WO2006023092A2 - Method and apparatus for preparation of spherical metal carbonates and lithium metal oxides for lithium rechargeable batteries - Google Patents

Method and apparatus for preparation of spherical metal carbonates and lithium metal oxides for lithium rechargeable batteries Download PDF

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WO2006023092A2
WO2006023092A2 PCT/US2005/023315 US2005023315W WO2006023092A2 WO 2006023092 A2 WO2006023092 A2 WO 2006023092A2 US 2005023315 W US2005023315 W US 2005023315W WO 2006023092 A2 WO2006023092 A2 WO 2006023092A2
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carbonate
lithium
cobalt
mixed
manganese
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WO2006023092A3 (en
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Sun-Ho Kang
Khalil Amine
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University of Chicago
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University of Chicago
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    • C01G45/1221—Manganates or manganites with trivalent manganese, tetravalent manganese or mixtures thereof
    • C01G45/1228—Manganates or manganites with trivalent manganese, tetravalent manganese or mixtures thereof of the type (MnO2)-, e.g. LiMnO2 or Li(MxMn1-x)O2
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    • C01G51/50—Complex oxides containing cobalt and at least one other metal element containing alkali metals, e.g. LiCoO2 containing manganese of the type (MnO2)n-, e.g. Li(CoxMn1-x)O2 or Li(MyCoxMn1-x-y)O2
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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
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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 Q 5 )O 2 exhibits rather small capacity for high-energy applications and rather high impedance for high- power applications.
  • 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.
  • spherical metal carbonates have been developed with a narrow size distribution and with a composition of (Ni a C ⁇ b Mn c )C ⁇ 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.
  • FIGURES 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;
  • FIGURES 2(a)-2(c) show the morphology of Li 1+x Ni ⁇ Mn ⁇ Co ⁇ ⁇ 2 prepared by calcinations of (Ni ⁇ Mn ⁇ Co ⁇ )-carbonate and lithium carbonate at 1000 0 C for 10h in air, using magnification factors of ⁇ 1 ,000, ⁇ 2,000, and ⁇ 12,000, respectively;
  • FIGURE 3 and FIGURE 4 are plots showing the X-ray diffraction patterns of various Li 1+ ⁇ Ni ⁇ Mn ⁇ Co ⁇ M' ⁇ O 2 z F z compounds;
  • FIGURE 5 is a plot showing the first charge/discharge curves of Li/Li(Ni ⁇ Mn ⁇ Co ⁇ ) O 2 2 F 2 ceils;
  • FIGURE 6 is a plot showing the cycling performance of Li/l_i(Ni ⁇ Mn ⁇ Co ⁇ )O 2 z F 2 cells;
  • FIGURE 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 30s-current interruption;
  • FIGURE 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;
  • FIGURES 9 and 10 show the cycling performance of uncoated
  • FIGURE 11 shows the variation of area specific impedance (ASI) with cycling of C/Li(Ni a Mn p Co y )O 2 measured by a 30s current interruption method;
  • FIGURE 12 shows the a.c. impedance spectroscopy of C/Li(Ni a Mn p Co r )O 2 cells as a function of cycle number measured with C/Li(Ni ⁇ Mn ⁇ Co ⁇ )O 2 cells;
  • FIGURE 13 presents the variation of area specific impedence at 60% SOC with a 55°C-storage time measured with C/Li(Ni ⁇ Mn p Co ⁇ )O 2 cells;
  • FIGURE 14 is a plot showing the first charge/discharge curves and variation of discharge capacity with cycle number of Li/Li 1+ ⁇ (Ni ⁇ Mn ⁇ Co ⁇ )O 2 cells;
  • FIGURE 15 is a plot showing the area specific impedance of C/Li 1+ ⁇ (Ni ⁇ Mn ⁇ Co ⁇ )O 2 cells as a function of state of charge measured by a 30s current interruption method;
  • FIGURE 16 is a plot showing the cycling performance of
  • FIGURE 17 is a plot showing the area specific impedance of Li/Li 1+ ⁇ (Ni ⁇ Mn ⁇ Co ⁇ )O 2.z F z cells measured by a 30s current interruption method;
  • FIGURE 18A shows scanning electron microscope (SEM) images of
  • FIGURE 18B is an enlarged view of FIGURE 18A;
  • FIGURES 20(a) and 20(b) represent the SEM images of
  • FIGURE 21 shows an SEM image of MnCO 3 precipitates prepared with
  • FIGURE 23 represents the X-ray diffraction (XRD) patterns of the
  • FIGURE 24A shows SEM images of Li[Nii/ 3 Coi /3 Mni /3 ]O 2 prepared using the (Nii/ 3 Coi /3 Mn 1/3 )CO 3 shown in Figure 18 with calcination carried out at 1000 0 C for
  • FIGURE 24B is an enlarged view of FIGURE 24A;
  • FIGURE 25 represents the XRD patterns of the Li[Nii /3 C ⁇ i /3 Mn 1/3 ]O 2 material shown in Figure 24;
  • FIGURE 26 shows the first charge/discharge curves of the
  • 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, Tl, 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 Li 1+ ⁇ Ni ⁇ Mn ⁇ Co ⁇ M' ⁇ O 2 .
  • z F z with the value M ⁇ Mg 1 Zn 1 AI 1 Ga 1 B 1 Zr 1 Ti.
  • (Ni,Mn,Co)-hydroxides or (Ni, Mn 1 Co)- carbonates may be prepared by a co-precipitation method.
  • 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 ).
  • the temperature of the overall solution is kept at 40-70 0 C.
  • the co-precipitated powders are filtered and dried.
  • the mixed powders are calcined at 450 ⁇ 700°C for 12-30 hours in air and then at 700-1000 0 C for 10-24 hours either in air or in an oxygen-containing atmosphere.
  • 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 8O 0 C for about 12-24 hours and evaporated in a rotary vacuum evaporator. Organic contents in the gel precursor are eliminated at 40O 0 C for 2 hours. Finally, the resulting powder is calcined at 800-1000 0 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 Lii+ ⁇ Ni ⁇ Mn ⁇ C ⁇ M' ⁇ ⁇ 2 -2 Fz 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 Lii+ ⁇ Ni ⁇ Mn ⁇ Co ⁇ M' ⁇ ⁇ 2-zF z . Thereafter, the surface-coated Lii+ ⁇ Ni ⁇ Mn ⁇ Co ⁇ M' ⁇ ⁇ 2 - z Fz powder is dried at temperatures between about 25 0 C and 700 0 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 Lii +x Ni a Mn p Co Y O 2 prepared by calcinations of (Ni a Mn p Co v )-carbonate and lithium carbonate at 1000 0 C for 10h 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 x 1 ,000, ⁇ 2,000, and ⁇ 12,000, respectively.
  • FIGS. 3 and 4 represent X-ray diffraction patterns of Li 1+ ⁇ Ni ⁇ Mn ⁇ Co ⁇ M' ⁇ O 2.
  • 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 p 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 30s-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. 9 and 10 show the cycling performance of uncoated Li(Ni ⁇ Mn ⁇ Co ⁇ ) ⁇ 2, Li(Ni ⁇ Mn p 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 0 C, respectively.
  • the coating solution is prepared by dissolving appropriate amount of Al-isopropoxide in ethanol.
  • Li(Ni ⁇ Mn p Co ⁇ )O 2 powders are then mixed thoroughly with the coating solution and dried at 100°C for 12h. The coated powders are subsequently heat-treated at 300°C for 3h in air.
  • FIG. 11 shows the variation of area specific impedance (ASl) with cycling of CVLi(N i a Mn p Co v ) O 2 measured by a 30s current interruption method with C/Li(Ni ⁇ Mn p Co ⁇ )O 2 cells.
  • 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.
  • 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/l_i 1+ ⁇ (Ni ⁇ Mn ⁇ Co ⁇ )O 2 cells.
  • FIG. 15 shows the area specific impedance of C/Li 1+ ⁇ (Ni ⁇ Mn ⁇ Co ⁇ )O 2 cells as a function of state of charge measured by a 30s current interruption method.
  • FIG. 16 shows cycling performance of Li/Li 1+ ⁇ (Ni ⁇ Mn ⁇ Co ⁇ )O 2.z F z cells at room temperature and at 55 0 C.
  • FIG. 17 shows the area specific impedance of Li/Li 1+ ⁇ (Ni ⁇ Mn ⁇ Co ⁇ )O 2 .
  • z F z cells measured by a 30s 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 C ⁇ 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.
  • spherical lithium metal oxides with composition Lii + ⁇ Ni ⁇ C ⁇ ⁇ Mn ⁇ M' ⁇ OyF z (M ⁇ Mg 1 Zn 1 AI 1 Ga 1 B 1 Zr 1 Ti) are created, where the x is between 0 and about 0.2, the ⁇ between 0 and about 1 , the ⁇ between 0 and about 1 , the Y between 0 and about 2, the ⁇ 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 (Ni a C ⁇ 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 is varied from about 0.01 M 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 0 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 24h. All of the precipitation reaction and aging are carried out under constant stirring. After aging, the coprecipitated powders are filtered and dried.
  • Lii +x Ni ⁇ C ⁇ ⁇ Mn ⁇ M' ⁇ OyF z (M ⁇ Mg 1 Zn 1 AI 1 Ga 1 B 1 Zr 1 Ti) compound appropriate amounts of lithium hydroxide (or lithium carbonate or lithium nitrate), (Ni a Co b Mn c )CO 3 , M'-hydroxides (or M'-carbonates or M'-oxides), and LiF (or NH 4 F) are mixed.
  • the mixed powers are calcined at about 450 0 C to about 700°C for about 12-30 hours either in air or in oxygen atmospheres and then at about 700 0 C to about 1000 0 C for about 10-24 hours either in air or in oxygen atmospheres.
  • the synthesized compound Lii + ⁇ Ni ⁇ C ⁇ ⁇ 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 LiPFe/ED:DEC (1 :1).
  • FIGS. 18A and 18B show SEM images of (Ni 1Z3 Co 1Z3 Mn 1Z3 )CO 3 precipitates.
  • the a metal solution (FIG. 18A) and ammonium hydrogen carbonate (AHC) (FIG. 18B) concentrations were 0.1 and 1.0M respectively; the reaction temperature (TR) and the aging time (t a ) were 65°C and 17h, 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 ⁇ m and a very narrow size distribution of about 1 to 50 microns.
  • D50 mean particle size
  • FIG. 19 shows additional SEM images of (Nii/3C ⁇ i/ 3 Mni /3 )CO 3 , prepared by different methods.
  • 19(b) shows the SEM images of
  • FIG. 23 represents the x-ray diffraction (XRD) patterns of the
  • FIGS. 24A and B show the SEM images of Li[Ni 1Z3 Co 1Z3 Mn I z 3 ]O 2 prepared using the (Ni I z 3 Co 1Z3 Mn 1Z3 )CO 3 shown in FIG. 18.
  • the calcinations were carried out at about 1000 0 C for about 10h in air. It can be seen in FIG. 24B that the
  • Li[Ni 1Z3 Co 1Z3 Mn 1 Z 3 ]O 2 material retained the size and morphology of the
  • FIG. 25 represents the XRD patterns of the Li[Ni 1Z3 Co- I z 3 Mn 1Z3 ]O 2 material shown in FIG. 24. The material exhibits the ordered rock-salt structure with crystallographic structure of R3m.
  • FIG. 26 shows the first charge/discharge curves of the Li/Li[Ni 1/3 Coi /3 Mni /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 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 Li<sub

Description

■ METHOD AND APPARATUS FOR PREPARATION OF SPHERICAL METAL CARBONATES AND LITHIUM METAL OXIDES FOR LITHIUM RECHARGEABLE
BATTERIES
This invention was made with government support under Contract No. W-31- 109-ENG-38 awarded to the U.S. Department of Energy. The United States Government has certain rights in this invention.
CROSS-REFERENCE TO RELATED PATENT APPLICATIONS
[0001] This application is a continuation in part of and claims priority to U.S. Patent Application No. 10/903,514, filed on July 30, 2004 which is a continuation in part of and claims priority to U.S. Patent Application No. 10/699,484, filed on October 31 , 2003, and incorporated herein by reference in its entirety, which claims priority to U.S. Provisional Patent Application No. 60/423,347, filed November 1 , 2002, also incorporated herein by reference in its entirety.
BACKGROUND OF THE INVENTION
[0002] 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. [0003] 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 5NiQ 5)O2 exhibits rather small capacity for high-energy applications and rather high impedance for high- power applications.
[0004] 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.
[0005] A need therefore remains for an improved layered cathode material for use with lithium ion rechargeable batteries.
SUMMARY OF THE INVENTION
[0006] It is therefore an object of the present invention to provide an improved cathode for rechargeable batteries that possesses improved impedance characteristics.
[0007] 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.
[0008] It is another object of the present invention to provide an improved cathode for rechargeable batteries that possesses improved packing density and thermal safety.
[0009] It is still another object of the present invention to provide an improved cathode for rechargeable batteries that possesses improved capacity characteristics.
[0010] In accordance with the above objects, a number of materials with composition Li1+χNiαMnβCoγM'δO2.zFz (M'=Mg,Zn,AI, Ga, B1Zr1Ti) 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, δ is between 0 and about 0.15, and z is between 0 and about 0.2. Surface-coated Lii+xNiαMnβCoγM'δθ2-zFz (M'=Mg,Zn,AI, Ga, B1Zr1Ti) 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.
[0011] 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 (NiaCθbMnc)Cθ3, 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 Lii+χNiαCθβMnyM'5θyFz (M'=Mg, Zn1AI, Ga1B1Zr1Ti), 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 Y 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
[0012] FIGURES 1 (a)-1 (c) show the morphology of (NiαMnβCoγ)-carbonate prepared by a co-precipitation method using ammonium hydrogen carbonate using magnification factors of χ500, χ2,000, and χ12,000, respectively;
[0013] FIGURES 2(a)-2(c) show the morphology of Li1+xNiαMnβCoγθ2 prepared by calcinations of (NiαMnβCoγ)-carbonate and lithium carbonate at 1000 0C for 10h in air, using magnification factors of χ1 ,000, χ2,000, and χ12,000, respectively;
[0014] FIGURE 3 and FIGURE 4 are plots showing the X-ray diffraction patterns of various Li1+χNiαMnβCoγM'δO2 z Fz compounds;
[0015] FIGURE 5 is a plot showing the first charge/discharge curves of Li/Li(NiαMnβCoγ) O2 2F2 ceils;
[0016] FIGURE 6 is a plot showing the cycling performance of Li/l_i(NiαMnβCoγ)O2 zF2 cells;
[0017] FIGURE 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 30s-current interruption;
[0018] FIGURE 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;
[0019] FIGURES 9 and 10 show the cycling performance of uncoated
Li(NiaMnpCoy)O2, Li(NiaMnpCoy)O2 coated with 0.5wt% Al-isopropoxide, and Li(NiaMnpCo7)O2 coated with 1.0wt% Al-isopropoxide at room temperature and 55°C, respectively;
[0020] FIGURE 11 shows the variation of area specific impedance (ASI) with cycling of C/Li(NiaMnpCoy)O2 measured by a 30s current interruption method;
[0021] FIGURE 12 shows the a.c. impedance spectroscopy of C/Li(NiaMnpCor)O2 cells as a function of cycle number measured with C/Li(NiαMnβCoγ)O2 cells;
[0022] FIGURE 13 presents the variation of area specific impedence at 60% SOC with a 55°C-storage time measured with C/Li(NiαMnpCoγ)O2 cells;
[0023] FIGURE 14 is a plot showing the first charge/discharge curves and variation of discharge capacity with cycle number of Li/Li1+χ(NiαMnβCoγ)O2 cells;
[0024] FIGURE 15 is a plot showing the area specific impedance of C/Li1+χ(NiαMnβCoγ)O2 cells as a function of state of charge measured by a 30s current interruption method;
[0025] FIGURE 16 is a plot showing the cycling performance of
Li/Li1+χ(NiαMnβCoγ)O2.zF2 cells at room temperature and at 55 0C;
[0026] FIGURE 17 is a plot showing the area specific impedance of Li/Li1+χ(NiαMnβCoγ)O2.zFz cells measured by a 30s current interruption method;
[0027] FIGURE 18A shows scanning electron microscope (SEM) images of
(Nii/3Cθi/3Mni/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 17h, respectively; FIGURE 18B is an enlarged view of FIGURE 18A;
[0028] FIGURE 19(a) shows SEM images of (NiIy3COiZ3MnIz3)CO3 precipitates prepared with [Me]=0.05M, [AHC]=0.5M, TR=65°C, ta=17h; and 19(b) shows SEM images of (Nii/3Cθi/3Mni/3)CO3 precipitates prepared with [Me]=0.2M, [AHC]=2.0M,
TR=65°C, ta=4h;
[0029] FIGURES 20(a) and 20(b) represent the SEM images of
(Nio.2igCoo.i25Mno.656)CO3 precipitates prepared with [Me]=O.1 M, [AHC]=LOM, ta=6h at different temperatures (20 and 400C, respectively);
[0030] FIGURE 21 shows an SEM image of MnCO3 precipitates prepared with
[Me]=0.1 M, [AHC]=LOM, TR=55°C, and ta=17h; [0031] FIGURE 22 shows an SEM image of (Cθo.5Mn0.5)CO3 precipitates prepared with [Me]=0.1 M, [AHC]=LOM, TR=50°C, and ta=17h;
[0032] FIGURE 23 represents the X-ray diffraction (XRD) patterns of the
(Nii/3Co1/3Mni/3)CO3 and MnCO3 precipitates shown in Figure 18 and 21 , respectively, together with the reported XRD patterns{of MnCO3 (JCPDS 86-173);
[0033] FIGURE 24A shows SEM images of Li[Nii/3Coi/3Mni/3]O2 prepared using the (Nii/3Coi/3Mn1/3)CO3 shown in Figure 18 with calcination carried out at 10000C for
10h in air; FIGURE 24B is an enlarged view of FIGURE 24A;
[0034] FIGURE 25 represents the XRD patterns of the Li[Nii/3Cθi/3Mn1/3]O2 material shown in Figure 24; and
[0035] FIGURE 26 shows the first charge/discharge curves of the
LiZLi[NiIz3COiZ3Mn1Z3]Oa 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
[0036] 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, Tl, 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. [0037] 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+χNiαMnβCoγM'δO2.zFz with the value M^Mg1Zn1AI1Ga1B1Zr1Ti. [0038] For the solid state reaction method, (Ni,Mn,Co)-hydroxides or (Ni, Mn1Co)- 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(NO3J2-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, Mn1Co)- 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 40-700C. The co-precipitated powders are filtered and dried. To prepare a Lii+xNiαMnβCoγM'δO2_zFz (M'=Mg,Zn,AI,Ga, B1Zr1Ti) 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 700-10000C for 10-24 hours either in air or in an oxygen-containing atmosphere.
[0039] 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 8O0C for about 12-24 hours and evaporated in a rotary vacuum evaporator. Organic contents in the gel precursor are eliminated at 40O0C for 2 hours. Finally, the resulting powder is calcined at 800-10000C for about 10-24 hours either in air or in an oxygen-containing atmosphere.
[0040] 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 45O0C for 5 hours in air. The decomposed powders are then fired at about 800-10000C for about 10-24 hours either in air or in an oxygen-containing atmosphere. [0041] For the surface-coating of the synthesized compound ,
Lii+χNiαMnβCoγM'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 Lii+χNiαMnβCθγM'δθ2-2Fz 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 Lii+χNiαMnβCoγM'δθ2-zFz. Thereafter, the surface-coated Lii+χNiαMnβCoγM'δθ2-zFz powder is dried at temperatures between about 250C and 7000C for approximately 1 to 24 hours.
[0042] 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).
[0043] 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 χ500, χ2,000, and χ12,000, respectively.
[0044] FIGS. 2(a)-2(c) show the morphology of Lii+xNiaMnpCoYO2 prepared by calcinations of (NiaMnpCov)-carbonate and lithium carbonate at 10000C for 10h 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 x 1 ,000, χ2,000, and χ12,000, respectively. [0045] FIGS. 3 and 4 represent X-ray diffraction patterns of Li1+χNiαMnβCoγM'δO2.
ZFZ compounds. All of the compounds exhibit the ordered rock-salt structure with crystallographic structure of R3m . For the Li-excess composition such as Li(Li02Ni0 2+0 52Co0.,Mn0 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. [0046] FIG. 5 shows the first charge/discharge curves of Li/Li(NiαMnβCoγ)O2_zFz cells, and FIG. 6 shows cycling performance of Li/Li(NiαMnpCoγ)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.
[0047] FIG. 7 shows area specific impedance (ASI) of C/Li(NiαMnβ)O2.zFz cells as a function of state of charge (SOC) measured by 30s-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.
[0048] FIGS. 9 and 10 show the cycling performance of uncoated Li(NiαMnβCoγ)θ2, Li(NiαMnpCoγ)O2 coated with 0.5 wt% Al-isopropoxide, and Li(NiαMnβCoγ)O2 coated with 1.0 wt% Al-isopropoxide at room temperature and 550C, respectively. The coating solution is prepared by dissolving appropriate amount of Al-isopropoxide in ethanol. Li(NiαMnpCoγ)O2 powders are then mixed thoroughly with the coating solution and dried at 100°C for 12h. The coated powders are subsequently heat-treated at 300°C for 3h in air. For FIG. 9, the data identified under group (a), α=0.4 , β=0.4, γ=0.2, with the Li(NiαMnpCoγ)θ2 uncoated. For the data identified under group (b), α=0.4 , β=0.4, γ=0.2, and the Li(NiaMnpCoy)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(NiaMnpCoY)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(NiaMnpCoY)O2 uncoated. For the data identified under group (b), α=0.4, , β=0.4, γ=0.2, and the Li(NiαMnpCoγ)O2 is coated with 0.5 wt% Al-isopropoxide. [0049] FIG. 11 shows the variation of area specific impedance (ASl) with cycling of CVLi(N iaMnpCov) O2 measured by a 30s current interruption method with C/Li(NiαMnpCoγ)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. [0050] 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(NiαMnβCoγ)O2 is coated with 1.0 wt% Al-isopropoxide. [0051] 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(NiαMnpCoγ)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. FIGS. 9-13 clearly show the surface coating greatly improving the cycle life, as well as calendar life, of the lithium-ion cells.
[0052] FIG. 14 shows the first charge/discharge curves and variation of discharge capacity with cycle number of Li/l_i1+χ(NiαMnβCoγ)O2 cells. FIG. 15 shows the area specific impedance of C/Li1+χ(NiαMnβCoγ)O2 cells as a function of state of charge measured by a 30s current interruption method.
[0053] FIG. 16 shows cycling performance of Li/Li1+χ(NiαMnβCoγ)O2.zFz cells at room temperature and at 550C. FIG. 17 shows the area specific impedance of Li/Li1+χ(NiαMnβCoγ)O2.zFz cells measured by a 30s current interruption method.
[0054] FIGS. 14-17 clearly show that substitution of oxygen with fluorine significantly improves cycling performance and lowers the impedance of the cathode materials.
[0055] 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, (NiaCθbMnc)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 (NiaCopMnY)CO3, spherical lithium metal oxides with composition Lii+χNiαCθβMnγM'δOyFz (M^Mg1Zn1AI1Ga1 B1Zr1Ti) 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 Y 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. [0056] The spherical (NiaCθbMnc)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 0.01 M 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 200C 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 24h. All of the precipitation reaction and aging are carried out under constant stirring. After aging, the coprecipitated powders are filtered and dried.
[0057] To prepare a Lii+xNiαCθβMnγM'δOyFz (M^Mg1Zn1AI1Ga1B1Zr1Ti) 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 4500C to about 700°C for about 12-30 hours either in air or in oxygen atmospheres and then at about 7000C to about 10000C for about 10-24 hours either in air or in oxygen atmospheres. [0058] In one exemplary embodiment, the synthesized compound Lii+χNiαCθβMnγM'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 LiPFe/ED:DEC (1 :1). [0059] FIGS. 18A and 18B show SEM images of (Ni1Z3Co1Z3Mn1Z3)CO3 precipitates.
The a metal solution (FIG. 18A) and ammonium hydrogen carbonate (AHC) (FIG. 18B) concentrations were 0.1 and 1.0M respectively; the reaction temperature (TR) and the aging time (ta) were 65°C and 17h, respectively. It can be seen in FIG. 18 that the carbonate precipitates have a spherical morphology with a mean particle size (D50) of about 5-6μm and a very narrow size distribution of about 1 to 50 microns.
[0060] FIG. 19 shows additional SEM images of (Nii/3Cθi/3Mni/3)CO3, prepared by different methods. FIG. 19(a) shows the SEM images of (NiIz3COiZ3Mn1Z3)CO3 precipitates prepared with a metal solution of about 0.05M, AHC concentration of about 0.5M, TR= about 65°C, ta= about 17h; 19(b) shows the SEM images of
(Niiz3Co-ιz3Mniz3)CO3 precipitates prepared with Me concentration of 0.2M, AHC concentration of 2.0M, TR= about 65°C, ta= about 4h.
[0061] FIGS. 20(a) and 20(b) show the SEM images of (Ni0.2i9Co0.i25Mn0.656)CO3 precipitates prepared with a metal solution concentration of 0.1 M, AHC concentration of about 1.0M, ta= about 6h at different temperatures (about 2O0C and about 400C, respectively).
[0062] FIG. 21 shows an SEM image of MnCO3 precipitates prepared with a metal solution concentration of about 0.1 M, AHC concentration of about 1.0M, TR= about
55°C, and ta= about 17h.
[0063] FIG. 22 shows an SEM image of (Cθo.sMno.5)CO3 precipitates prepared with a metal solution concentration of about 0.1 M, AHC concentration of about 1.0M, TR= about 500C, and ta= about 17h.
[0064] FIG. 23 represents the x-ray diffraction (XRD) patterns of the
(Niiz3Co-iz3Mni/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).
[0065] FIGS. 24A and B show the SEM images of Li[Ni1Z3Co1Z3MnIz3]O2 prepared using the (NiIz3Co1Z3Mn1Z3)CO3 shown in FIG. 18. The calcinations were carried out at about 10000C for about 10h in air. It can be seen in FIG. 24B that the
Li[Ni1Z3Co1Z3Mn1Z3]O2 material retained the size and morphology of the
(Ni1Z3Co1Z3Mn1Z3)CO3 precursor.
[0066] FIG. 25 represents the XRD patterns of the Li[Ni1Z3Co-Iz3Mn1Z3]O2 material shown in FIG. 24. The material exhibits the ordered rock-salt structure with crystallographic structure of R3m. [0067] FIG. 26 shows the first charge/discharge curves of the Li/Li[Ni1/3Coi/3Mni/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. [0068] 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. [0069] 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

WHAT IS CLAIMED IS:
1. A method of preparing a mixed nickel-cobalt-manganese carbonate comprising the steps of: dissolving in water about 0.01 M to about 2M of a metal solution comprising: a nickel compound selected from the group consisting of Ni-acetate, Ni-nitrate, Ni-sulfate and combinations thereof; a cobalt compound selected from the group consisting of Co-acetate, Co-nitrate, Co-sulfate, and combinations thereof; and a manganese compound chosen from the group consisting of Mn- acetate, Mn-nitrate, Mn-sulfate, and combinations thereof; adding the metal solution to an aqueous solution of about 0.1 M to about 5M of a carbonate chosen from the group consisting of ammonium hydrogen carbonate, sodium carbonate and combinations thereof; aging precipitates in the metal solution at a temperature increased from about 200C to about 65°C wherein the metal solution is reacted at each temperature for about 1h to about 24h.
2. The method of preparing a mixed nickel-cobalt-manganese carbonate of Claim 1 , wherein the steps of reacting and aging are carried out with constant stirring.
3. The method of preparing a mixed nickel-cobalt-manganese carbonate of Claim 1 further comprising the steps of, after aging, filtering and drying the precipitates.
4. The method of preparing a mixed nickel-cobalt-manganese carbonate of Claim 1 , wherein the carbonate solution has a pH which is varied from about 7 to about 10 using a hydroxide selected from the group consisting of ammonium hydroxide, sodium hydroxide, and combinations thereof.
5. The method of preparing a mixed nickel-cobalt-manganese carbonate of Claim 1 , wherein the mixed nickel-cobalt-manganese comprises a narrow size distribution of about 1 to about 50 microns of substituted lithium nickel-manganese oxide.
6. The method of preparing a mixed nickel-cobalt-manganese carbonate of Claim 1 , wherein the water comprises distilled water.
7. 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, M'-hydroxide (or M'-carbonate or M'-oxide;
M'=Mg,Zn,AI, Ga, B1Zr1Ti), and LiF (or NH4F) for about 12 to 24 hours to form a mixed powder; calcinating the mixed powder at about 450 to 7000C 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.
8. The method of claim 7 further comprising the step of adding a carbon additive and a polyvinylidene fluoride (PVDF) wherein the positive active composition forms a laminate.
9. A method of preparing a positive active composition comprising the steps of: preparing a mixed mixed nickel-cobalt-manganese carbonate by: forming a metal solution by disolving in water about 0.01 M to about 2M of: a nickel compound selected from the group consisting of Ni-acetate, Ni-nitrate, Ni-sulfate and combinations thereof; a cobalt compound selected from the group consisting of Co-acetate, Co-nitrate, Co-sulfate, and combinations thereof; and a manganese compound chosen from the group consisting of Mn- acetate, Mn-nitrate, Mn-sulfate, and combinations thereof; adding the metal solution to an aqueous solution of about 0.1 M to about 5M of a carbonate chosen from the group consisting of ammonium hydrogen carbonate, sodium carbonate and combinations thereof; aging precipitates in the metal solution at a temperature increased from about 200C to about 65°C wherein the solution is reacted at each temperature for about 1 h to about 24h.; mixing amounts of the mixed mixed nickel-cobalt-manganese carbonate, lithium hydroxide (or lithium carbonate or lithium nitrate), M'-hydroxide (or M'- carbonate or M'-oxide; M'=Mg,Zn,AI, Ga, B1Zr1Ti), and LiF (or NH4F) for about 12 to 24 hours to form a mixed powder; calcinating the mixed powder at about 450 to 7000C for about 12 to 30 hours either in air or in oxygen atmospheres; and calcinating the mixed powder at about 700 to 10000C for about 10 to 24 hours either in air or in oxygen atmospheres.
10. The method of claim 9, wherein the steps of reacting and aging are carried out with constant stirring.
11. The method of claim 9 further comprising the steps of, after aging, filtering and drying the precipitates.
12. The method of claim 9, wherein the carbonate solution has a pH which is varied from about 7 to about 10 using a hydroxide selected from the group consisting of ammonium hydroxide, sodium hydroxide, and combinations thereof.
13. The method of claim 9, wherein the mixed nickel-cobalt-manganese comprises a narrow size distribution of about 1 to about 50 microns of substituted lithium nickel-manganese oxide.
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