Abstract:
The present invention relates to a positive active material and a method for producing same and, more specifically, to a positive active material comprising LiAlO2 at the surface thereof as a result of reacting an Al compound with residual lithium and to a method for producing same.

Description:
CROSS-REFERENCE TO RELATED APPLICATIONS 
       [0001]    This application is a continuation-in-part of PCT/KR2015/007719, filed Jul. 24, 2015, which claims the benefit of Korean Patent Application No. 10-2014-0195504, filed Dec. 31, 2014, the contents of each of which are incorporated herein by reference. 
     
    
     FIELD OF THE INVENTION 
       [0002]    Embodiments of the inventive concept relate to a positive active material and a method for producing the same, and more particularly, relate to a positive active material including LiAlO 2  which is generated from a reaction with an Al compound and a residual lithium on the surface, and a method for producing the same. 
       BACKGROUND OF THE INVENTION 
       [0003]    A general method for producing a lithium oxide composite includes sequential operations of preparing a transition metal precursor, mixing the transition metal precursor with a lithium compound, and then firing the mixture. 
         [0004]    In this course, LiOH and/or Li 2 O 3  are used as the lithium compound. Usually, in the case that a positive active material has Ni content equal to or smaller than 65% of the positive active material, Li 2 O 3  is employed therein. In the case that Ni content is equal to or smaller than 65% of the positive active material, it is preferred to employ LiOH for a low temperature reaction. However, a Ni-rich system, in which Ni content is equal to or larger than 65% of the positive active material, has a problem with a high amount of residual lithium which remains in forms of LiOH and Li 2 CO 3  on the surface of the positive active material due to a low temperature reaction. Such residual lithium, that is, non-reacted LiOH and Li 2 CO 3 , reacts with an electrolyte to cause gas generation and a swelling effect, incurring severe degradation of high temperature stability. Furthermore, the non-reacted LiOH may cause gelation due to its high viscosity while mixing slurry before manufacturing electrode plates. 
         [0005]    Although a washing process is generally executed to remove the non-reacted Li component, this could still cause surface damage of a positive active material during a washing process, hence degrading the characteristics of capacity and rates and further inducing an additional problem such as an increase of resistance in high temperature storage. 
       SUMMARY OF THE INVENTION 
       [0006]    Embodiments of the inventive concept provide a new positive active material capable of improving the characteristics of lifetime, high temperature storage, and particle strength, while removing a non-reacted Li component, and a method for producing the positive active material. 
         [0007]    According to an aspect of the inventive concept, a positive active material includes LiAlO 2  in a surface. 
         [0008]    The positive active material may include LiAlO 2  exhibiting a peak, where 2θ is ranged from 45° to 46°, in XRD. 
         [0009]    The positive active material may be given in Formula 1 that is L 1+a Ni b M1 c M2 d O 2  where 0.95≧b≧0.75, a+b+c=1, M1 is one or more selected from a group of Co, B, Ba, Cr, F, Li, Mo, P, Sr, Ti, and Zr, and M2 is one or more selected from a group of Mn, Al, B, Ba, Cr, F, Li, Mo, P, Sr, Ti, and Zr. 
         [0010]    Residual lithium of the positive active material may be equal to or smaller than 0.6 wt %. 
         [0011]    Particle strength of the positive active material is equal to or larger than 150 MPa. 
         [0012]    According to another aspect of the inventive concept, a method for producing a positive active material includes preparing the positive active material, and mixedly thermally treating the positive active material with a compound including Al. 
         [0013]    In the method for producing a positive active material, the compound including the Al may be selected from a group of Al(OH) 3 , Al 2 O 3 , Al(NO 3 ) 3 , Al 2 (SO 4 ) 3 , AlCl 3 , AlH 3 , AlF 3 , and AlPO 4 . 
         [0014]    The method for producing a positive active material further includes, between the preparing of the positive active material and the mixedly agitating of the positive active material, preparing a washing solution in uniform temperature, agitating the positive active material in the washing solution, and drying the washed positive active material. 
         [0015]    In the method for producing a positive active material, the washing solution may be distilled water or an alkaline solution. 
         [0016]    In the method for producing a positive active material, the drying may include vacuum-drying the washed positive active material at 80 to 200° C. for 5 to 20 hours. 
         [0017]    Other aspects, advantages, and salient features of the disclosure will become apparent to those skilled in the art from the following detailed description, which, taken in conjunction with the annexed drawings, discloses various embodiments of the present disclosure. 
         [0018]    A positive active material has an effect of increasing particle strength as well as reducing an amount of residual lithium component due to presence of LiAlO 2  by doping aluminum in the positive active material and then by reacting the doped aluminum with the residual lithium which remains on the surface thereof. 
     
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         [0019]    The patent or application file contains at least one drawing executed in color. Copies of this patent or patent application publication with color drawing(s) will be provided by the Office upon request and payment of the necessary fee. 
           [0020]      FIG. 1  shows results of measuring active materials, which are manufactured through a comparison and an embodiment according to the inventive concept, by using XRD measurement. 
           [0021]      FIG. 2  shows results of measuring particle strength of active materials manufactured through a comparison and an embodiment according to the inventive concept. 
           [0022]      FIG. 3  shows result of measuring amounts of residual lithium components of active materials manufactured through comparisons and embodiments according to the inventive concept. 
           [0023]      FIG. 4  shows results of measuring lifetime characteristics of batteries including active materials manufactured through comparisons and embodiments according to the inventive concept. 
           [0024]      FIG. 5  shows results of high temperature storage characteristics of active materials manufactured through comparisons and embodiments according to the inventive concept. 
       
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
       [0025]    Hereinafter, embodiments of the inventive concept will be described in conjunction with the accompanying drawings, but the inventive concept may not be restrictive to the following embodiments. 
       Embodiment 
     Coating Concentration Gradient Positive Active Material 
       [0026]    After inputting distilled water of 20 L and ammonia of 840 g as a chelating agent into a batch reactor (having capacity of 70 L and a rotation motor&#39;s power equal to or larger than 80 W), agitation was performed with a motor rate of 400 rpm while maintaining internal temperature of the reactor at 50° C. 
         [0027]    As a second operation, a first precursor solution having concentration of 2.5 M, which was mixed with nickel sulfate, cobalt sulfate, and manganese sulfate in a mole ratio of 9:1:0, was input in a rate of 2.2 L/hour and continuously an ammonia solution having concentration of 28% was input in a rate of 0.15 L/hour. Additionally, for adjusting pH, a sodium hydroxide solution having concentration of 25% was supplied to maintain pH on 11. An impeller speed was adjusted at 400 rpm. The first precursor solution, the ammonia solution, and the sodium hydroxide solution, which are prepared, was input continuously into the reactor in an amount of 27 L. 
         [0028]    Next, as a third operation, a concentration gradient layer forming solution was prepared with concentration of 2.5 M where nickel sulfate, cobalt sulfate, and manganese sulfate were mixed in a mole ratio of 65:15:20. After fixing an amount of the first precursor solution of 2.5-M concentration, which was mixedly manufactured with nickel sulfate, cobalt sulfate, and manganese sulfate in a mole ratio of 9:1:0 through the second operation in an agitator in addition to the batch reactor, in 10 L, the concentration gradient layer forming solution was input in a rate 2.2 L/hour and agitated with the first precursor solution to make a second precursor solution. At the same time, the second precursor solution was introduced into the batch reactor. Until a mole ratio of nickel sulfate, cobalt sulfate, and manganese sulfate of the second precursor solution reaches concentration of a shell layer that is 4:2:4, the concentration gradient layer forming solution was mixedly introduced into the batch reactor, an ammonia solution having concentration of 28% was input in a rate of 0.08 L/hour, and a sodium hydroxide solution was maintained in pH of 11. In this case, an input amount of the second precursor solution, the ammonia solution, and the sodium hydroxide solution was 17 L. 
         [0029]    Next, as a fourth operation, a third precursor solution, which was mixed with nickel sulfate, cobalt sulfate, and manganese sulfate in a mole ratio of 4:2:4, was input into the batch reactor until the volume thereof reaches 5 L. After completing a reaction, a spherical nickel-manganese-cobalt composite hydroxide precipitate was obtained from the batch reactor. 
         [0030]    After filtering the precipitated composite metal hydroxide and washing the composite metal hydroxide by water, the washed composite metal hydroxide was dried in a hot blower at 110° C. for 12 hours to obtain a precursor powder having a structure of metal oxide composite where an inner core layer had a continuous concentration gradient to (Ni 0.9 Co 0.1 )(OH) 2  and an outer shell layer had a continuous concentration gradient from (Ni 0.9 Co 0.1 )(OH) 2  to (Ni 0.4 Co 0.2 Mn 0.4 )(OH) 2 . 
         [0031]    After mixing the metal hydroxide composite and hydroxide lithium (LiOH) in a mole ratio of 1:1.02, heating the mixture in a temperature elevation rate of 2° C./min, and firing the mixture at 790° C. for 20 hours, there was obtained a positive active material powder where an inner core layer had a continuous concentration gradient to Li(Ni 0.9 Co 0.1 )O 2  and an outer shell layer had a continuous concentration gradient from Li(Ni 0.9 Co 0.1 )O 2  to Li(Ni 0.4 Co 0.2 Mn 0.4 )O 2 . 
         [0032]    After dry and wet coating of positive active material particles with an Al compound, the particles were processed in thermal treatment at 720° C. 
       Embodiment 
     Synthesizing NCA Particles 
       [0033]    A NiCo(OH) 2  precursor was first manufactured through a coprecipitation reaction to obtain an NCA-series positive active material. After mixing the metal hydroxide composite and the lithium hydroxide in a mole ratio of 1:1.02, heating the mixture in a temperature elevation rate of 2° C./min, and firing the mixture at 750° C. for 20 hours, a positive active material powder was obtained. 
         [0034]    After dry and wet coating of positive active material particles with an Al compound, the particles were processed in thermal treatment at 720° C. 
         [0000]    
       
         
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
             
           
               
                   
                 TABLE 1 
               
             
             
               
                   
                   
               
               
                   
                   
                   
                   
                   
                 Thermal 
               
               
                   
                 Washing 
                   
                   
                 Calcination 
                 treatment 
               
               
                   
                 time 
                 1st introduction 
                 2nd introduction 
                 temp. 
                 temp. 
               
             
          
           
               
                 No 
                 [min] 
                 Al(OH) 3   
                 Al 2 O 3   
                 Al(OH) 3   
                 Al 2 O 3   
                 Al(NO 3 ) 3   
                 [° C.] 
                 [° C.] 
               
               
                   
               
             
          
           
               
                 Comparison-1 
                 0 
                 — 
                 — 
                 — 
                 — 
                 — 
                 790 
                 — 
               
               
                 Comparison-2 
                 0 
                 — 
                 — 
                 — 
                 — 
                 — 
                 830 
                 — 
               
               
                 Comparison-3 
                 30 
                   
                 — 
                 — 
                 — 
                 — 
                 810 
                 720 
               
               
                 Comparison-4 
                 0 
                 4.0 
                 — 
                 — 
                 — 
                 — 
                 750 
                 — 
               
               
                 Comparison-5 
                 30 
                 3.5 
                 — 
                 — 
                 — 
                 — 
                 750 
                 720 
               
               
                 Comparison-6 
                 0 
                 4.0 
                 — 
                 — 
                 — 
                 — 
                 750 
                 — 
               
               
                 Embodiment-1 
                 0 
                 — 
                 — 
                 — 
                 2.0 
                 — 
                 790 
                 720 
               
               
                 Embodiment-2 
                 0 
                 — 
                 — 
                   
                 2.0 
                 — 
                 810 
                 720 
               
               
                 Embodiment-3 
                 0 
                 — 
                 — 
                   
                 2.0 
                 — 
                 840 
                 720 
               
               
                 Embodiment-4 
                 0 
                 — 
                 — 
                 1.0 
                 — 
                 — 
                 830 
                 500 
               
               
                 Embodiment-5 
                 30 
                 — 
                 — 
                 — 
                 1.0 
                 — 
                 810 
                 720 
               
               
                 Embodiment-6 
                 120 
                 — 
                 — 
                 — 
                 — 
                 1.0 
                 810 
                 720 
               
               
                 Embodiment-7 
                 0 
                 — 
                 — 
                 2.0 
                 — 
                 — 
                 750 
                 720 
               
               
                 Embodiment-8 
                 30 
                 2.5 
                 — 
                 1.0 
                 — 
                 — 
                 750 
                 720 
               
               
                 Embodiment-9 
                 120 
                 1.5 
                 — 
                 — 
                 — 
                 2.0 
                 750 
                 720 
               
               
                 Embodiment- 
                 0 
                 — 
                 — 
                 4.0 
                 — 
                 — 
                 750 
                 720 
               
               
                 10 
               
               
                 Embodiment- 
                 120 
                 1.4 
                 — 
                 1.0 
                 — 
                 — 
                 750 
                 700 
               
               
                 11 
               
               
                 Embodiment- 
                 120 
                 3.0 
                 — 
                 — 
                 — 
                 2.0 
                 750 
                 700 
               
               
                 12 
               
               
                   
               
             
          
         
       
     
       Experimental Example 
     Measuring XRD Characteristics 
       [0035]      FIG. 1  shows results of measuring XRD of active materials which are manufactured through Comparison-6 and Embodiment-2. 
         [0036]    Different from Comparison-6, particles manufactured through Embodiment-2 according to the inventive concept has a peak between 45° and 46°. 
       Experimental Example 
     Measuring Particle Strength 
       [0037]      FIG. 2  shows results of measuring particle strength of active materials manufactured through Comparison-6 and Embodiment-10. 
         [0038]    From  FIG. 2 , it may be seen that particles manufactured through Embodiment-10 are more improved about 20% than particles of Comparison-6 in strength. 
       Experimental Example 
     Measuring Non-Reacted Lithium 
       [0039]    Non-reacted lithium was measured as an amount of 0.1 M HCl which had been used until pH 4 by pH titration. First, after inputting a positive active material of 5 g into distilled water (DIW) of 100 ml, agitating the mixed solution for 15 minutes, filtering the agitated solution, and taking the filtered solution of 50 ml, 0.1 M HCl was added thereto and a consumption amount of HCl dependent on pH variation was measured to determine Q1 and Q2. Then, amounts of non-reacted LiOH and Li 2 CO 3  were calculated by equations as follows. 
         [0000]      M1=23.94 (LiOH molecular weight) 
         [0000]      M2=73.89 (Li 2 CO 3  molecular weight) 
         [0000]        SPL  size=(Sample weight×Solution weight)/Water weight
 
         [0000]      LiOH (wt %)=[( Q 1− Q 2)× C×M 1×100]/( SPL  size×1000)
 
         [0000]      Li 2 CO 3  (wt. %)=[2× Q 2 ×C×M 2/2×100]/( SPL  size×1000)
 
         [0040]    Table 2 and  FIG. 3  show results of measuring concentration of non-reacted LiOH and Li 2 CO 3  from NCA-series lithium oxide composites manufactured through the aforementioned Embodiments and Comparisons, as follows. 
         [0000]    
       
         
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
             
           
               
                   
                 TABLE 2 
               
             
             
               
                   
                   
               
               
                   
                 Residual lithium [ppm] 
                 Discharge 
                 Lifetime 
                 Before 
                 After 
               
             
          
           
               
                   
                   
                   
                 Total 
                 capacity 
                 100th 
                 storage 
                 storage 
               
               
                 No 
                 LiOH 
                 Li 2 CO 3   
                 Li [%] 
                 [0.1 C] 
                 [%] 
                 ohm 
                 ohm 
               
               
                   
               
             
          
           
               
                 Comparison-1 
                 7.376 
                 4,552 
                 0.0431 
                 206 
                 92 
                 — 
                 — 
               
               
                 Comparison-2 
                 3,211 
                 4,128 
                 0.0246 
                 204 
                 92 
                 18  
                 131  
               
               
                 Comparison-3 
                 3,445 
                 1,220 
                 0.0177 
                 206 
                 84 
                 — 
                 — 
               
               
                 Comparison-4 
                 5,035 
                 3,076 
                 0.0293 
                 201 
                 82 
                 5 
                 11 
               
               
                 Comparison-5 
                 2,727 
                 1,433 
                 0.0153 
                 202 
                 70 
                 7 
                 16 
               
               
                 Comparison-6 
                 7.422 
                 3,862 
                 0.0414 
                 210 
                 74 
                 — 
                 — 
               
               
                 Embodiment-1 
                 4,930 
                 4,735 
                 0.0334 
                 196 
                 93 
                 — 
                 — 
               
               
                 Embodiment-2 
                 3,035 
                 1,831 
                 0.0176 
                 188 
                 98 
                 — 
                 — 
               
               
                 Embodiment-3 
                 1,903 
                 869 
                 0.0103 
                 191 
                 83 
                 20  
                 90 
               
               
                 Embodiment-4 
                 2,632 
                 2,756 
                 0.0184 
                 205 
                 80 
                 — 
                 — 
               
               
                 Embodiment-5 
                 2,254 
                 1,082 
                 0.0123 
                 204 
                 90 
                 — 
                 — 
               
               
                 Embodiment-6 
                 1,690 
                 1,069 
                 0.0100 
                 203 
                 88 
                 — 
                 — 
               
               
                 Embodiment-7 
                 2,090 
                 1,080 
                 0.0117 
                 206 
                 77 
                 8 
                 20 
               
               
                 Embodiment-8 
                 2,272 
                 1,268 
                 0.0129 
                 202 
                 77 
                 6 
                 13 
               
               
                 Embodiment-9 
                 2,116 
                 1,239 
                 0.0122 
                 203 
                 77 
                 11  
                 35 
               
               
                 Embodiment- 
                 2,049 
                 1,702 
                 0.0132 
                 204 
                 60 
                 — 
                 — 
               
               
                 10 
               
               
                 Embodiment- 
                 2,096 
                 1,349 
                 0.0124 
                 209 
                 55 
                 8 
                 13 
               
               
                 11 
               
               
                 Embodiment- 
                 2,314 
                 1,650 
                 0.0141 
                 204 
                 75 
                 33  
                 92 
               
               
                 12 
               
               
                   
               
             
          
         
       
     
         [0041]    As shown in  FIG. 3 , residual lithium of Comparison-4 was measured in a high level because a washing or surface processing was not performed. Residual lithium of Embodiment-7 executing thermal treatment after coating an aluminum compound was reduced than that of Comparison-4 in amount. 
         [0042]    Additionally, as shown in  FIG. 3 , Embodiment-3 executing thermal treatment after coating an aluminum compound with a concentration gradient NCM positive active material was more improved than Comparison-2, which did not execute post-treatment, for residual lithium. 
       Experimental Example 
     Evaluating Charge/Discharge Characteristics 
       [0043]    Table 2 and  FIG. 4  show results of performing charge/discharge experiments between 3 V and 4.3 V in rates of C/10 charge and C/10 discharge after manufacturing respective coin cells by using positive active materials, which are manufactured through the aforementioned Embodiments and Comparisons, as positive electrodes and by using lithium metals as negative electrodes. 
         [0044]    From  FIG. 4 , it may be seen that an embodiment executing an Al coating after washing is better in lifetime. In  FIG. 4 , Comparison-3 and Comparison-5 correspond to concentration gradient NCM and NCA positive active materials which are respectively washed. Embodiment-5 for a concentration gradient NCM positive active material made executing an Al coating after washing and Embodiment-8 for a concentration gradient NCA positive active material executing an Al coating after washing were improved in lifetimes. 
       Experimental Example 
     Results of Measuring Impedance Before/After High Temperature Storage 
       [0045]    Table 2 and  FIG. 5  show results of measuring impedance before/after high temperature storage of Embodiment 3 for an NCM-series positive active material having a continuous concentration gradient. 
         [0046]    From  FIG. 5 , it may be seen that impedance of Embodiment-3 executing thermal treatment after an Al coating is more reduced than that of Comparison-2 which does not execute washing and surface treatment. 
         [0047]    Embodiments of the inventive concept relate to a positive active material including LiAlO 2  and a method for producing the same, being highly useful for enhancing particle strength, as well as reducing residual lithium, due to presence of LiAlO 2  by doping the positive active material with aluminum and then reacting the residual lithium, which is existing in the surface, with the aluminum.