DETAILED DESCRIPTION OF THE INVENTION

[0020] A positive active material of the present invention for lithium rechargeable batteries includes a LiCoO ₂ core and a metal selected from a group consisting of Al, Mg, Sn, Ca, Ti, Mn and mixtures thereof. The metal has a concentration gradient from the surface of the core to the center of the core. It is preferable that a ratio of the concentrations between the surface and the center is 3 to 10:1, and more preferably 5 to 10:1.

[0021] A method of preparing the positive active material for lithium rechargeable batteries of the present invention will now be described.

[0022] A metal compound is dissolved in alcohol to prepare a metal compound solution in a sol state. The metal compound may be an alkoxide of Al, Mg, Sn, Ca, Ti or Mn, or mixtures thereof and the exemplary thereof may be tin (IV) ethyl hexano-isopropoxide (Sn(OOC ₈ H ₁₅ ) ₂ (OC ₃ H ₇ ) ₂ ) or isopropoxide. The alcohol may be isopropanol, ethanol or methanol.

[0023] The metal compound solution (“sol”) is coated on LiCoO ₂ . At this time, a concentration of the metal in the metal compound solution is preferably 0.1 to 6 mol % of a mixture amount of the metal and Co, and more preferably, 3 to 4 mol %. The coating process is preferably performed at a temperature of 300 to 800° C. for 2 to 12 hours.

[0024] During the coating process, the metal compound, e.g. metal alkoxide in the metal compound solution (“sol”) is hydrolyzed by moisture in the atmosphere, and then the hydrolyzed product polycondenses to form a metal compound gel. Thereafter, the metal compound gel reacts with functional groups on a surface of LiCoO ₂ and the metal compound gel is adhered to the surface of LiCoO ₂ .

[0025] The metal compound gel-adhered LiCoO ₂ is dried at a temperature of 50 to 150° C. for 2 to 12 hours and the dried product is sintered at 150-500° C. for 2 to 12 hours. In case that the metal compound is a metal alkoxide, the metal alkoxide adhered to the surface is decomposed into an amorphous metal oxide in the drying process and then is crystallized to form a crystalline metal oxide in the sintering process. The formed metal oxide reacts with LiCoO ₂ to form LiCo _1−x M _x O ₂ solid solution where M is a metal selected from a group consisting of Al, Mg, Sn, Ca, Ti, Mn and mixtures thereof.

[0026] In the case where Sn is used as the metal in the coating process, the following chemical equations result.

Hydrolysis: Sn(OR) ₄ +H ₂ O→Sn(OR) ₃ (OH)+ROH Equation 1

Polycondensation: n[Sn(OR) ₃ (OH)]+n[Sn(OR) ₃ (OH)]→[(OR) ₃ Sn—O—Sn(OR) ₃ ] _n +nH ₂ O Equation 2

Particle surface—OH+[(OR) ₃ Sn—O—Sn(OR) ₃ ] _n →particle surface—O—Sn(OR) ₃ +[Sn(OR) ₃ (OH)] _n Equation 3

[0027] In the above equations OR is an alkoxy group and ROH is an alcohol.

[0028] With reference to Equation 2, the Sn—OH group is condensed to produce water and a polycondensate having Sn—O—Sn bond to form a tin alkoxide gel. Also, with reference to Equation 3, the tin alkoxy group of the gel reacts with the OH group of the LiCoO ₂ particle surface, and a tin alkoxide gel is adhered to the LiCoO ₂ surface. In subsequent processes, the tin alkoxide gel is decomposed into amorphous SnO ₂ in a drying process, and it is crystallized to form crystalline SnO ₂ in a sintering process. The crystalline SnO ₂ reacts with LiCoO ₂ to form LiCo _1−x Sn _x O ₂ solid solution.

[0029] Since the formed metal oxide reacts not only on the surface of the LiCoO ₂ but within the LiCoO ₂ , metal is present all throughout the LiCoO ₂ . However, since the reaction occurs more actively on the surface than within the LiCoO ₂ , a concentration of the metal on the surface of the LiCoO ₂ is greater than the concentration of the metal within the LiCoO ₂ . This is not the case when the sintering temperature is increased. That is, there is an increase in the amount of metal oxide intercalated within the LiCoO ₂ with increases in the sintering temperature. Accordingly, if the sintering temperature is made too high, equal amounts of metal oxide are present on the surface and within the LiCoO ₂ , resulting in a reduction in cycle life characteristics.

[0030] In particular, if the sintering process is performed at a temperature exceeding 500° C., the ratio of the concentrations of the metal oxide between the surface and center of the LiCoO ₂ falls below 3:1 such that a monoclinic phase active material is prepared, thereby reducing the cyclic life. On the other hand, if the sintering process is performed at less than 150° C., the charge-discharge efficiency significantly decreases.

[0031] It is possible to use LiCoO ₂ which is commercially available or prepared by the following method.

[0032] A cobalt oxide such as Co ₃ O ₄ is mixed with a lithium salt such as LiOH. The mixing process is performed using an automatic mixer, and the two substances are homogenized for 1 to 3 hours. At this time, although the mole ratio of cobalt to lithium is intended to be 1:1, a slight excess amount of Li is used in the mixture, since a portion of the Li is lost during the subsequent heating process.

[0033] The resulting mixture is heat-treated at about 900° C. for a period of about 24 hours. The heat-treating process is performed in an oxygen stream. The mixture is sieved to prepare a positive active material for a rechargeable lithium battery. It is preferable to use a two-step heat-treating process for the preparation, the first step at 500° C. for 6 to 12 hours and the second step at 900° C. for 24 hours. By heat-treating the mixture in two steps rather than a single step, the crystallinity is improved.

[0034] The rechargeable lithium battery applying the positive active material of the present invention may use the commonly utilized carbonaceous active material of graphite, carbon, etc., which enables the intercalation-deintercalation of lithium ions for the negative electrode. The commonly used non-aqueous liquid electrolyte, polymer electrolyte, etc. may be used for the electrolyte. A microporous membrane separator may be used in the rechargeable lithium battery of the present invention, if needed.

[0035] The following examples further illustrate the present invention.

EXAMPLE 1

[0036] As a starter material, Co ₃ O ₄ (average particle size of 5 mm) and LiOH.H ₂ O powder finely ground were placed in an automatic mixer in a mole ratio of 1:1.05 and homogenized for 2 hours to prepare LiCoO ₂ . An excess of Li was used since a portion of the Li is lost in the heat-treating process. The resulting compound was heat-treated at 500° C. for 5 hours in an oxygen stream, and then was again heat-treated at 900° C. for 24 hours in an oxygen stream. The compound LiCoO ₂ was then sieved by passing it through a 500-mesh screen (26 mm). The sieved compound LiCoO ₂ is sieved additionally to obtain LiCoO ₂ having an average particle size of 10 μm.

[0037] Subsequently, tin(IV) ethyl hexano-isopropoxide (Sn(OOC ₈ H ₁₅ ) ₂ (OC ₃ H ₇ ) ₂ ) was dissolved in isopropanol, then agitated at 21° C. for 20 hours, thereby producing a sol metal solution. The sol metal solution was coated on a surface of the LiCoO ₂ . The amount of Sn in the coated material was 3 mol % of the total amount of Sn and Co. The coated LiCoO ₂ was dried at 150° C. for 10 hours, then sintered at 150° C. for 10 hours to prepare a positive active material for a rechargeable lithium battery.

EXAMPLE 2

[0038] A positive active material was prepared by the same procedure as in Example 1 except that the LiCoO ₂ dried at 150° C. for 10 hours was sintered at 400° C. for 10 hours.

EXAMPLE 3

[0039] A positive active material was prepared by the same procedure as in Example 1 except that the LiCoO ₂ dried at 150° C. for 10 hours was sintered at 500° C. for 10 hours.

COMPARATIVE EXAMPLE 1

[0040] A positive active material was prepared by the same procedure as in Example 1 except that the LiCoO ₂ dried at 150° C. for 10 hours was sintered at 600° C. for 10 hours.

COMPARATIVE EXAMPLE 2

[0041] A positive active material was prepared by the same procedure as in Example 1 except that the LiCoO ₂ was not coated with the Sn solution.

COMPARATIVE EXAMPLE 3

[0042] 1 g of H ₃ BO ₃ was dissolved in 20 ml of acetone, and then the resulting solution and 10 g of LiCoO ₂ were mixed well. The mixture was heat-treated at 600° C. for 10 hours.

[0043] XRD Results of the Materials

[0044] XRD patterns for the positive active materials of Examples 1-3 and Comparative Example 1 were measured. The results are shown, respectively, in (A), (B), (C), and (D) of FIG. 1 . “•” in FIG. 1 indicates a Si reference peak and (E) in FIG. 1 shows the XRD pattern for SnO ₂ heat-treated at 400° C. As shown in FIG. 1 , the active materials according to Examples 1 to 3 have no SnO ₂ peak. This observation may be due to either the fact that the thickness of the SnO ₂ coating the surfaces is too thin for the X-ray signal or that LiCo _1−x Sn _x O ₂ solid solution is formed.

[0045] To determine these possibilities, lattice constants (a, c) of the active materials prepared at various heat-treating temperatures were measured. The results are shown in FIG. 2 . As shown in FIG. 2 , when sintering at 150° C., SnO ₂ existed on the surface, as with the LiCoO ₂ . With an increase in temperature, there is a change in the value of the constants. It is evident from this result that a structure of the Sn atoms present on the surface changes according to their reaction with a LiCoO ₂ bulk.

[0046] EPMA Results of the Materials

[0047] EPMA (electron probe mass analysis) results are shown in FIG. 3 . Values of the horizontal axis (x-axis) in FIG. 3 represent a distance within a particle. When a line is drawn through a center of the particles, a center value of the x-axis is a center of the particles. The smallest and largest values at both ends are surfaces of the particles. As shown in FIGS. 3 (A) to (D), the concentration of Sn at the surface decreases with increases in temperature, while the bulk (internal and center) concentration increases. At 600° C., the Sn concentration in the bulk approached that at the surface forming a nearly homogeneous solid solution. Results of a chemical analysis of the active material of Example 3 showed that the overall content of Sn was 3 mole % (x= 0.03 in LiCo _1−x Sn _x O ₂ ). The concentrations of Sn in the active material in FIGS. 3 (A) to (D) were normalized using this value.

[0048] As shown in FIG. 4 , an EPMA of the positive active material of the Comparative Example 3 showed that the concentration of B in the bulk region was lower than that at the surface. The concentration of B at the surface appears to be reduced significantly, although it is possible that the B at the surface might be present as a boron compound. The elevated temperature (600° C.) might be the cause of the relatively even dispersion of B through the bulk of the particle in a similar manner to the case of Sn as shown in FIG. 3 (D).

[0049] Electrochemical Evaluation Test

[0050] Charge and discharge voltages curves and performance with continuous cycling of the positive electrodes containing the coated materials of Examples 2 and 3 (heat-treated at 400 and 500° C., respectively), Comparative Example 1 (heat-treated at 600° C.), and Comparative Example 2 (the uncoated LiCoO ₂ ) are shown in FIGS. 5 and 6 . The cycling test was carried out with charge and discharge voltage limits of 4.4V and 2.75V against a lithium metal counter electrode, respectively. Initial two cycles were carried out at 0.2C rate and subsequent 48 cycles at 0.5C rate for both charge and discharge. Although the coated materials of Examples 2 and 3 showed slightly lower initial capacity than the materials of Comparative Examples 1 and 2 as shown in FIG. 6 , their performance with cycling is greatly improved. Even though the cycling performance data are not available presently, the cycling performance of the active material heat-treated at 150° C. (Example 1) was superior as well.

[0051] Cyclic voltammogram results of the powders sintered at 400 (Example 2), 500 (Example 3) and 600° C. (Comparative Example 1) are shown in FIG. 7 . The powder heat-treated at 400 and 500° C. did not show peaks representing typical monoclinic transition at around 4.15V. On the other hand, with the powder heat-treated at 600° C. as well as uncoated LiCoO ₂ (not shown in FIG. 7 ), a monoclinic phase transition appears to occur. This observation might be due to the fact that the powders heat-treated at 400 and 500° C. have a higher concentration of Sn at the surface than powder heat-treated at 600° C. and uncoated LiCoO ₂ . The high concentration of Sn on the surface limits the formation of a monoclinic phase and improves cycle life characteristics.

[0052] For the positive active material for a rechargeable lithium battery of the present invention, specific capacity as well as the cycle life has been improved significantly through a surface coated material.

[0053] The present invention has been described in detail herein above. It should be understood that many variations and/or modifications of the basic inventive concepts taught herein which may appear to those skilled in the present art will still fall within the spirit and scope of the present invention, as defined in the appended claims.