US20090087746A1 - Spherical Metal Carbonates and Lithium Metal Oxides for Lithium Rechargeable Batteries - Google Patents

Spherical Metal Carbonates and Lithium Metal Oxides for Lithium Rechargeable Batteries Download PDF

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US20090087746A1
US20090087746A1 US12/249,799 US24979908A US2009087746A1 US 20090087746 A1 US20090087746 A1 US 20090087746A1 US 24979908 A US24979908 A US 24979908A US 2009087746 A1 US2009087746 A1 US 2009087746A1
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lithium
carbonate
active composition
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nickel
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Sun-Ho Kang
Khalil Amine
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UChicago Argonne LLC
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    • 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
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    • C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
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    • 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
    • H01M4/1315—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx containing halogen atoms, e.g. LiCoOxFy
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    • Y02E60/10—Energy storage using batteries

Definitions

  • Rechargeable lithium batteries have become widely used in both consumer and industrial applications. Rechargeable lithium batteries have a higher volumetric and gravimetric energy densities than other rechargeable batteries such as nickel metal hydride (NiMH) batteries and Ni—Cd batteries. Furthermore, the rechargeable lithium batteries have no memory effects and do not contain any poisonous metal elements such as mercury, lead, and cadmium.
  • the applications of lithium batteries encompass a wide range of applications including small portable electronics such as notebook computers and personal digital assistants to electric vehicles and satellites.
  • Li(Mn 0.5 Ni 0.5 )O 2 is a promising cathode material for Li-ion rechargeable batteries due to its lower cost, improved thermal safety performance, and lower toxicity compared with LiNiO 2 and LiCoO 2 .
  • Li(Mn 0.5 Ni 0.5 )O 2 exhibits rather small capacity for high-energy applications and rather high impedance for high-power applications.
  • spherical metal carbonates have been developed with a narrow size distribution and with a composition of (Ni a CO b Mn c )CO 3 , where the a is between 0 and about 1, the b between 0 and about 1, and the c between 0 and about 1.
  • Extensive testing was conducted to investigate the effect of various experimental factors—concentration of metal solutions, concentration of precipitating agent solutions, reaction temperature, and aging time—on the size and morphology of the precipitates.
  • Spherical lithium metal oxides were synthesized by using the spherical metal carbonates.
  • FIGS. 1( a )- 1 ( c ) show the morphology of (Ni ⁇ Mn ⁇ Co ⁇ )-carbonate prepared by a co-precipitation method using ammonium hydrogen carbonate using magnification factors of ⁇ 500, ⁇ 2,000, and ⁇ 12,000, respectively;
  • FIGS. 2( a )- 2 ( c ) show the morphology of Li 1+x Ni ⁇ Mn ⁇ Co ⁇ O 2 prepared by calcinations of (Ni ⁇ Mn ⁇ Co ⁇ )-carbonate and lithium carbonate at 1000° C. for 10 h in air, using magnification factors of ⁇ 1,000, ⁇ 2,000, and ⁇ 12,000, respectively;
  • FIG. 3 and FIG. 4 are plots showing the X-ray diffraction patterns of various Li 1+x Ni ⁇ Mn ⁇ Co ⁇ M′ ⁇ O 2 ⁇ z F z compounds;
  • FIG. 5 is a plot showing the first charge/discharge curves of Li/Li(Ni ⁇ Mn ⁇ Co ⁇ )O 2 ⁇ z F z cells;
  • FIG. 6 is a plot showing the cycling performance of Li/Li(Ni ⁇ Mn ⁇ Co ⁇ )O 2 ⁇ z F z cells;
  • FIG. 7 is a plot showing the area specific impedance of C/Li(Ni ⁇ Mn ⁇ )O 2 ⁇ z F z cells as a function of state of charge measured by 30 s-current interruption;
  • FIG. 8 is a plot showing the variation of the area specific impedance values at 50% state of charge of C/Li(Ni ⁇ Mn ⁇ )O 2 ⁇ z F z cells;
  • FIGS. 9 and 10 show the cycling performance of uncoated Li(Ni ⁇ Mn ⁇ Co ⁇ )O 2 , Li(Ni ⁇ Mn ⁇ Co ⁇ )O 2 coated with 0.5 wt % Al-isopropoxide, and Li(Ni ⁇ Mn ⁇ Co ⁇ )O 2 coated with 1.0 wt % Al-isopropoxide at room temperature and 55° C., respectively;
  • FIG. 11 shows the variation of area specific impedance (ASI) with cycling of C/Li(Ni ⁇ Mn ⁇ Co ⁇ )O 2 measured by a 30 s current interruption method;
  • FIG. 12 shows the a.c. impedance spectroscopy of C/Li(Ni ⁇ Mn ⁇ Co ⁇ )O 2 cells as a function of cycle number measured with C/Li(Ni ⁇ Mn ⁇ Co ⁇ )O 2 cells;
  • FIG. 13 presents the variation of area specific impedance at 60% SOC with a 55° C.-storage time measured with C/Li(Ni ⁇ Mn ⁇ Co ⁇ )O 2 cells;
  • FIG. 14 is a plot showing the first charge/discharge curves and variation of discharge capacity with cycle number of Li/Li 1+x (Ni ⁇ Mn ⁇ Co ⁇ )O 2 cells;
  • FIG. 15 is a plot showing the area specific impedance of C/Li 1+x (Ni ⁇ Mn ⁇ Co ⁇ )O 2 cells as a function of state of charge measured by a 30 s current interruption method;
  • FIG. 16 is a plot showing the cycling performance of Li/Li 1+x (Ni ⁇ Mn ⁇ Co ⁇ )O 2 ⁇ z F z cells at room temperature and at 55° C.;
  • FIG. 17 is a plot showing the area specific impedance of Li/Li 1+x (Ni ⁇ Mn ⁇ Co ⁇ )O 2 ⁇ z F z cells measured by a 30 s current interruption method;
  • FIG. 18 shows scanning electron microscope (SEM) images of (Ni 1/3 Co 1/3 Mn 1/3 )CO 3 precipitates with the concentration of metal solutions [Me] and concentrations of ammonium hydrogen carbonate solution [AHC] at 0.1 and 1.0M respectively; the reaction temperature (T R ) and the aging time (t a ) 65° C. and 17 h, respectively;
  • FIG. 23 represents the X-ray diffraction (XRD) patterns of the (Ni 1/3 Co 1/3 Mn 1/3 )CO 3 and MnCO 3 precipitates shown in FIGS. 18 and 21 , respectively, together with the reported XRD patterns of MnCO 3 (JCPDS 86-173);
  • XRD X-ray diffraction
  • FIG. 24 shows SEM images of Li[Ni 1/3 Co 1/3 Mn 1/3 ]O 2 prepared using the (Ni 1/3 Co 1/3 Mn 1/3 )CO 3 shown in FIG. 18 with calcination carried out at 1000° C. for 10 h in air;
  • FIG. 25 represents the XRD patterns of the Li[Ni 1/3 Co 1/3 Mn 1/3 ]O 2 material shown in FIG. 24 ;
  • FIGS. 26( a ) and 26 ( b ) show the first charge/discharge curves of the Li/Li[Ni 1/3 Co 1/3 Mn 1/3 ]O 2 cells cycled in the voltage range of 2.8-4.6V and the variation of the discharge capacities as a function of cycle number, respectively.
  • the present invention presents layered lithium nickel manganese oxide cathode materials for lithium secondary batteries such as: (1) cathode materials doped with fluorine on oxygen sites to reduce impedance and to improve cycling stability at high temperature as well as at room temperature; (2) cathode materials doped with various metal ions on transition metal site to stabilize layered structure, suppress cation mixing and, consequently, improve electrochemical properties; lithium, cobalt, magnesium, zinc, aluminum, gallium, boron, zirconium, and titanium ions were chosen for the latter purposes; and (3) cathode materials surface-coated to improve cycling/power performance and thermal safety, wherein the coating element of the coating material source is at least one element selected from the group consisting of Al, Bi, Ga, Ge, In, Mg, Pb, Si, Sn, Ti, TI, Zn, Zr.
  • Another aspect of the present invention relates to a method of preparing: 1) spherical mixed nickel-cobalt-manganese carbonates with a narrow size distribution, and 2) spherical lithium nickel cobalt manganese oxide using the spherical carbonate precursors.
  • (Ni,Mn,Co)-hydroxides or (Ni, Mn,Co)-carbonates may be prepared by a co-precipitation method.
  • NH 4 OH ammonium hydroxide
  • NaOH sodium hydroxide
  • the pH of the overall solution is kept at 10 ⁇ 12 using NaOH.
  • NiSO 4 or Ni(CH 3 COO) 2 .xH 2 O or Ni(NO 3 ) 2 .xH 2 O
  • MnSO 4 or Mn(CH 3 COO) 2 .xH 2 O or Mn(NO 3 ) 2 .xH 2 O
  • CoSO 4 or Co(CH 3 COO) 2 .xH 2 O or Co(NO 3 ) 2 .xH 2 O
  • ammonium hydrogen carbonate [(NH) 4 HCO 3 ] or sodium carbonate (Na 2 CO 3 ).
  • aqueous solution method For the aqueous solution method, appropriate amounts of lithium hydroxide, lithium fluoride, nickel hydroxide, cobalt hydroxide, and M′-hydroxide (or M′-nitrate) are dissolved in distilled water whose pH is adjusted with nitric acid. An aqueous solution of manganese acetate is added to the above solution. The mixed solution is refluxed in a round bottom flask attached with a condenser at 80° C. for about 12-24 hours and evaporated in a rotary vacuum evaporator. Organic contents in the gel precursor are eliminated at 400° C. for 2 hours. Finally, the resulting powder is calcined at 800-1000° C. for about 10-24 hours either in air or in an oxygen-containing atmosphere.
  • coating solutions are prepared by dissolving coating material sources in organic solvents or water.
  • the coating material sources include A′-alkoxide, A′-salt or A′-oxide, where A′ includes Al, Bi, Ga, Ge, In, Mg, Pb, Si, Sn, Ti, Tl, Zn, Zr or mixtures thereof.
  • the coating solutions are mixed with the synthesized compound Li 1+x Ni ⁇ Mn ⁇ Co ⁇ M′ ⁇ O 2 ⁇ z F z by an impregnation method such as dip coating.
  • the amount of coating material sources may be between about 0.05 and 10 weight percent of Li 1+x Ni ⁇ Mn ⁇ Co ⁇ M′ ⁇ O 2 ⁇ z F z . Thereafter, the surface-coated Li 1+x Ni ⁇ Mn ⁇ Co ⁇ M′ ⁇ O 2 ⁇ z F z powder is dried at temperatures between about 25° C. and 700° C. for approximately 1 to 24 hours.
  • the synthesized compound is mixed with a carbon additive and a PVDF binder to form a laminate film on an aluminum foil.
  • This laminate is used for electrochemical testing in the presence of lithium or carbon counter electrodes and non-aqueous electrolytes made of LiPF 6 /EC:DEC (1:1).
  • FIGS. 1( a )- 1 ( c ) show the morphology of (Ni ⁇ Mn ⁇ Co ⁇ )-carbonate prepared by the co-precipitation method using ammonium hydrogen carbonate. Spherical shape precursors with homogeneous size distribution are obtained by the co-precipitation.
  • the magnification factors of FIGS. 1( a ), 1 ( b ), and 1 ( c ) are ⁇ 500, ⁇ 2,000, and ⁇ 12,000, respectively.
  • FIGS. 2( a )- 2 ( c ) show the morphology of Li 1+x Ni ⁇ Mn ⁇ Co ⁇ O 2 prepared by calcinations of (Ni ⁇ Mn ⁇ Co ⁇ )-carbonate and lithium carbonate at 1000° C. for 10 h in air. The spherical shape of the precursor is preserved after calcinations.
  • the magnification factors of FIGS. 2( a ), 2 ( b ) and 2 ( c ) are ⁇ 1,000, ⁇ 2,000, and ⁇ 12,000, respectively.
  • FIGS. 3 and 4 represent X-ray diffraction patterns of Li 1+x Ni ⁇ Mn ⁇ Co ⁇ M′ ⁇ O 2 ⁇ z F z compounds. All of the compounds exhibit the ordered rock-salt structure with crystallographic structure of R 3 m.
  • the Li-excess composition such as Li(Li 0.2 Ni 0.2+0.5 z Co 0.1 Mn 0.5-0.5z )O 2 ⁇ z F z , extra peaks appear at 20 ⁇ 25°, as shown in FIG. 4 , which are generally attributed to cation ordering in the transition metal layer.
  • FIG. 5 shows the first charge/discharge curves of Li/Li(Ni ⁇ Mn ⁇ Co ⁇ )O 2 ⁇ z F z cells
  • FIG. 6 shows cycling performance of Li/Li(Ni ⁇ Mn ⁇ Co ⁇ )O 2 ⁇ z F z cells.
  • FIGS. 5 and 6 clearly show that the discharge capacity increases by more than 10%, and the cycling performance improves by the simultaneous substitution of cations and anions.
  • FIG. 7 shows area specific impedance (ASI) of C/Li(Ni ⁇ Mn ⁇ )O 2 ⁇ z F z cells as a function of state of charge (SOC) measured by 30 s-current interruption.
  • FIG. 8 shows the variation of the ASI values at 50% SOC of C/Li(Ni ⁇ Mn ⁇ )O 2 ⁇ z F z cells.
  • FIGS. 7 and 8 clearly show that fluorine doping lowers impedance and enhances cycling stability.
  • FIGS. 9 and 10 show the cycling performance of uncoated Li(Ni ⁇ Mn ⁇ Co ⁇ )O 2 , Li(Ni ⁇ Mn ⁇ Co ⁇ )O 2 coated with 0.5 wt % Al-isopropoxide, and Li(Ni ⁇ Mn ⁇ Co ⁇ )O 2 coated with 1.0 wt % Al-isopropoxide at room temperature and 55° C., respectively.
  • the coating solution is prepared by dissolving appropriate amount of Al-isopropoxide in ethanol.
  • Li(Ni ⁇ Mn ⁇ Co ⁇ )O 2 powders are then mixed thoroughly with the coating solution and dried at 100° C. for 12 h. The coated powders are subsequently heat-treated at 300° C.
  • FIG. 11 shows the variation of area specific impedance (ASI) with cycling of C/Li(Ni ⁇ Mn ⁇ Co ⁇ )O 2 measured by a 30 s current interruption method with C/Li(Ni ⁇ Mn ⁇ Co ⁇ )O 2 cells.
  • ASI area specific impedance
  • FIG. 12 shows the a.c. impedance spectroscopy of C/Li(Ni ⁇ Mn ⁇ Co ⁇ )O 2 cells as a function of cycle number measured with C/Li(Ni ⁇ Mn ⁇ Co ⁇ )O 2 cells.
  • This representation indicates the surface coating significantly improves the stability of the cathode surface/electrolyte interface.
  • FIG. 13 presents the impedance variation with a 55° C.-storage time measured with C/Li(Ni ⁇ Mn ⁇ Co ⁇ )O 2 cells.
  • FIGS. 9-13 clearly show the surface coating greatly improving the cycle life, as well as calendar life, of the lithium-ion cells.
  • FIG. 14 shows the first charge/discharge curves and variation of discharge capacity with cycle number of Li/Li 1+x (Ni ⁇ Mn ⁇ Co ⁇ )O 2 cells.
  • FIG. 15 shows the area specific impedance of C/Li 1+x (Ni ⁇ Mn ⁇ Co ⁇ )O 2 cells as a function of state of charge measured by a 30 s current interruption method.
  • FIG. 16 shows cycling performance of Li/Li 1+x (Ni ⁇ Mn ⁇ Co ⁇ )O 2-z F z cells at room temperature and at 55° C.
  • FIG. 17 shows the area specific impedance of Li/Li 1+x (Ni ⁇ Mn ⁇ Co ⁇ )O 2-z F z cells measured by a 30 s current interruption method.
  • FIGS. 14-17 clearly show that substitution of oxygen with fluorine significantly improves cycling performance and lowers the impedance of the cathode materials.
  • Another aspect of the present invention relates to a method for preparing spherical, mixed nickel-cobalt-manganese carbonates with a narrow size distribution and a method for preparing spherical lithium nickel cobalt manganese oxide using the spherical precursors, a coprecipitation method is used to prepare the spherical precursors, (Ni a CO b Mn c )CO 3 , where the a is between 0 and 1, the b between 0 and 1, and the c between 0 and 1.
  • Ammonium hydrogen carbonate (NH 4 HCO 3 ) or sodium carbonate (Na 2 CO 3 ) is used for precipitating agents for the coprecipitation.
  • the spherical (Ni a Co b Mn c )CO 3 is prepared by coprecipitation as follows. Appropriate amounts of Ni-acetate (or Ni-nitrate or Ni-sulfate), Co-acetate (or Co-nitrate or Co-sulfate), and Mn-acetate (or Mn-nitrate or Ni-sulfate) are dissolved in distilled water and the metal solution is added to another aqueous solution of ammonium hydrogen carbonate or sodium carbonate.
  • the concentration of metal solutions ([Me]) is varied from about 0.01M to about 2M; the concentrations of ammonium hydrogen carbonate solution ([AHC]) or sodium carbonate ([SC]) is varied from about 0.1 M to about 5M.
  • the pH of the ammonium hydrogen carbonate solution or the sodium carbonate solution is varied from about 7 to about 12 using ammonium hydroxide or sodium hydroxide.
  • the reaction temperature is varied from about 20° C. to about 65° C.
  • the metal solution is added to the ammonium hydrogen carbonate solution, the precipitates form instantly.
  • the precipitates are then aged in the solution at each temperature from about 1 h to about 24 h. All of the precipitation reaction and aging are carried out under constant stirring. After aging, the coprecipitated powders are filtered and dried.
  • the mixed powers are calcined at about 450° C. to about 700° C. for about 12-30 hours either in air or in oxygen atmospheres and then at about 700° C. to about 1000° C. for about 10-24 hours either in air or in oxygen atmospheres.
  • the synthesized compound Li 1+x Ni ⁇ Co ⁇ Mn ⁇ M′ ⁇ O y F z is mixed with a carbon additive and a PVDF binder to form a laminate film on aluminum foil.
  • This laminate is used, for example, in electrochemical testing in the presence of lithium or carbon counter electrode and non-aqueous electrolyte made of LiPF 6 /ED:DEC (1:1).
  • FIG. 18 shows SEM images of (Ni 1/3 Co 1/3 Mn 1/3 )CO 3 precipitates.
  • the a metal solution and ammonium hydrogen carbonate (AHC) concentrations were 0.1 and 1.0M respectively; the reaction temperature (T R ) and the aging time (t a ) were 65° C. and 17 h, respectively.
  • T R reaction temperature
  • t a aging time
  • FIG. 19 shows additional SEM images of (Ni 1/3 Co 1/3 Mn 1/3 )CO 3 , prepared by different methods
  • FIG. 23 represents the x-ray diffraction (XRD) patterns of the (Ni 1/3 Co 1/3 Mn 1/3 )CO 3 and MnCO 3 precipitates shown in FIGS. 18 and 21 , respectively, together with the reported XRD patterns of MnCO 3 .
  • the XRD patterns of the coprecipitated materials are well matched with the reported XRD patterns of MnCO 3 with rhombohedral structure (space group of R3c).
  • FIG. 24 shows the SEM images of Li[Ni 1/3 Co 1/3 Mn 1/3 ]O 2 prepared using the (Ni 1/3 Co 1/3 Mn 1/3 )CO 3 shown in FIG. 18 .
  • the calcinations were carried out at about 1000° C. for about 10 h in air. It can be seen in FIG. 24 that the Li[Ni 1/3 Co 1/3 Mn 1/3 ]O 2 material retained the size and morphology of the (Ni 1/3 Co 1/3 Mn 1/3 )CO 3 precursor.
  • FIG. 25 represents the XRD patterns of the Li[Ni 1/3 Co 1/3 Mn 1/3 ]O 2 material shown in FIG. 24 .
  • the material exhibits the ordered rock-salt structure with crystallographic structure of R3m.
  • FIGS. 26( a ) and 26 ( b ) show the first charge/discharge curves of the Li/Li[Ni 1/3 Co 1/3 Mn 1/3 ]O 2 cells cycled in the voltage range of 2.8-4.6V and the variation of the discharge capacities as a function of cycle number, respectively.
  • the materials described herein can be used as cathodes in lithium-ion rechargeable batteries for products such as electric vehicles, hybrid electric vehicles, portable electronics, and a variety of other products.
  • the materials described herein are less expensive and thermally safer than existing cathode materials such as LiCoO 2 and LiNiO 2 .
  • the materials of the present invention also exhibit improved calendar/cycle life when compared to existing cathode materials.

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Abstract

A number of materials with the composition Li1+xNiαMnβCoγM′δO2−zFz (M′=Mg, Zn, Al, Ga, B, Zr, Ti) for use with rechargeable batteries, wherein x is between about 0 and 0.3, α is between about 0.2 and 0.6, β is between about 0.2 and 0.6, γ is between about 0 and 0.3, δ is between about 0 and 0.15, and z is between about 0 and 0.2. Adding the above metal and fluorine dopants affects capacity, impedance, and stability of the layered oxide structure during electrochemical cycling. Another aspect of the invention includes materials with the composition Li1+xNiαCoβMnγM′δOyFz (M′=Mg, Zn, Al, Ga, B, Zr, Ti), where the x is between 0 and 0.2, the α between 0 and 1, the β between 0 and 1, the γ between 0 and 2, the δ between about 0 and about 0.2, the y is between 2 and 4, and the z is between 0 and 0.5.

Description

    CROSS-REFERENCE TO RELATED PATENT APPLICATIONS
  • This application is a divisional application and claims priority to U.S. patent application Ser. No. 10/903,514, titled “Method and Apparatus for Preparation of Spherical Metal Carbonates and Lithium Metal Oxides for Lithium Metal Oxides for Lithium Rechargeable Batteries”, filed on Jul. 30, 2004, and incorporated herein by reference in its entirety, which is a continuation in part of and claims priority to U.S. patent application Ser. No. 10/699,484, titled “Layered Cathode materials for Lithium Ion Rechargeable Batteries”, filed on Oct. 31, 2003, and incorporated herein by reference in its entirety, which claims priority to U.S. Provisional Patent Application No. 60/423,347, filed Nov. 1, 2002, also incorporated herein by reference in its entirety.
    • STATEMENT OF GOVERNMENT INTEREST
  • This invention was made with government support under Contract No. W-31-109-ENG-38 awarded to the Department of Energy. The Government has certain rights in this invention.
    • BACKGROUND OF THE INVENTION
  • Rechargeable lithium batteries have become widely used in both consumer and industrial applications. Rechargeable lithium batteries have a higher volumetric and gravimetric energy densities than other rechargeable batteries such as nickel metal hydride (NiMH) batteries and Ni—Cd batteries. Furthermore, the rechargeable lithium batteries have no memory effects and do not contain any poisonous metal elements such as mercury, lead, and cadmium. The applications of lithium batteries encompass a wide range of applications including small portable electronics such as notebook computers and personal digital assistants to electric vehicles and satellites.
  • Li(Mn0.5Ni0.5)O2 is a promising cathode material for Li-ion rechargeable batteries due to its lower cost, improved thermal safety performance, and lower toxicity compared with LiNiO2 and LiCoO2. However, Li(Mn0.5Ni0.5)O2 exhibits rather small capacity for high-energy applications and rather high impedance for high-power applications.
  • In addition to new types of cathode materials, various changes in the uses of lithium batteries have brought focus upon the energy density and packing density of the batteries. To achieve the high packing density of the cathode composite, spherical cathode particles with a narrow size distribution are desired. Furthermore, since a sphere has the smallest surface area among other morphology with the same volume, it is believed that thermal safety is increased with the use of spherical particles by way of reducing the contact areas between the cathode materials and liquid electrolyte.
  • A need therefore remains for an improved layered cathode material for use with lithium ion rechargeable batteries
    • SUMMARY OF THE INVENTION
  • It is therefore an object of the present invention to provide an improved cathode for rechargeable batteries that possesses improved impedance characteristics.
  • It is another object of the present invention to provide an improved cathode for rechargeable batteries that possesses improved stability of the layered oxide structure during electrochemical cycling.
  • It is another object of the present invention to provide an improved cathode for rechargeable batteries that possesses improved packing density and thermal safety.
  • It is still another object of the present invention to provide an improved cathode for rechargeable batteries that possesses improved capacity characteristics.
  • In accordance with the above objects, a number of materials with composition Li1+xNiαMnβCoγM′δO2−zFz (M′=Mg, Zn, Al, Ga, B, Zr, Ti) have been developed for use with rechargeable batteries, wherein x is between 0 and about 0.3, α is between about 0.2 and about 0.6, β is between about 0.2 and about 0.6, γ is between 0 and about 0.3, 8 is between 0 and about 0.15, and z is between 0 and about 0.2. Surface-coated Li1+xNiαMnβCoγM′δO2−zFz (M′=Mg, Zn, Al, Ga, B, Zr, Ti) has also been developed, wherein x is between 0 and about 0.3, α is between about 0.2 and about 0.6, β is between about 0.2 and about 0.6, γ is between 0 and about 0.3, δ is between 0 and about 0.15, and z is between 0 and about 0.2. Extensive testing has been conducted to investigate the effect of adding the above metal and fluorine dopants and the surface modification on capacity, impedance, and stability of the layered oxide structure during electrochemical cycling.
  • Further, in accordance with the above objects, a number of spherical metal carbonates have been developed with a narrow size distribution and with a composition of (NiaCObMnc)CO3, where the a is between 0 and about 1, the b between 0 and about 1, and the c between 0 and about 1. Extensive testing was conducted to investigate the effect of various experimental factors—concentration of metal solutions, concentration of precipitating agent solutions, reaction temperature, and aging time—on the size and morphology of the precipitates. Spherical lithium metal oxides were synthesized by using the spherical metal carbonates. The composition of the spherical lithium metal oxides thus synthesized is Li1+xNiαCoβMnγM′δOyFz (M′=Mg, Zn, Al, Ga, B, Zr, Ti), where the x is between 0 and about 0.2, the α between 0 and about 1, the β between 0 and about 1, the γ between 0 and about 2, the δ between 0 and about 0.2, the y is between about 2 and about 4, and the z is between 0 and about 0.5.
    • BRIEF DESCRIPTION OF THE DRAWINGS
  • FIGS. 1( a)-1(c) show the morphology of (NiαMnβCoγ)-carbonate prepared by a co-precipitation method using ammonium hydrogen carbonate using magnification factors of ×500, ×2,000, and ×12,000, respectively;
  • FIGS. 2( a)-2(c) show the morphology of Li1+xNiαMnβCoγO2 prepared by calcinations of (NiαMnβCoγ)-carbonate and lithium carbonate at 1000° C. for 10 h in air, using magnification factors of ×1,000, ×2,000, and ×12,000, respectively;
  • FIG. 3 and FIG. 4 are plots showing the X-ray diffraction patterns of various Li1+xNiαMnβCoγM′δO2−zFz compounds;
  • FIG. 5 is a plot showing the first charge/discharge curves of Li/Li(NiαMnβCoγ)O2−zFz cells;
  • FIG. 6 is a plot showing the cycling performance of Li/Li(NiαMnβCoγ)O2−zFz cells;
  • FIG. 7 is a plot showing the area specific impedance of C/Li(NiαMnβ)O2−zFz cells as a function of state of charge measured by 30 s-current interruption;
  • FIG. 8 is a plot showing the variation of the area specific impedance values at 50% state of charge of C/Li(NiαMnβ)O2−zFz cells;
  • FIGS. 9 and 10 show the cycling performance of uncoated Li(NiαMnβCoγ)O2, Li(NiαMnβCoγ)O2 coated with 0.5 wt % Al-isopropoxide, and Li(NiαMnβCoγ)O2 coated with 1.0 wt % Al-isopropoxide at room temperature and 55° C., respectively;
  • FIG. 11 shows the variation of area specific impedance (ASI) with cycling of C/Li(NiαMnβCoγ)O2 measured by a 30 s current interruption method;
  • FIG. 12 shows the a.c. impedance spectroscopy of C/Li(NiαMnβCoγ)O2 cells as a function of cycle number measured with C/Li(NiαMnβCoγ)O2 cells;
  • FIG. 13 presents the variation of area specific impedance at 60% SOC with a 55° C.-storage time measured with C/Li(NiαMnβCoγ)O2 cells;
  • FIG. 14 is a plot showing the first charge/discharge curves and variation of discharge capacity with cycle number of Li/Li1+x(NiαMnβCoγ)O2 cells;
  • FIG. 15 is a plot showing the area specific impedance of C/Li1+x(NiαMnβCoγ)O2 cells as a function of state of charge measured by a 30 s current interruption method;
  • FIG. 16 is a plot showing the cycling performance of Li/Li1+x(NiαMnβCoγ)O2−zFz cells at room temperature and at 55° C.;
  • FIG. 17 is a plot showing the area specific impedance of Li/Li1+x(NiαMnβCoγ)O2−zFz cells measured by a 30 s current interruption method;
  • FIG. 18 shows scanning electron microscope (SEM) images of (Ni1/3Co1/3Mn1/3)CO3 precipitates with the concentration of metal solutions [Me] and concentrations of ammonium hydrogen carbonate solution [AHC] at 0.1 and 1.0M respectively; the reaction temperature (TR) and the aging time (ta) 65° C. and 17 h, respectively;
  • FIG. 19( a) shows SEM images of (Ni1/3Co1/3Mn1/3)CO3 precipitates prepared with [Me]=0.05M, [AHC]=0.5M, TR=65° C., ta=17 h; and 19(b) shows SEM images of (Ni1/3Co1/3Mn1/3)CO3 precipitates prepared with [Me]=0.2M, [AHC]=2.0M, TR=65° C., ta=4 h;
  • FIGS. 20( a) and 20(b) represent the SEM images of (Ni0.219Co0.125Mn0.656)CO3 precipitates prepared with [Me]=0.1M, [AHC]=1.0M, ta=6 h at different temperatures (20 and 40° C., respectively);
  • FIG. 21 shows an SEM image of MnCO3 precipitates prepared with [Me]=0.1M, [AHC]=1.0M, TR=55° C., and ta=17 h;
  • FIG. 22 shows an SEM image of (Cu0.5Mn0.5)CO3 precipitates prepared with [Me]=0.1M, [AHC]=1.0M, TR=50° C., and ta=17 h;
  • FIG. 23 represents the X-ray diffraction (XRD) patterns of the (Ni1/3Co1/3Mn1/3)CO3 and MnCO3 precipitates shown in FIGS. 18 and 21, respectively, together with the reported XRD patterns of MnCO3 (JCPDS 86-173);
  • FIG. 24 shows SEM images of Li[Ni1/3Co1/3Mn1/3]O2 prepared using the (Ni1/3Co1/3Mn1/3)CO3 shown in FIG. 18 with calcination carried out at 1000° C. for 10 h in air;
  • FIG. 25 represents the XRD patterns of the Li[Ni1/3Co1/3Mn1/3]O2 material shown in FIG. 24; and
  • FIGS. 26( a) and 26(b) show the first charge/discharge curves of the Li/Li[Ni1/3Co1/3Mn1/3]O2 cells cycled in the voltage range of 2.8-4.6V and the variation of the discharge capacities as a function of cycle number, respectively.
    •  DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
  • The present invention presents layered lithium nickel manganese oxide cathode materials for lithium secondary batteries such as: (1) cathode materials doped with fluorine on oxygen sites to reduce impedance and to improve cycling stability at high temperature as well as at room temperature; (2) cathode materials doped with various metal ions on transition metal site to stabilize layered structure, suppress cation mixing and, consequently, improve electrochemical properties; lithium, cobalt, magnesium, zinc, aluminum, gallium, boron, zirconium, and titanium ions were chosen for the latter purposes; and (3) cathode materials surface-coated to improve cycling/power performance and thermal safety, wherein the coating element of the coating material source is at least one element selected from the group consisting of Al, Bi, Ga, Ge, In, Mg, Pb, Si, Sn, Ti, TI, Zn, Zr. Another aspect of the present invention relates to a method of preparing: 1) spherical mixed nickel-cobalt-manganese carbonates with a narrow size distribution, and 2) spherical lithium nickel cobalt manganese oxide using the spherical carbonate precursors.
  • Either a solid-state reaction method or an aqueous solution method or a sol-gel method may be employed for the preparation of the compounds Li1+xNiαMnβCoγM′δO2−zFz with the value M′=Mg, Zn, Al, Ga, B, Zr, Ti.
  • For the solid state reaction method, (Ni,Mn,Co)-hydroxides or (Ni, Mn,Co)-carbonates may be prepared by a co-precipitation method. For preparation of (Ni,Mn, Co)-hydroxides, appropriate amount of NiSO4 [or Ni(CH3COO)2.xH2O or Ni(NO3)2.xH2O], MnSO4 [or Mn(CH3COO)2.xH2O or Mn(NO3)2.xH2O], and CoSO4 [or Co(CH3COO)2.xH2O or Co(NO3)2.xH2O] are dissolved in distilled water, and the solution is added to another solution of ammonium hydroxide (NH4OH) and sodium hydroxide (NaOH) with a pH=10˜12. During the co-precipitation process, the pH of the overall solution is kept at 10˜12 using NaOH. For preparation of (Ni,Mn,Co)-carbonates, appropriate amount of NiSO4 [or Ni(CH3COO)2.xH2O or Ni(NO3)2.xH2O], MnSO4 [or Mn(CH3COO)2.xH2O or Mn(NO3)2.xH2O], and CoSO4 [or Co(CH3COO)2.xH2O or Co(NO3)2.xH2O] are dissolved in distilled water, and the solution is added to another aqueous solution of ammonium hydrogen carbonate [(NH)4HCO3] or sodium carbonate (Na2CO3). During the co-precipitation process, the temperature of the overall solution is kept at 40-70° C. The co-precipitated powders are filtered and dried. To prepare a Li1+xNiαMnβCoγM′δO2−zFz (M′=Mg, Zn, Al, Ga, B, Zr, Ti) compound, appropriate amounts of lithium hydroxide (or lithium carbonate), lithium fluoride, (Ni,Mn,Co)-hydroxide [or (Ni,Mn,Co)-carbonate], and M′-hydroxides (or M′-oxides) are mixed. The mixed powders are calcined at 450˜700° C. for 12-30 hours in air and then at 700-1000° C. for 10-24 hours either in air or in an oxygen-containing atmosphere.
  • For the aqueous solution method, appropriate amounts of lithium hydroxide, lithium fluoride, nickel hydroxide, cobalt hydroxide, and M′-hydroxide (or M′-nitrate) are dissolved in distilled water whose pH is adjusted with nitric acid. An aqueous solution of manganese acetate is added to the above solution. The mixed solution is refluxed in a round bottom flask attached with a condenser at 80° C. for about 12-24 hours and evaporated in a rotary vacuum evaporator. Organic contents in the gel precursor are eliminated at 400° C. for 2 hours. Finally, the resulting powder is calcined at 800-1000° C. for about 10-24 hours either in air or in an oxygen-containing atmosphere.
  • For the sol-gel method, appropriate amounts of lithium acetate, lithium fluoride, nickel acetate, manganese acetate, cobalt acetate, and M′-acetate are dissolved in distilled water and added to a glycolic/tartaric acid solution that is used as a chelating agent. The solution pH is adjusted to around 7 using ammonium hydroxide. The entire process is conducted under continuous stirring and heating on a hot plate. The resulting gel precursor is decomposed at 450° C. for 5 hours in air. The decomposed powders are then fired at about 800-1000° C. for about 10-24 hours either in air or in an oxygen-containing atmosphere.
  • For the surface-coating of the synthesized compound Li1+xNiαMnβCoγM′δO2−zFz, coating solutions are prepared by dissolving coating material sources in organic solvents or water. The coating material sources include A′-alkoxide, A′-salt or A′-oxide, where A′ includes Al, Bi, Ga, Ge, In, Mg, Pb, Si, Sn, Ti, Tl, Zn, Zr or mixtures thereof. The coating solutions are mixed with the synthesized compound Li1+xNiαMnβCoγM′δO2−zFz by an impregnation method such as dip coating. The amount of coating material sources may be between about 0.05 and 10 weight percent of Li1+xNiαMnβCoγM′δO2−zFz. Thereafter, the surface-coated Li1+xNiαMnβCoγM′δO2−zFz powder is dried at temperatures between about 25° C. and 700° C. for approximately 1 to 24 hours.
  • The synthesized compound is mixed with a carbon additive and a PVDF binder to form a laminate film on an aluminum foil. This laminate is used for electrochemical testing in the presence of lithium or carbon counter electrodes and non-aqueous electrolytes made of LiPF6/EC:DEC (1:1).
  • FIGS. 1( a)-1(c) show the morphology of (NiαMnβCoγ)-carbonate prepared by the co-precipitation method using ammonium hydrogen carbonate. Spherical shape precursors with homogeneous size distribution are obtained by the co-precipitation. The magnification factors of FIGS. 1( a), 1(b), and 1(c) are ×500, ×2,000, and ×12,000, respectively.
  • FIGS. 2( a)-2(c) show the morphology of Li1+xNiαMnβCoγO2 prepared by calcinations of (NiαMnβCoγ)-carbonate and lithium carbonate at 1000° C. for 10 h in air. The spherical shape of the precursor is preserved after calcinations. The magnification factors of FIGS. 2( a), 2(b) and 2(c) are ×1,000, ×2,000, and ×12,000, respectively.
  • FIGS. 3 and 4 represent X-ray diffraction patterns of Li1+xNiαMnβCoγM′δO2−zFz compounds. All of the compounds exhibit the ordered rock-salt structure with crystallographic structure of R 3m. For the Li-excess composition such as Li(Li0.2Ni0.2+0.5 zCo0.1Mn0.5-0.5z)O2−zFz, extra peaks appear at 20˜25°, as shown in FIG. 4, which are generally attributed to cation ordering in the transition metal layer.
  • FIG. 5 shows the first charge/discharge curves of Li/Li(NiαMnβCoγ)O2−zFz cells, and
  • FIG. 6 shows cycling performance of Li/Li(NiαMnβCoγ)O2−zFz cells. FIGS. 5 and 6 clearly show that the discharge capacity increases by more than 10%, and the cycling performance improves by the simultaneous substitution of cations and anions.
  • FIG. 7 shows area specific impedance (ASI) of C/Li(NiαMnβ)O2−zFz cells as a function of state of charge (SOC) measured by 30 s-current interruption. FIG. 8 shows the variation of the ASI values at 50% SOC of C/Li(NiαMnβ)O2−zFz cells. FIGS. 7 and 8 clearly show that fluorine doping lowers impedance and enhances cycling stability.
  • FIGS. 9 and 10 show the cycling performance of uncoated Li(NiαMnβCoγ)O2, Li(NiαMnβCoγ)O2 coated with 0.5 wt % Al-isopropoxide, and Li(NiαMnβCoγ)O2 coated with 1.0 wt % Al-isopropoxide at room temperature and 55° C., respectively. The coating solution is prepared by dissolving appropriate amount of Al-isopropoxide in ethanol. Li(NiαMnβCoγ)O2 powders are then mixed thoroughly with the coating solution and dried at 100° C. for 12 h. The coated powders are subsequently heat-treated at 300° C. for 3 h in air. For FIG. 9, the data identified under group (a), α=0.4, β=0.4, γ=0.2, with the Li(NiαMnβCoγ)O2 uncoated. For the data identified under group (b), α=0.4, β=0.4, γ=0.2, and the Li(NiαMnβCoγ)O2 is coated with 0.5 wt % Al-isopropoxide. For the data identified under group (c), α=0.4, β=0.4, γ=0.2, and the Li(NiαMnβCoγ)O2 is coated with 1.0 wt % Al-isopropoxide. In FIG. 10, for the data identified under group (a), α=0.4, β=0.4, γ=0.2, with the Li(NiαMnβCoγ)O2 uncoated. For the data identified under group (b), α=0.4, β=0.4, γ=0.2, and the Li(NiαMnβCoγ)O2 is coated with 0.5 wt % Al-isopropoxide.
  • FIG. 11 shows the variation of area specific impedance (ASI) with cycling of C/Li(NiαMnβCoγ)O2 measured by a 30 s current interruption method with C/Li(NiαMnβCoγ)O2 cells. The cells with coated cathode materials exhibit a very limited increase of ASI, whereas the cells with uncoated cathode material show a large impedance increase with cycling.
  • FIG. 12 shows the a.c. impedance spectroscopy of C/Li(NiαMnβCoγ)O2 cells as a function of cycle number measured with C/Li(NiαMnβCoγ)O2 cells. This representation indicates the surface coating significantly improves the stability of the cathode surface/electrolyte interface. In FIGS. 11 and 12, for the data identified under chart (a), α=0.4, β=0.4, γ=0.2, with the Li(NiαMnβCoγ)O2 uncoated. For the data identified under chart (b), α=0.4, β=0.4, γ=0.2, and the Li(NiαMnβCoγ)O2 is coated with 0.5 wt % Al-isopropoxide. For the data identified under chart (c), α=0.4, β=0.4, γ=0.2, and the Li(NiβMnβCoγ) O2 is coated with 1.0 wt % Al-isopropoxide.
  • FIG. 13 presents the impedance variation with a 55° C.-storage time measured with C/Li(NiαMnβCoγ)O2 cells. For the data identified under group (a), α=0.4, β=0.4, γ=0.2, with the Li(NiαMnβCoγ) O2 uncoated. For the data identified under group (b), α=0.4, β=0.4, γ=0.2, and the Li(NiαMnβCoγ)O2 is coated with 0.5 wt % Al-isopropoxide. For the data identified under group (c), α=0.4, β3=0.4, γ=0.2, and the Li(NiαMnβCoγ)O2 is coated with 1.0 wt % Al-isopropoxide. FIGS. 9-13 clearly show the surface coating greatly improving the cycle life, as well as calendar life, of the lithium-ion cells.
  • FIG. 14 shows the first charge/discharge curves and variation of discharge capacity with cycle number of Li/Li1+x(NiαMnβCoγ)O2 cells. FIG. 15 shows the area specific impedance of C/Li1+x(NiαMnβCoγ)O2 cells as a function of state of charge measured by a 30 s current interruption method.
  • FIG. 16 shows cycling performance of Li/Li1+x(NiαMnβCoγ)O2-zFz cells at room temperature and at 55° C. FIG. 17 shows the area specific impedance of Li/Li1+x(NiαMnβCoγ)O2-zFz cells measured by a 30 s current interruption method.
  • FIGS. 14-17 clearly show that substitution of oxygen with fluorine significantly improves cycling performance and lowers the impedance of the cathode materials.
  • Another aspect of the present invention relates to a method for preparing spherical, mixed nickel-cobalt-manganese carbonates with a narrow size distribution and a method for preparing spherical lithium nickel cobalt manganese oxide using the spherical precursors, a coprecipitation method is used to prepare the spherical precursors, (NiaCObMnc)CO3, where the a is between 0 and 1, the b between 0 and 1, and the c between 0 and 1. Ammonium hydrogen carbonate (NH4HCO3) or sodium carbonate (Na2CO3) is used for precipitating agents for the coprecipitation. Using the spherical (NiαCoβMnγ)CO3 spherical lithium metal oxides with composition Li1+xNiαCo βMnγM′δOyFz (M′=Mg, Zn, Al, Ga, B, Zr, Ti) are created, where the x is between 0 and about 0.2, the α between 0 and about 1, the β between 0 and about 1, the γ between 0 and about 2, the δ between about 0 and about 0.2, the y is between about 2 and about 4, z is between 0 and about 0.5.
  • The spherical (NiaCobMnc)CO3 is prepared by coprecipitation as follows. Appropriate amounts of Ni-acetate (or Ni-nitrate or Ni-sulfate), Co-acetate (or Co-nitrate or Co-sulfate), and Mn-acetate (or Mn-nitrate or Ni-sulfate) are dissolved in distilled water and the metal solution is added to another aqueous solution of ammonium hydrogen carbonate or sodium carbonate. The concentration of metal solutions ([Me]) is varied from about 0.01M to about 2M; the concentrations of ammonium hydrogen carbonate solution ([AHC]) or sodium carbonate ([SC]) is varied from about 0.1 M to about 5M. The pH of the ammonium hydrogen carbonate solution or the sodium carbonate solution is varied from about 7 to about 12 using ammonium hydroxide or sodium hydroxide. The reaction temperature is varied from about 20° C. to about 65° C. When the metal solution is added to the ammonium hydrogen carbonate solution, the precipitates form instantly. The precipitates are then aged in the solution at each temperature from about 1 h to about 24 h. All of the precipitation reaction and aging are carried out under constant stirring. After aging, the coprecipitated powders are filtered and dried.
  • To prepare a Li1+xNiαCoβMnγM′δOyFz (M′=Mg, Zn, Al, Ga, B, Zr, Ti) compound, appropriate amounts of lithium hydroxide (or lithium carbonate or lithium nitrate), (NiaCobMnc)CO3, M′-hydroxides (or M′-carbonates or M′-oxides), and LiF (or NH4F) are mixed. The mixed powers are calcined at about 450° C. to about 700° C. for about 12-30 hours either in air or in oxygen atmospheres and then at about 700° C. to about 1000° C. for about 10-24 hours either in air or in oxygen atmospheres.
  • In one exemplary embodiment, the synthesized compound Li1+xNiαCoβMnγM′δOyFz is mixed with a carbon additive and a PVDF binder to form a laminate film on aluminum foil. This laminate is used, for example, in electrochemical testing in the presence of lithium or carbon counter electrode and non-aqueous electrolyte made of LiPF6/ED:DEC (1:1).
  • FIG. 18 shows SEM images of (Ni1/3Co1/3Mn1/3)CO3 precipitates. The a metal solution and ammonium hydrogen carbonate (AHC) concentrations were 0.1 and 1.0M respectively; the reaction temperature (TR) and the aging time (ta) were 65° C. and 17 h, respectively. It can be seen in FIG. 18 that the carbonate precipitates have a spherical morphology with a mean particle size (D50) of about 5-6 pm and a very narrow size distribution of about 1 to 50 microns.
  • FIG. 19 shows additional SEM images of (Ni1/3Co1/3Mn1/3)CO3, prepared by different methods FIG. 19( a) shows the SEM images of (Ni1/3Co1/3Mn1/3)CO3 precipitates prepared with a metal solution of about 0.05M, AHC concentration of about 0.5M, TR=about 65° C., ta=about 17 h; 19(b) shows the SEM images of (Ni1/3Co1/3Mn1/3)CO3 precipitates prepared with Me concentration of 0.2M, AHC concentration of 2.0M, TR=about 65° C., ta=about 4 h.
  • FIGS. 20( a) and 20(b) show the SEM images of (Ni0.219Co0.125Mn0.656)CO3 precipitates prepared with a metal solution concentration of 0.1M, AHC concentration of about 1.0M, ta=about 6 h at different temperatures (about 20° C. and about 40° C., respectively).
  • FIG. 21 shows an SEM image of MnCO3 precipitates prepared with a metal solution concentration of about 0.1M, AHC concentration of about 1.0M, TR=about 55° C., and ta=about 17 h.
  • FIG. 22 shows an SEM image of (Cu0.5Mn0.5)CO3 precipitates prepared with a metal solution concentration of about 0.1M, AHC concentration of about 1.0M, TR=about 50° C., and ta=about 17 h.
  • FIG. 23 represents the x-ray diffraction (XRD) patterns of the (Ni1/3Co1/3Mn1/3)CO3 and MnCO3 precipitates shown in FIGS. 18 and 21, respectively, together with the reported XRD patterns of MnCO3. The XRD patterns of the coprecipitated materials are well matched with the reported XRD patterns of MnCO3 with rhombohedral structure (space group of R3c).
  • FIG. 24 shows the SEM images of Li[Ni1/3Co1/3Mn1/3]O2 prepared using the (Ni1/3Co1/3Mn1/3)CO3 shown in FIG. 18. The calcinations were carried out at about 1000° C. for about 10 h in air. It can be seen in FIG. 24 that the Li[Ni1/3Co1/3Mn1/3]O2 material retained the size and morphology of the (Ni1/3Co1/3Mn1/3)CO3 precursor.
  • FIG. 25 represents the XRD patterns of the Li[Ni1/3Co1/3Mn1/3]O2 material shown in FIG. 24. The material exhibits the ordered rock-salt structure with crystallographic structure of R3m.
  • FIGS. 26( a) and 26(b) show the first charge/discharge curves of the Li/Li[Ni1/3Co1/3Mn1/3]O2 cells cycled in the voltage range of 2.8-4.6V and the variation of the discharge capacities as a function of cycle number, respectively.
  • The materials described herein can be used as cathodes in lithium-ion rechargeable batteries for products such as electric vehicles, hybrid electric vehicles, portable electronics, and a variety of other products. The materials described herein are less expensive and thermally safer than existing cathode materials such as LiCoO2 and LiNiO2. The materials of the present invention also exhibit improved calendar/cycle life when compared to existing cathode materials.
  • It should be understood that the above description of the invention and specific examples and embodiments, while indicating the preferred embodiments of the present invention, are given by demonstration and not limitation. Many changes and modifications within the scope of the present invention may therefore be made without departing from the spirit thereof and the present invention includes all such changes and modifications.

Claims (13)

1. A mixed nickel-cobalt-manganese carbonate comprising:
(NiaCobMnc)CO3 having a spherical morphology, wherein a is between 0 and about 1, b is between 0 and about 1, and c is between 0 and about 1.
2. The mixed nickel-cobalt-manganese carbonate of claim 1, further comprising a narrow size distribution of about 1 to about 50 microns of (NiaCobMnc)CO3.
3. A positive active composition comprising:
a substituted lithium nickel-manganese oxide having a spherical morphology; and
the substituted lithium nickel-manganese oxide has the formula Li1+xNiαCoβMnγM′δOyFz (M′=Mg, Zn, Al, Ga, B, Zr, Ti), wherein x is between about 0 and about 0.3, α is between about 0 and about 1, β is between about 0 and about 1, γ is between about 0 and about 2, 6 is between about 0 and about 0.2, y is between about 2 and about 4, and z is between about 0 and about 0.5.
4. The positive active composition of claim 3, further comprising a narrow size distribution of about 1 to about 50 microns of substituted lithium nickel-manganese oxide.
5. A positive electrode material having the positive active composition of claim 3 further comprising a conducting agent and a binder.
6. A non-aqueous lithium cell having the positive electrode material of claim 5 further comprising a negative electrode and a non-aqueous electrolyte.
7. The non-aqueous lithium cell of claim 6, wherein the negative electrode is chosen from the group consisting of lithium metal, graphite, silicon, silver, lithium titanium oxospinel (Li4Ti5O12), tin oxide, and intermetallic compounds A-B (A, B: Ag, Al, Cu, Fe, Mg, Mo, Ni, Sb, Si, Sn, Ti).
8. The non-aqueous lithium cell of claim 6, wherein the non-aqueous electrolyte is chosen from the group consisting of LiBF4, LiClO4, LiPF6, and LiB(C2O4)2 dissolved in a solvent chosen from the group consisting of ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), polyethylene carbonate (PC), ethyl nonafluorobutyl ether (EFE), vinylene carbonate (VC), methyl difluoroacetate (MFA), vinyl pyridine (VP), vinyl ethylene carbonate (VEC), siloxane, and combinations thereof.
9. A positive active composition for use in a rechargeable battery comprising:
a substituted lithium nickel-manganese oxide; and
the substituted lithium nickel-manganese oxide has the formula Li1+xNiαMnβCoγM′δO2-zFz (M′=Mg, Zn, Al, Ga, B, Zr, Ti), wherein x is between about 0 and about 0.3, α is between about 0.2 and about 0.6, β is between about 0.2 and about 0.6, γ is between about 0 and about 0.3, 6 is between about 0 and about 0.15, and z is between about 0 and about 0.2.
10. The positive active composition of claim 9, further comprising a surface-coat on the substituted lithium nickel-manganese oxide
11. The positive active composition of claim 10, wherein the surface-coat is chosen from the group consisting of A′-alkoxide, A′-salt, and A′-oxide, wherein A′ includes Al, Bi, Ga, Ge, In, Mg, Pb, Si, Sn, Ti, Tl, Zn, Zr or mixtures thereof.
12. The positive active composition of claim 11, wherein the surface-coat comprises Al-isopropoxide between about 0.5 wt % and about 1.0 wt % of substituted lithium nickel-manganese oxide.
13. A method of preparing a positive active composition comprising the steps of:
mixing amounts of lithium hydroxide (or lithium carbonate or lithium nitrate), (Ni,Co,Mn)-carbonate of claim 1, M′-hydroxide (or M′-carbonate or M′-oxide; M′=Mg, Zn, Al, Ga, B, Zr, Ti), and LiF (or NH4F) for about 12 to 24 hours to form a mixed powder;
calcinating the mixed powder at about 450 to 700° C. for about 12 to 30 hours either in air or in oxygen atmospheres; and
calcinating the mixed powder at about 700 to 1000° C. for about 10 to 24 hours either in air or in oxygen atmospheres.
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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110114900A1 (en) * 2008-02-01 2011-05-19 Nippon Chemical Industrial Co., Ltd. Composite carbonate and method for producing the same
US20120228544A1 (en) * 2009-12-04 2012-09-13 Kanagawa University Positive electrode material for electrical device, and electrical device produced using same
CN104134795A (en) * 2014-07-25 2014-11-05 江南大学 Preparation method of spherical layer-structured anode material externally coated with nanocrystalline metal oxide for lithium ion battery
WO2015093725A1 (en) * 2013-12-17 2015-06-25 전자부품연구원 Non-aqueous, high capacity cathode material for lithium secondary battery, and method for preparing same
US9583790B2 (en) 2013-11-22 2017-02-28 Samsung Electronics Co., Ltd. Electrolyte for lithium battery and lithium battery including the same
US9620771B2 (en) 2013-01-07 2017-04-11 Samsung Sdi Co., Ltd. Cathode active material, cathode and lithium battery including cathode active material, and method of preparing the cathode active material
EP3595059A4 (en) * 2017-03-06 2020-01-15 Panasonic Intellectual Property Management Co., Ltd. Positive electrode active material, and cell
US10862106B2 (en) 2015-10-28 2020-12-08 Samsung Electronics Co., Ltd. Composite positive electrode active material, positive electrode including the same, and lithium battery including the positive electrode
US10892488B2 (en) 2017-01-17 2021-01-12 Samsung Electronics Co., Ltd. Electrode active material, lithium secondary battery containing the electrode active material, and method of preparing the electrode active material
US11011746B2 (en) 2015-07-13 2021-05-18 Samsung Electronics Co., Ltd. Composite cathode active material for lithium battery, cathode for lithium battery including the same, and lithium battery including the cathode
US11271200B2 (en) 2017-03-06 2022-03-08 Panasonic Intellectual Property Management Co., Ltd. Positive-electrode active material containing lithium composite oxide, and battery including the same
US11401167B2 (en) * 2017-03-15 2022-08-02 Umicore Nitrate process for manufacturing transition metal hydroxide precursors
US11557760B2 (en) 2017-04-24 2023-01-17 Panasonic Intellectual Property Management Co., Ltd. Positive-electrode active material containing lithium composite oxide, and battery including the same
US11605814B2 (en) 2017-05-29 2023-03-14 Panasonic Intellectual Property Management Co., Ltd. Positive-electrode active material containing lithium composite oxide, and battery including the same

Families Citing this family (96)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4172423B2 (en) * 2004-05-26 2008-10-29 ソニー株式会社 Positive electrode active material and non-aqueous electrolyte secondary battery
KR100688732B1 (en) * 2005-03-30 2007-03-02 에스케이 주식회사 Method for producing spherical manganese carbonate and product thereof
KR100674287B1 (en) * 2005-04-01 2007-01-24 에스케이 주식회사 Anode active material for lithium secondary battery having a nuclear / shell multilayer structure, method for manufacturing the same and lithium secondary battery using same
US20080032196A1 (en) 2005-04-13 2008-02-07 Lg Chem, Ltd. Method of preparing material for lithium secondary battery of high performance
US20070298512A1 (en) 2005-04-13 2007-12-27 Lg Chem, Ltd. Material for lithium secondary battery of high performance
US20070292761A1 (en) 2005-04-13 2007-12-20 Lg Chem, Ltd. Material for lithium secondary battery of high performance
US8062792B2 (en) * 2005-04-26 2011-11-22 Uchicago Argonne Llc Processes for making dense, spherical active materials for lithium-ion cells
US8367253B2 (en) * 2006-02-02 2013-02-05 U Chicago Argonne Llc Lithium-ion batteries with intrinsic pulse overcharge protection
US8168330B2 (en) * 2006-04-11 2012-05-01 Enerdel, Inc. Lithium titanate cell with reduced gassing
US8492030B2 (en) * 2006-06-19 2013-07-23 Uchicago Argonne Llc Cathode material for lithium batteries
KR100784637B1 (en) 2006-12-19 2007-12-12 한국원자력연구원 Method for preparing lithium titanate spinel powder using lithium molten salt
US8338037B2 (en) * 2007-12-13 2012-12-25 Uchicago Argonne, Llc Positive electrode for a lithium battery
US8187752B2 (en) 2008-04-16 2012-05-29 Envia Systems, Inc. High energy lithium ion secondary batteries
US8277974B2 (en) * 2008-04-25 2012-10-02 Envia Systems, Inc. High energy lithium ion batteries with particular negative electrode compositions
CN102171868A (en) * 2008-09-30 2011-08-31 安维亚系统公司 Fluorine doped lithium rich metal oxide positive electrode battery materials with high specific capacity and corresponding batteries
US8389160B2 (en) * 2008-10-07 2013-03-05 Envia Systems, Inc. Positive electrode materials for lithium ion batteries having a high specific discharge capacity and processes for the synthesis of these materials
US9012073B2 (en) * 2008-11-11 2015-04-21 Envia Systems, Inc. Composite compositions, negative electrodes with composite compositions and corresponding batteries
KR101064299B1 (en) * 2008-11-17 2011-09-14 한국과학기술연구원 Nickel-Manganese Bicomponent Composite Electrode Materials for Electrochemical Supercapacitors and Methods for Manufacturing the Same
US8465873B2 (en) * 2008-12-11 2013-06-18 Envia Systems, Inc. Positive electrode materials for high discharge capacity lithium ion batteries
US10056644B2 (en) * 2009-07-24 2018-08-21 Zenlabs Energy, Inc. Lithium ion batteries with long cycling performance
EP2471133A4 (en) * 2009-08-27 2014-02-12 Envia Systems Inc Metal oxide coated positive electrode materials for lithium-based batteries
EP2471134B1 (en) * 2009-08-27 2022-01-05 Zenlabs Energy, Inc. Layer-layer lithium rich complex metal oxides with high specific capacity and excellent cycling
US9843041B2 (en) * 2009-11-11 2017-12-12 Zenlabs Energy, Inc. Coated positive electrode materials for lithium ion batteries
US8993177B2 (en) 2009-12-04 2015-03-31 Envia Systems, Inc. Lithium ion battery with high voltage electrolytes and additives
US8765306B2 (en) * 2010-03-26 2014-07-01 Envia Systems, Inc. High voltage battery formation protocols and control of charging and discharging for desirable long term cycling performance
US8741484B2 (en) 2010-04-02 2014-06-03 Envia Systems, Inc. Doped positive electrode active materials and lithium ion secondary battery constructed therefrom
US9083062B2 (en) 2010-08-02 2015-07-14 Envia Systems, Inc. Battery packs for vehicles and high capacity pouch secondary batteries for incorporation into compact battery packs
US20130168599A1 (en) * 2010-08-06 2013-07-04 Tdk Corporation Precursor, process for production of precursor, process for production of active material, and lithium ion secondary battery
US8928286B2 (en) 2010-09-03 2015-01-06 Envia Systems, Inc. Very long cycling of lithium ion batteries with lithium rich cathode materials
US8663849B2 (en) 2010-09-22 2014-03-04 Envia Systems, Inc. Metal halide coatings on lithium ion battery positive electrode materials and corresponding batteries
US9166222B2 (en) 2010-11-02 2015-10-20 Envia Systems, Inc. Lithium ion batteries with supplemental lithium
US9171652B2 (en) 2010-11-25 2015-10-27 Basf Se Process for preparing precursors for transition metal mixed oxides
WO2012070011A1 (en) * 2010-11-25 2012-05-31 Basf Se Process for preparing precursors for transition metal mixed oxides
JP6062865B2 (en) * 2010-11-25 2017-01-18 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ Process for producing precursor of transition metal composite oxide
US20120177921A1 (en) 2011-01-10 2012-07-12 Basf Se Process for preparing transition metal carbonates
KR101282014B1 (en) * 2011-03-14 2013-07-05 주식회사 에코프로 Manufacturing method of positive active material for lithium secondary battery and positive active material for lithium secondary battery made by the same
US9601228B2 (en) 2011-05-16 2017-03-21 Envia Systems, Inc. Silicon oxide based high capacity anode materials for lithium ion batteries
US9159990B2 (en) 2011-08-19 2015-10-13 Envia Systems, Inc. High capacity lithium ion battery formation protocol and corresponding batteries
KR102014983B1 (en) 2011-11-18 2019-08-28 삼성전자주식회사 Cathode and lithium battery using same
US10170762B2 (en) 2011-12-12 2019-01-01 Zenlabs Energy, Inc. Lithium metal oxides with multiple phases and stable high energy electrochemical cycling
US9070489B2 (en) 2012-02-07 2015-06-30 Envia Systems, Inc. Mixed phase lithium metal oxide compositions with desirable battery performance
US20130202502A1 (en) * 2012-02-08 2013-08-08 Martin Schulz-Dobrick Process for preparing mixed carbonates which may comprise hydroxide(s)
CN102544481B (en) * 2012-02-20 2014-04-09 东莞新能源科技有限公司 Lithium ion battery and cathode material thereof
DE102012102831A1 (en) * 2012-04-02 2013-10-02 Karlsruher Institut für Technologie Doped spinel, process for its preparation, its use and lithium-ion battery
US10553871B2 (en) 2012-05-04 2020-02-04 Zenlabs Energy, Inc. Battery cell engineering and design to reach high energy
US9780358B2 (en) 2012-05-04 2017-10-03 Zenlabs Energy, Inc. Battery designs with high capacity anode materials and cathode materials
US9552901B2 (en) 2012-08-17 2017-01-24 Envia Systems, Inc. Lithium ion batteries with high energy density, excellent cycling capability and low internal impedance
US10115962B2 (en) 2012-12-20 2018-10-30 Envia Systems, Inc. High capacity cathode material with stabilizing nanocoatings
HK1218992A1 (en) 2013-03-12 2017-03-17 Apple Inc. High voltage, high volumetric energy density li-ion battery using advanced cathode materials
CN103117387B (en) * 2013-03-19 2015-06-03 南通瑞翔新材料有限公司 Preparation method of cathode material lithium nickel manganese aluminum oxide of lithium ion battery
US10020491B2 (en) 2013-04-16 2018-07-10 Zenlabs Energy, Inc. Silicon-based active materials for lithium ion batteries and synthesis with solution processing
US10886526B2 (en) 2013-06-13 2021-01-05 Zenlabs Energy, Inc. Silicon-silicon oxide-carbon composites for lithium battery electrodes and methods for forming the composites
CN103326015B (en) * 2013-06-25 2015-06-17 深圳市美尼电子有限公司 Preparation method of niobium-doped lithium manganese aluminum cobalt composite positive pole material
WO2015024004A1 (en) 2013-08-16 2015-02-19 Envia Systems, Inc. Lithium ion batteries with high capacity anode active material and good cycling for consumer electronics
EP3060526A1 (en) 2013-10-24 2016-08-31 Dow Global Technologies LLC Improved lithium metal oxide cathode materials and method to make them
JP6156078B2 (en) 2013-11-12 2017-07-05 日亜化学工業株式会社 Method for producing positive electrode active material for non-aqueous electrolyte secondary battery, positive electrode for non-aqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery
JP6524651B2 (en) 2013-12-13 2019-06-05 日亜化学工業株式会社 Positive electrode active material for non-aqueous electrolyte secondary battery and method for producing the same
WO2015094847A1 (en) 2013-12-17 2015-06-25 Dow Global Technologies Llc Improved lithium metal oxide cathode materials and method to make them
WO2015183599A1 (en) 2014-05-27 2015-12-03 Dow Global Technologies Llc Lithium battery electrolyte solution containing methyl (2,2,3,3,-tetrafluoropropyl) carbonate
US9716265B2 (en) 2014-08-01 2017-07-25 Apple Inc. High-density precursor for manufacture of composite metal oxide cathodes for Li-ion batteries
US20170309963A1 (en) 2014-11-11 2017-10-26 Dow Global Technologies Llc High volumetric energy density lithium battery with long cycle life
CN104393281B (en) * 2014-12-03 2017-01-25 梁贺君 Preparation method of manganese, nickel and lithium cathode material
WO2017058650A1 (en) 2015-09-30 2017-04-06 Hongli Dai Cathode-active materials, their precursors, and methods of preparation
CN105514409B (en) * 2015-12-08 2018-01-05 中国电子科技集团公司第十八研究所 A kind of preparation method of power NCM positive electrodes
CN109075333B (en) 2016-03-14 2022-11-18 苹果公司 Cathode active material for lithium ion battery
CN114665089B (en) 2016-05-09 2024-03-01 日亚化学工业株式会社 Method for producing nickel-cobalt composite hydroxide and method for producing positive electrode active material for nonaqueous electrolyte secondary battery
CN109565048B (en) * 2016-08-09 2022-04-15 住友金属矿山株式会社 Positive electrode active material for nonaqueous electrolyte secondary battery, and method for producing positive electrode active material for nonaqueous electrolyte secondary battery
US10297823B2 (en) 2016-09-20 2019-05-21 Apple Inc. Cathode active materials having improved particle morphologies
CN109715562B (en) 2016-09-21 2022-03-11 苹果公司 Surface stable cathode material for lithium ion battery and synthesis method thereof
CN106784825A (en) * 2017-03-15 2017-05-31 北京理工大学 A kind of spherical nickeliferous carbonic acid manganese material and its preparation method and application
US11094925B2 (en) 2017-12-22 2021-08-17 Zenlabs Energy, Inc. Electrodes with silicon oxide active materials for lithium ion cells achieving high capacity, high energy density and long cycle life performance
CN108258221B (en) * 2018-01-17 2019-07-09 扬州大学 A spherical S/C@MoO2 composite material and its preparation method and application
US11695108B2 (en) 2018-08-02 2023-07-04 Apple Inc. Oxide mixture and complex oxide coatings for cathode materials
US11749799B2 (en) 2018-08-17 2023-09-05 Apple Inc. Coatings for cathode active materials
US12136732B2 (en) * 2018-11-30 2024-11-05 Posco Holdings Inc. Cathode active material for lithium secondary battery, and lithium secondary battery comprising same
CN109704413B (en) * 2018-12-07 2021-10-12 北京理工大学 High-nickel anode material and method for improving storage performance of high-nickel anode material
US12074321B2 (en) 2019-08-21 2024-08-27 Apple Inc. Cathode active materials for lithium ion batteries
US12206100B2 (en) 2019-08-21 2025-01-21 Apple Inc. Mono-grain cathode materials
US11757096B2 (en) 2019-08-21 2023-09-12 Apple Inc. Aluminum-doped lithium cobalt manganese oxide batteries
CN110862108A (en) * 2019-11-21 2020-03-06 桂林理工大学 A method for improving the electrochemical performance of high nickel ternary cathode materials by fluorine doping modification
CN114982008B (en) * 2019-12-26 2024-11-22 汉阳大学校产学协力团 Fluorine-containing positive electrode active material for lithium secondary battery and lithium secondary battery containing the same
CN110931772B (en) 2020-02-12 2020-06-19 湖南长远锂科股份有限公司 A kind of preparation method of high-power lithium ion battery cathode material
EP4112560B1 (en) * 2020-02-28 2024-12-04 Panasonic Intellectual Property Management Co., Ltd. Positive electrode active material for non-aqueous electrolyte secondary battery and non-aqueous electrolyte secondary battery
CN111377487A (en) * 2020-03-26 2020-07-07 江苏海基新能源股份有限公司 Preparation method of Al and F co-doped high-nickel ternary cathode material
US20220029161A1 (en) * 2020-07-24 2022-01-27 Uchicago Argonne, Llc Cathode materials for use in lithium cells and batteries
US20220029160A1 (en) * 2020-07-24 2022-01-27 Uchicago Argonne, Llc Cathode materials for use in lithium cells and batteries
US20220029156A1 (en) * 2020-07-24 2022-01-27 Uchicago Argonne, Llc Cobalt-free lithiated spinel cathode materials for use in lithium cells and batteries
CN112919554B (en) * 2021-05-11 2021-10-15 蜂巢能源科技有限公司 Fluorine-doped lithium cathode material, preparation method and application thereof
CN113299906A (en) * 2021-05-26 2021-08-24 中南大学 Cation and fluorine anion double-doped modified ternary cathode material and preparation method thereof
CN113584591B (en) * 2021-09-30 2022-01-14 中南大学 High-entropy single crystal metal oxide of cation disordered salt rock structure and preparation method and application thereof
CN114455647A (en) * 2022-01-24 2022-05-10 浙江格派钴业新材料有限公司 Preparation method of surface confinement treatment full-concentration gradient quaternary high-nickel NCMA positive electrode material
CN114516664B (en) * 2022-03-31 2024-04-02 高点(深圳)科技有限公司 Carbonate grafted carbonate cathode material precursor and its preparation method and application
CN114873654B (en) * 2022-03-31 2024-04-02 高点(深圳)科技有限公司 A grafted cathode material precursor and its preparation method and application
CN116639740A (en) * 2023-05-29 2023-08-25 格林美（无锡）能源材料有限公司 Cobalt-free lithium-rich manganese-based positive electrode material and preparation method thereof
CN116655003A (en) * 2023-06-29 2023-08-29 湖南航天天麓新材料检测有限责任公司 Fluorine-doped high-nickel ternary lithium ion battery positive electrode material, preparation method thereof and lithium ion battery
CN116741974B (en) * 2023-08-15 2023-11-17 宁波容百新能源科技股份有限公司 Positive electrode material, preparation method thereof and lithium ion battery

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5910296A (en) * 1996-12-31 1999-06-08 Samsung Display Devices Co., Ltd. Method of preparing Ni-M hydroxycarbonate having a high density
US20020055042A1 (en) * 2000-03-13 2002-05-09 Kweon Ho-Jin Positive active material for rechargeable lithium battery and method of preparing same
US20020119374A1 (en) * 1999-12-29 2002-08-29 Kaiyuan Yang Nickel-rich quaternary metal oxide materials as cathodes for lithium-ion polymer batteries
US6677082B2 (en) * 2000-06-22 2004-01-13 The University Of Chicago Lithium metal oxide electrodes for lithium cells and batteries
US6680143B2 (en) * 2000-06-22 2004-01-20 The University Of Chicago Lithium metal oxide electrodes for lithium cells and batteries
US6811925B2 (en) * 2000-11-20 2004-11-02 Chuo Denki Kogyo Co., Ltd. Nonaqueous electrolyte secondary cell and a tungsten or molybdenum substituted lithium positive electrode active material

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5910296A (en) * 1996-12-31 1999-06-08 Samsung Display Devices Co., Ltd. Method of preparing Ni-M hydroxycarbonate having a high density
US20020119374A1 (en) * 1999-12-29 2002-08-29 Kaiyuan Yang Nickel-rich quaternary metal oxide materials as cathodes for lithium-ion polymer batteries
US20020055042A1 (en) * 2000-03-13 2002-05-09 Kweon Ho-Jin Positive active material for rechargeable lithium battery and method of preparing same
US6677082B2 (en) * 2000-06-22 2004-01-13 The University Of Chicago Lithium metal oxide electrodes for lithium cells and batteries
US6680143B2 (en) * 2000-06-22 2004-01-20 The University Of Chicago Lithium metal oxide electrodes for lithium cells and batteries
US6811925B2 (en) * 2000-11-20 2004-11-02 Chuo Denki Kogyo Co., Ltd. Nonaqueous electrolyte secondary cell and a tungsten or molybdenum substituted lithium positive electrode active material

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US11271200B2 (en) 2017-03-06 2022-03-08 Panasonic Intellectual Property Management Co., Ltd. Positive-electrode active material containing lithium composite oxide, and battery including the same
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US11605814B2 (en) 2017-05-29 2023-03-14 Panasonic Intellectual Property Management Co., Ltd. Positive-electrode active material containing lithium composite oxide, and battery including the same

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