09-29 2001-06-19 Kerr-Mcgee Chemical Llc Cathode intercalation compositions, production methods and rechargeable lithium batteries containing the same
AU766225B2 (en) * 1999-09-29 2003-10-09 Tronox Llc Cathode intercalation compositions, production methods and rechargeable lithium batteries containing the same
EP1311013A3 (fr) * 2001-11-08 2006-12-27 Saft Finance S.à.r.l. Composé d'insertion du lithium à haute tension utilisable comme matière active cathodique de générateur électrochimique rechargeable au lithium
US8734998B2 (en) 2010-07-16 2014-05-27 Mitsui Mining & Smelting Co., Ltd. Spinel-type lithium transition metal oxide and positive electrode active material for lithium battery
CN114467200A (zh) * 2019-09-30 2022-05-10 松下知识产权经营株式会社 非水电解质二次电池用正极活性物质、和非水电解质二次电池

Also Published As

Publication number Publication date
JP2000500280A (ja) 2000-01-11

Similar Documents

Publication Publication Date Title
US6040089A (en) Multiple-doped oxide cathode material for secondary lithium and lithium-ion batteries
EP1189296B9 (fr) Matériau à base d'oxide lithié et sa méthode de fabrication
US5759717A (en) Method for manufacturing a positive electrode active material for lithium battery
TWI437753B (zh) 鋰基電池之經金屬氧化物塗佈之正電極材料
EP1837937B1 (fr) Oxyde composite à base de manganèse au lithium et son procédé de préparation
US7468223B2 (en) Lithium metal oxide electrodes for lithium cells and batteries
US6613479B2 (en) Positive electrode material and battery for nonaqueous electrolyte secondary battery
EP1130665B1 (fr) Matière active positive pour électrode et pile secondaire à électrolyte non aqueux
KR20200141457A (ko) O3/p2 혼합상 나트륨을 함유하는 도핑된 층상 산화물 재료
US20090224212A1 (en) Surface and Bulk Modified High Capacity Layered Oxide Cathodes with Low Irreversible Capacity Loss
US20090127520A1 (en) Lithium metal oxide compositions
CN104795533A (zh) 锂电池用氧化锰复合电极
CN100371254C (zh) 硼取代的锂嵌入化合物、电极的活性材料、电池以及电致变色装置
EP1132985A2 (fr) Matière active positive pour utilisation dans une pile secondaire à electrolyte non-aqueux et pile l'utilisant
US5908716A (en) Lithium--containing sulfates, method of preparation and uses thereof
EP0734085B1 (fr) Oxyde mixte de manganèse et de lithium de type spinel en tant que matériau actif cathodique pour piles secondaires au lithium à électrolyte non-aqueux
Sanchez et al. Synthesis and electrochemical characterization of a new Li‐Co‐Mn‐O spinel phase for rechargeable lithium batteries
KR20220023569A (ko) 이차전지용 양극활물질 및 양극활물질 제조방법
WO1998038648A1 (fr) Cathodes dopees a oxydes pour accumulateur electrique au lithium et pour accumulateur aux ions de lithium
JP7676851B2 (ja) 遷移金属複合水酸化物粒子、遷移金属複合水酸化物粒子の製造方法、リチウムイオン二次電池用正極活物質、及びリチウムイオン二次電池
EP1130664B1 (fr) Matière active positive pour électrode et pile secondaire à électrolyte non aqueux
CN117423828A (zh) 正极活性材料及其制备方法、正极片和二次电池
JPH11189419A (ja) リチウム二次電池用スピネル系マンガン酸化物
KR102618005B1 (ko) 양극 활물질의 제조 방법
KR100237311B1 (ko) 졸-겔법을 이용한 리튬 이차전지용 양극 활물질, 그 제조방법 및 이 물질을 이용한 리튬이차전지

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): JP

ENP Entry into the national phase

Ref country code: JP

Ref document number: 1998 537881

Kind code of ref document: A

Format of ref document f/p: F

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载