Abstract:
The present invention provides a positive electrode active material for lithium ion batteries having satisfactory battery characteristics. The positive electrode active material for lithium ion batteries, is represented by the following composition formula:
 
Li(Li x Ni 1-x-y M y )O 2+α 
 
wherein M represents one or more selected from the group consisting of scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), copper (Cu), zinc (Zn), gallium (Ga), germanium (Ge), bismuth (Bi), tin (Sn), magnesium (Mg), calcium (Ca), boron (B) and zirconium (Zr); 0≦x≦0.1; 0&lt;y≦0.7; and α&gt;0,
       wherein the particle size of primary particles is 1.6 to 2.3 μm,   the alkali amount at the particle surfaces measured by two-stage neutralization titration is 1.2% by mass or less, and   when the amount of lithium hydroxide in the alkali amount at the particle surfaces is designated as A % by mass, and the amount of lithium carbonate is designated as B % by mass, the ratio A/B is 1 or less.

Description:
BACKGROUND 
     1. Technical Field 
     The present invention relates to a positive electrode active material for lithium ion batteries, a positive electrode for lithium ion batteries, and a lithium ion battery. 
     2. Related Art 
     In regard to the positive electrode active material for lithium ion batteries, lithium-containing transition metal oxides have been generally used. Specific examples thereof include lithium cobaltate (LiCoO 2 ), lithium nickelate (LiNiO 2 ), and lithium manganate (LiMn 2 O 4 ), and in order to improve characteristics (an increase in capacity, cycle characteristics, storage characteristics, reduction of internal resistance, and rate characteristics) or to increase safety, compositization of these materials is in progress. Lithium ion batteries for large-sized applications such as for automobiles and for load leveling, are required to have characteristics that are different from batteries for mobile telephones or personal computers up to date. 
     For an improvement of battery characteristics, various methods have been hitherto used, and for example, Patent document 1 (Japanese Patent No. 4175026) discloses a method for producing a positive electrode material for lithium secondary batteries, the method including passing a lithium nickel composite oxide represented by the composition of:
 
Li x Ni 1-y M y O 2-δ 
 
wherein 0.8≦x≦1.3; 0&lt;y≦0.5; M represents at least one element selected from the group consisting of cobalt (Co), manganese (Mn), iron (Fe), chromium (Cr), vanadium (V), titanium (Ti), copper (Cu), aluminum (Al), gallium (Ga), bismuth (Bi), tin (Sn), zinc (Zn), magnesium (Mg), germanium (Ge), niobium (Nb), tantalum (Ta), beryllium (Be), boron (B), calcium (Ca), scandium (Sc) and zirconium (Zr); δ corresponds to the amount of oxygen deficiency or oxygen excess, and represents −0.1&lt;δ&lt;0.1,
 
     through a classifier, separating the composite oxide into particles having large particle sizes and particles having small particle sizes at an equilibrium separation particle size Dh=1 to 10 μm, and blending particles having large particle sizes with particles having small particle sizes at a weight ratio of 0:100 to 100:0. The Patent Literature recites that according to this method, a positive electrode material for lithium secondary batteries with various balances between rate characteristics and capacity can be easily manufactured. 
     Patent document 1: Japanese Patent No. 4175026 
     SUMMARY 
     The lithium nickel composite oxide described in Patent document 1 (Japanese Patent No. 4175026) is a material having an excess amount of oxygen in the composition; however, there is still room for an improvement to be used as a positive electrode active material for lithium ion batteries of higher quality. 
     Thus, it is an object of the present invention to provide a positive electrode active material for lithium ion batteries having satisfactory battery characteristics. 
     The inventors of the present invention conducted a thorough investigation, and as a result, they found that there is a close correlation between the amount of oxygen in the positive electrode active material, the particle size of primary particles, and the battery characteristics. That is, the inventors found that when the amount of oxygen in the positive electrode active material is adjusted to a certain value or more, and the particle size of primary particles of the positive electrode active material is controlled to an appropriate range, satisfactory battery characteristics are obtained. 
     Furthermore, the inventors found that there is a close correlation between the alkali content at the particle surfaces of the positive electrode active material, as well as the ratio between the amount of lithium hydroxide A and the amount of lithium carbonate B in the alkali amount at the particle surfaces, and the battery characteristics. That is, the inventors found that when the alkali content at the particle surfaces of the positive electrode active material is less than or equal to a certain value, and when the ratio A/B between the amount of lithium hydroxide A and the amount of lithium carbonate B in the alkali amount at the particle surfaces is less than or equal to a certain value, particularly satisfactory battery characteristics are obtained. 
     The present invention was achieved based on the findings described above, and according to one aspect of the present invention, there is provided a positive electrode active material for lithium ion batteries, which is represented by the following composition formula:
 
Li(Li x Ni 1-x-y M y )O 2+α 
 
wherein in the above formula, M represents one or more selected from the group consisting of Sc, Ti, V, Cr, Mn, Fe, Co, Cu, Zn, Ga, Ge, Bi, Sn, Mg, Ca, B, and Zr; 0≦x≦0.1; 0&lt;y≦0.7; and α&gt;0, and
 
     in which the particle size of primary particles is 1.6 μm to 2.3 μm, the alkali amount at the particle surfaces measured by two-stage neutralization and titration is 1.2% by mass or less, and when the amount of lithium hydroxide in the alkali amount at the particle surfaces is designated as A % by mass, and the amount of lithium carbonate is designated as B % by mass, the ratio A/B is 1 or less. 
     According to an embodiment of the positive electrode active material for lithium ion batteries related to the present invention, the alkali amount at the particle surfaces measured by two-stage neutralization and titration is 0.8% by mass or less. 
     According to another embodiment of the positive electrode active material for lithium ion batteries related to the present invention, the ratio A/B is 0.7 or less. 
     According to still another embodiment of the positive electrode active material for lithium ion batteries related to the present invention, M represents one or more selected from Mn and Co. 
     According to still another embodiment of the positive electrode active material for lithium ion batteries related to the present invention, in the composition formula, α&gt;0.05. 
     According to still another embodiment of the positive electrode active material for lithium ion batteries related to the present invention, in the composition formula, α&gt;0.1. 
     According to another aspect, there is provided a positive electrode for lithium ion batteries, which uses the positive electrode active material for lithium ion batteries related to the present invention. 
     According to still another aspect, there is provided a lithium ion battery which uses the positive electrode for lithium ion batteries related to the present invention. 
     According to the present invention, a positive electrode active material for lithium ion batteries having satisfactory battery characteristics can be provided. 
    
    
     
       BRIEF DESCRIPTION OF DRAWINGS 
         FIG. 1  is a photograph of the external appearance of primary particles and secondary particles of the positive electrode active material. 
     
    
    
     DETAILED DESCRIPTION 
     (Configuration of Positive Electrode Active Material for Lithium Ion Batteries) 
     Regarding the material of the positive electrode active material for lithium ion batteries of the present invention, a wide variety of compounds which are useful as a positive electrode active material for the positive electrode of general lithium ion batteries can be used; however, it is particularly preferable to use lithium-containing transition metal oxides such as lithium cobaltate (LiCoO 2 ), lithium nickelate (LiNiO 2 ), and lithium manganate (LiMn 2 O 4 ). The positive electrode active material for lithium ion batteries of the present invention that is produced by using such a material is represented by the following composition formula:
 
Li(Li x Ni 1-x-y M y )O 2+α 
 
wherein in the formula, M represents one or more selected from Sc, Ti, V, Cr, Mn, Fe, Co, Cu, Zn, Ga, Ge, Bi, Sn, Mg, Ca, B and Zr; 0≦x≦0.1; 0&lt;y≦0.7; and α&gt;0.
 
     In the positive electrode active material for lithium ion batteries of the present invention, the proportion of oxygen is represented by O 2+α  (α&gt;0) in the composition formula as described above, and oxygen is contained in excess. Therefore, when the positive electrode active material is used in lithium ion batteries, battery characteristics such as capacity, rate characteristics, and capacity retention ratio are improved. Here, α is preferably such that α&gt;0.05, and more preferably α&gt;0.1. 
     The positive electrode active material for lithium ion batteries is composed of primary particles, secondary particles formed as a result of aggregation of primary particles, or a mixture of primary particles and secondary particles (see  FIG. 1 ). Among these, the particle size of the primary particles is 1.6 μm to 2.3 μm. If the particle size of the primary particles is less than 1.6 μm, there may occur breakage of particles caused by pressing at the time of battery production, or a problem of deterioration caused by cracking of particles at the time of battery cycling. Furthermore, if the particle size of the primary particles is larger than 2.3 μm, a problem of battery deterioration occurs as a result of degradation of the electrolyte solution or an increase in the amount of the electrolyte solution. The particle size of the primary particles is preferably 1.8 μm to 2.1 μm. 
     The positive electrode active material for lithium ion batteries of the present invention is such that the alkali amount at the particle surfaces measured by two-stage neutralization titration is 1.2% by mass or less. If the alkali amount at the particle surfaces in the positive electrode active material for lithium ion batteries is greater than 1.2% by mass, a lithium ion battery using the positive electrode active material reacts with the electrolyte solution when charge and discharge is repeated. Furthermore, if the alkali amount is large, gases are generated. Therefore, deterioration of the battery occurs, and battery characteristics, particularly cycle characteristics, of lithium ion batteries become defective. The alkali amount measured by two-stage neutralization titration is preferably 0.8% by mass or less, and more preferably 0.6% by mass or less. 
     The positive electrode active material for lithium ion batteries of the present invention is such that in the alkali amount at the particle surfaces, when the amount of lithium hydroxide is designated as A % by mass, and the amount of lithium carbonate is designated as B % by mass, the ratio A/B is 1 or less. The alkalis contained in the positive electrode active material for lithium ion batteries are lithium hydroxide and lithium carbonate. Between these, if the ratio A/B, which is the ratio of the amount of lithium hydroxide to the amount of lithium carbonate, is greater than 1, because the proportion of lithium hydroxide which is a strong alkali becomes larger than the proportion of lithium carbonate which is a weak alkali, the pH value increases. Thus, battery characteristics, particularly cycle characteristics, of a lithium ion battery using the positive electrode active material become defective. The ratio A/B is preferably 0.7 or less, and more preferably 0.4 or less. 
     For the two-stage neutralization titration of the positive electrode active material for lithium ion batteries, a conventional method can be used, and for example, the method is defined in JIS K1201-3-1 (neutralization titration). Specifically, the relevant titration method is based on the following reactions between alkalis and acids.
 
LiOH+HCl→LiCl+H 2 O  (1)
 
Li 2 CO 3 +HCl→LiCl+LiHCO 3   (2)
 
LiHCO 3 +HCl→LiCl+CO 2 +H 2 O  (3)
 
     In a conventional titration method of using an indicator, pH 7.8 is detected for the reactions of (1) and (2), and this point of measurement is designated as a first endpoint. Also, pH 3.9 is detected for the reaction of (3), and this point of measurement is designated as a second endpoint. Furthermore, in the titration method according to JIS K1201-3-2 (potential difference titration), inflection points are detected from two sites, and the points are designated as a first endpoint and a second endpoint, respectively. Then, the mass percentages of lithium hydroxide and lithium carbonate are calculated from the amounts of HCl used to the respective endpoints. 
     (Positive Electrode for Lithium Ion Batteries, and Configuration of Lithium Ion Battery Using the Positive Electrode) 
     The positive electrode for lithium ion batteries according to an embodiment of the present invention has a structure in which, for example, a positive electrode mixture prepared by mixing the positive electrode active material for lithium ion batteries having the constitution described above, a conductive aid, and a binder, is provided on one surface or on both surfaces of a collector formed from aluminum foil or the like. Furthermore, the lithium ion battery related to an embodiment of the present invention includes the positive electrode for lithium ion batteries having such a configuration. 
     (Method for Producing Positive Electrode Active Material for Lithium Ion Batteries) 
     Next, the method for producing a positive electrode active material for lithium ion batteries according to an embodiment of the present invention will be described in detail. 
     First, a metal salt solution is prepared. The relevant metals are Ni, and one or more selected from Sc, Ti, V, Cr, Mn, Fe, Co, Cu, Zn, Ga, Ge, Bi, Sn, Mg, Ca, B, and Zr. Furthermore, examples of metal salts include sulfates, chlorides, nitrates, and acetates, and particularly, nitrates are preferred. This is because, even if incorporated as impurities into a calcination raw material, since nitrates can be directly calcined, the number of washing processes can be reduced, and also, nitrates function as oxidizing agents and have a function of promoting oxidation of metals in the calcination raw material. The various metals contained in the metal salts are adjusted so as to be present at a desired molar ratio. Thereby, the molar ratio of the various metals in the positive electrode active material is determined. 
     Subsequently, lithium carbonate is suspended in pure water, and then the metal salt solution of the metals described above is introduced therein, to thereby prepare a metal carbonate solution slurry. At this time, lithium-containing carbonates in the form of fine grains are precipitated in the slurry. Note that, in the case of metal salts such as sulfates and chlorides whose lithium compounds do not react at the time of a heat treatment, the salts are washed with a saturated lithium carbonate solution and then separated by filtration. In the case of metal salts such as nitrates and acetates whose lithium compounds react as lithium raw materials during a heat treatment, the metal salts are not washed but are directly separated by filtration and dried, so that the metal salts can be used as calcination precursors. 
     Next, the lithium-containing carbonates that have been separated by filtration are dried, and thereby a powder of a composite of lithium salts (precursor for lithium ion battery positive electrode material) is obtained. 
     Next, a calcining container having a predetermined capacity is provided, and the powder of the precursor for lithium ion battery positive electrode material is filled in this calcining container. Subsequently, the calcining container filled with the powder of the precursor for lithium ion battery positive electrode material is transferred into a calcination furnace, and calcination is carried out. Calcination is carried out by heating and retaining the powder for a predetermined time in an oxygen atmosphere. Furthermore, it is preferable that calcination is carried out under pressure at 101 to 202 kPa because the amount of oxygen in the composition is further increased. 
     The heating and retention temperature in the calcination process affects the particle size of the primary particles of the lithium ion battery positive electrode material. In the present invention, since lithium carbonate is used in the raw material, reactivity is weak compared with the case of using lithium hydroxide as a raw material. Therefore, calcination for a long time at a high temperature is required, but due to this calcination for a long time at a high temperature, crystallinity of the particles is enhanced, and the particle size of the primary particles of the positive electrode material increases. In the present invention, the particle size of the primary particles is controlled to 1.6 to 2.3 μm by using lithium carbonate in the raw material, and performing calcination for 12 hours or longer at a temperature of 750° C. or higher. To the contrary, when lithium hydroxide is used as the raw material, since reactivity is usually high, the calcination temperature becomes lower, and the calcination time becomes shorter. Therefore, the particle size of the primary particles thus produced decreases to about 0.5 μm. 
     Thereafter, the powder is taken out from the calcining container, and the powder is subjected to cracking using a commercially available cracking apparatus or the like. Thereby, a powder of a positive electrode active material is obtained. Cracking at this time is carried out by appropriately adjusting the cracking strength and the cracking time so that the production of a fine powder is suppressed as much as possible. Specifically, through this cracking, the volume percentage of fine particles having a particle size of 6 μm or less after cracking is adjusted to be 4.0% to 7.0%, and preferably 4.3% to 6.9%. 
     As such, by controlling the production of a fine powder at the time of cracking, the surface area of the powder per unit volume decreases, and therefore, the amount of lithium hydroxide at the particle surfaces can be suppressed. 
     Furthermore, since lithium carbonate is converted to lithium hydroxide in a place where moisture is present, incorporation of moisture is controlled by performing the cracking in a dry air atmosphere. 
     EXAMPLES 
     Hereinafter, Examples will be described so as to help better understanding of the present invention and advantages thereof, but the present invention is not intended to be limited to these Examples. 
     Examples 1 to 15 
     First, lithium carbonate in the feed amount described in Table 1 was suspended in 3.2 liters of pure water, and then 4.8 liters of a metal salt solution was introduced therein. Here, in regard to the metal salt solution, hydrides of nitrates of various metals were adjusted such that the various metals would be contained at the composition ratio described in Table 1, and such that the total mole number of metals would be 14 moles. 
     A lithium-containing carbonate in the form of fine grains was precipitated in the solution through this treatment, but this precipitate was separated by filtration using a filter press. 
     Subsequently, the precipitate was dried, and thus a lithium-containing carbonate (precursor for lithium ion battery positive electrode material) was obtained. 
     Next, a calcining container was provided, and the lithium-containing carbonate was filled in this calcining container. Subsequently, the calcining container was placed in a furnace in an oxygen atmosphere at atmospheric pressure, heated and retained for 10 hours at the calcination temperature described in Table 1, and then cooled to obtain an oxide. 
     Subsequently, the oxide thus obtained was cracked using a small-sized pulverizer (ACM-2EC manufactured by Hosokawa Micron, Ltd.) such that fine particles having a predetermined particle size would occupy a predetermined distribution width in the particle size distribution, and thus a powder of a lithium ion secondary battery positive electrode material was obtained. 
     Example 16 
     In Example 16, the same treatment as in Examples 1 to 15 was carried out, except that the various metals of the raw material for Example 16 were used at the composition indicated in Table 1, the metal salts used were chlorides, and after the lithium-containing carbonate was precipitated out, the precipitate was washed with a saturated lithium carbonate solution and filtered. 
     Example 17 
     The same treatment as in Examples 1 to 15 was carried out, except that the various metals of the raw material for Example 17 were used at the composition indicated in Table 1, the metal salts used were sulfates, and after the lithium-containing carbonate was precipitated out, the precipitate was washed with a saturated lithium carbonate solution and filtered. 
     Example 18 
     The same treatment as in Examples 1 to 15 was carried out, except that the various metals of the raw material for Example 18 were used at the composition indicated in Table 1, and calcination was carried out under pressure at a pressure of 120 kPa instead of atmospheric pressure. 
     Example 19 
     The same treatment as in Examples 1 to 15 was carried out, except that the various metals of the raw material for Example 19 were used at the composition indicated in Table 1, the metal salts used were nitrates, and after the lithium-containing carbonate was precipitated out, the precipitate was washed with a saturated lithium carbonate solution and filtered. 
     Comparative Examples 1 to 3 
     The same treatment as in Examples 1 to 15 was carried out, except that the various metals of the raw materials for Comparative Examples 1 to 3 were used at the respective compositions indicated in Table 1, and for the cracking of the final oxide, the conditioning such as that carried out in Examples 1 to 15 was not carried out. 
     Comparative Examples 4 to 6 
     The same treatment as in Comparative Example 1 was carried out, except that the various metals of the raw materials for Comparative Examples 4 to 6 were used at the respective compositions indicated in Table 1, and the calcination process was carried out in an atmosphere of air instead of an oxygen atmosphere. 
     Evaluation 
     —Evaluation of Positive Electrode Material Composition— 
     The metal contents of each of the various positive electrode materials were measured using an inductively coupled plasma emission spectrometer (ICP-OES), and the composition ratio (molar ratio) of the various metals was calculated. Also, the oxygen content was measured by the LECO method, and the value of a was calculated. It was confirmed that these results were as described in Table 1. 
     —Evaluation of Particle Size of Primary Particles— 
     A powder of each of the positive electrode materials was collected, and the particle size of the primary particles was measured using a laser diffraction particle size distribution analyzer (MICROTRACK MT3300EX II). 
     —Evaluation of Alkali Amount— 
     The alkali amount in the positive electrode material was measured by a two-stage neutralization titration method. Specifically, 1 g of a powder of each of the various positive electrode materials was collected and added to 50 mL of pure water. The mixture was stirred for 10 minutes, and then was filtered. Subsequently, 10 mL of the filtrate and 15 mL of pure water were introduced into a 50-mL tall beaker using a micropipette. Subsequently, phenolphthalein was added to the beaker as an indicator, a stirring bar was placed in the beaker, and the beaker was mounted on a magnetic stirrer. Electrodes were set up in the beaker. Subsequently, while the solution in the beaker was stirred, 0.01 N HCl was added dropwise thereto. 
     Here, the two-stage neutralization titration method is based on the following reactions between alkalis and acids.
 
LiOH+HCl→LiCl+H 2 O  (1)
 
Li 2 CO 3 +HCl→LiCl+LiHCO 3   (2)
 
LiHCO 3 +HCl→LiCl+CO 2 +H 2 O  (3)
 
     pH 7.8 was detected for the reactions of (1) and (2), and this point of measurement was designated as a first endpoint. Also, pH 3.9 was detected for the reaction of (3), and this point of measurement was designated as a second endpoint. Then, while the amount of HCl used up to the first endpoint was designated as x (mL), and the amount of HCl used up to the second endpoint was designated as y (mL), the amount of Li 2 CO 3  was determined by the formula: (y−x)×0.369% by mass, and the amount of LiOH was determined by the formula: (2x−y)×0.12% by mass. 
     Furthermore, ratio of the amount of LiOH and the amount of Li 2 CO 3  (amount of LiOH/amount of Li 2 CO 3 ) was determined from those amounts thus calculated. 
     Note that, the calculation formula: (y−x)×0.369% by mass related to the amount of Li 2 CO 3 , and the calculation formula: (2x−y)×0.12% by mass related to the amount of LiOH were induced from the following formula.
         The mole number of HCl in the formula (3) is determined by the following formula.
 
( y−x )× 1/1000×0.01 mol/L=10 −5 ×( y−x ) mol
   The mole number of Li 2 CO 3  of the formula (2) is the same as the mole number of HCl, and since the molecular weight of Li 2 CO 3  is 73.89, 10 mL out of 50 mL is used for the titration, and the original feed amount of the positive electrode material is 1 g, the amount of Li 2 CO 3  is determined by the following formula:
 
73.89 g/mol×10 −5 ×( y−x ) mol×(50 mL/10 mL)÷1 g×100%=( y−x )×0.369% by mass
   The mole number of LiOH of the formula (1) is determined by the following formula:
 
 x×  1/1000×0.01 mol/L−10 −5 ×( y−x ) mol=10 −5 ×(2 x−y ) mol
   Since the molecular weight of LiOH is 23.95, 10 mL our of 50 mL is used for the titration, and the original feed amount of the positive electrode material is 1 g, the amount of LiOH is determined by the following formula:
 
23.95 g/mol×10 −5 ×(2 x−y ) mol×(50 mL/10 mL)÷1 g×100%=(2 x−y )×0.12% by mass
       

     —Evaluation of Battery Characteristics— 
     Each of the positive electrode materials, a conductive material, and a binder were weighed at a ratio of 85:8:7, and the positive electrode material and the conductive material were mixed with a solution prepared by dissolving the binder in an organic solvent (N-methylpyrrolidone) to obtain a slurry. The slurry was applied on an aluminum (Al) foil, dried and then pressed, and thus a positive electrode was produced. Subsequently, a 2032 type coin cell for evaluation was produced using Li for the opposite electrode, and the discharge capacity at a current density of 0.2 C was measured using a solution prepared by dissolving 1 M LiPF 6  in EC-DMC (1:1) as an electrolyte solution. Furthermore, the ratio of the discharge capacity at a current density of 2 C with respect to the battery capacity at a current density of 0.2 C was calculated to obtain the rate characteristics. Furthermore, the capacity retention ratio was measured by making a comparison between the initial discharge capacity and the discharge capacity after 100 cycles, which were obtained at a discharge current of 1 C at room temperature. 
     These results are presented in Tables 1 and 2. 
     
       
         
               
               
               
               
               
             
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
             
           
               
                   
                 TABLE 1 
               
             
             
               
                   
                   
               
               
                   
                 Amount of 
                   
                   
                 Fine particles having 
               
             
          
           
               
                   
                 suspension of 
                   
                 Retention 
                   
                 particle size of 6 μm or 
               
               
                   
                 lithium 
                 Composition ratio of various metals in all metals except for Li 
                 temperature 
                   
                 less after cracking 
               
             
          
           
               
                   
                 carbonate (g) 
                 Ni 
                 Co 
                 Mn 
                 Ti 
                 Cr 
                 Fe 
                 Cu 
                 Sn 
                 Mg 
                 (° C.) 
                 χ 
                 α 
                 (volume %) 
               
               
                   
                   
               
             
          
           
               
                 Example 1 
                 1393 
                 33.3 
                 33.3 
                 33.3 
                   
                   
                   
                   
                   
                   
                 1000 
                 0.00 
                 0.15 
                 6.2 
               
               
                 Example 2 
                 1393 
                 33.3 
                 33.3 
                 33.3 
                   
                   
                   
                   
                   
                   
                 1000 
                 0.00 
                 0.12 
                 5.2 
               
               
                 Example 3 
                 1393 
                 33.3 
                 33.3 
                 33.3 
                   
                   
                   
                   
                   
                   
                 1000 
                 0.00 
                 0.15 
                 4.9 
               
               
                 Example 4 
                 1393 
                 33.3 
                 33.3 
                 33.3 
                   
                   
                   
                   
                   
                   
                 1000 
                 0.00 
                 0.14 
                 4.3 
               
               
                 Example 5 
                 1442 
                 33.3 
                 33.3 
                 33.3 
                   
                   
                   
                   
                   
                   
                 970 
                 0.025 
                 0.17 
                 6.3 
               
               
                 Example 6 
                 1393 
                 33.3 
                 33.3 
                 33.3 
                   
                   
                   
                   
                   
                   
                 950 
                 0.050 
                 0.19 
                 5.3 
               
               
                 Example 7 
                 1393 
                 33 
                 33 
                 33 
                   
                   
                   
                   
                 1 
                   
                 1000 
                 0.00 
                 0.12 
                 4.9 
               
               
                 Example 8 
                 1393 
                 60 
                 15 
                 25 
                   
                   
                   
                   
                   
                   
                 920 
                 0.00 
                 0.17 
                 6.1 
               
               
                 Example 9 
                 1393 
                 60 
                 15 
                 25 
                   
                   
                   
                   
                   
                   
                 900 
                 0.00 
                 0.15 
                 6.8 
               
               
                 Example 10 
                 1393 
                 80 
                 10 
                 10 
                   
                   
                   
                   
                   
                   
                 800 
                 0.00 
                 0.11 
                 4.9 
               
               
                 Example 11 
                 1393 
                 80 
                 15 
                   
                 2.5 
                   
                   
                   
                   
                 2.5 
                 800 
                 0.00 
                 0.13 
                 6.7 
               
               
                 Example 12 
                 1393 
                 80 
                 15 
                   
                   
                 5 
                   
                   
                   
                   
                 800 
                 0.00 
                 0.11 
                 6.2 
               
               
                 Example 13 
                 1393 
                 80 
                 15 
                   
                   
                   
                 5 
                   
                   
                   
                 800 
                 0.00 
                 0.21 
                 6.6 
               
               
                 Example 14 
                 1393 
                 80 
                 15 
                   
                   
                   
                   
                 5 
                   
                   
                 800 
                 0.00 
                 0.11 
                 6.2 
               
               
                 Example 15 
                 1442 
                 80 
                 10 
                 10 
                   
                   
                   
                   
                   
                   
                 850 
                 0.06 
                 0.11 
                 6.1 
               
               
                 Example 16 
                 1393 
                 33.3 
                 33.3 
                 33.3 
                   
                   
                   
                   
                   
                   
                 1000 
                 0.00 
                 0.07 
                 6.8 
               
               
                 Example 17 
                 1393 
                 33.3 
                 33.3 
                 33.3 
                   
                   
                   
                   
                   
                   
                 1000 
                 0.00 
                 0.10 
                 6.9 
               
               
                 Example 18 
                 1393 
                 33.3 
                 33.3 
                 33.3 
                   
                   
                   
                   
                   
                   
                 950 
                 0.00 
                 0.23 
                 4.5 
               
               
                 Example 19 
                 1393 
                 80 
                 10 
                 10 
                   
                   
                   
                   
                   
                   
                 850 
                 0.09 
                 0.09 
                 5.2 
               
               
                 Comparative 
                 1393 
                 33.3 
                 33.3 
                 33.3 
                   
                   
                   
                   
                   
                   
                 1000 
                 0.00 
                 0.18 
                 8.1 
               
               
                 Example 1 
               
               
                 Comparati2ve 
                 1393 
                 60 
                 15 
                 25 
                   
                   
                   
                   
                   
                   
                 920 
                 0.00 
                 0.09 
                 8.3 
               
               
                 Example 2 
               
               
                 Comparati2ve 
                 1393 
                 80 
                 10 
                 10 
                   
                   
                   
                   
                   
                   
                 800 
                 0.00 
                 0.12 
                 9 
               
               
                 Example 3 
               
               
                 Comparati4ve 
                 1393 
                 80 
                 10 
                 10 
                   
                   
                   
                   
                   
                   
                 800 
                 0.00 
                 −0.01 
                 8 
               
               
                 Example 4 
               
               
                 Comparative 
                 1442 
                 80 
                 10 
                 10 
                   
                   
                   
                   
                   
                   
                 850 
                 0.11 
                 0.08 
                 7.9 
               
               
                 Example 5 
               
               
                 Comparative 
                 1393 
                 80 
                 15 
                   
                 2.5 
                   
                   
                   
                   
                 2.5 
                 800 
                 0.10 
                 0.00 
                 7.8 
               
               
                 Example 6 
               
               
                   
               
             
          
         
       
     
     
       
         
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
             
           
               
                   
                 TABLE 2 
               
               
                   
                   
               
               
                   
                   
                   
                 Amount of 
                 Amount of 
                   
                   
                   
                   
               
               
                   
                 Particle size 
                 Alkali 
                 lithium 
                 lithium 
                   
                 Discharge 
                 Rate 
                 Capacity 
               
               
                   
                 of primary 
                 amount 
                 hydroxide A 
                 carbonate B 
                   
                 capacity 
                 characteristics 
                 retention 
               
               
                   
                 particles (μm) 
                 (mass %) 
                 (mass %) 
                 (mass %) 
                 A/B 
                 (mAh/g) 
                 (%) 
                 ratio (%) 
               
               
                   
                   
               
             
             
               
                   
               
             
          
           
               
                 Example 1 
                 2.3 
                 0.134 
                 0.024 
                 0.110 
                 0.218 
                 153 
                 92 
                 92 
               
               
                 Example 2 
                 2.1 
                 0.134 
                 0.024 
                 0.110 
                 0.218 
                 154 
                 92 
                 91 
               
               
                 Example 3 
                 2 
                 0.158 
                 0.019 
                 0.139 
                 0.137 
                 157 
                 95 
                 92 
               
               
                 Example 4 
                 2 
                 0.121 
                 0.048 
                 0.073 
                 0.658 
                 155 
                 95 
                 93 
               
               
                 Example 5 
                 1.9 
                 0.135 
                 0.015 
                 0.120 
                 0.125 
                 155 
                 93 
                 92 
               
               
                 Example 6 
                 1.9 
                 0.102 
                 0.016 
                 0.086 
                 0.186 
                 160 
                 92 
                 89 
               
               
                 Example 7 
                 1.7 
                 0.123 
                 0.012 
                 0.111 
                 0.108 
                 158 
                 92 
                 88 
               
               
                 Example 8 
                 1.8 
                 0.248 
                 0.02 
                 0.268 
                 0.075 
                 175 
                 88 
                 87 
               
               
                 Example 9 
                 1.8 
                 0.637 
                 0.211 
                 0.426 
                 0.495 
                 172 
                 89 
                 88 
               
               
                 Example 10 
                 1.8 
                 0.544 
                 0.172 
                 0.372 
                 0.461 
                 195 
                 87 
                 85 
               
               
                 Example 11 
                 1.8 
                 0.537 
                 0.159 
                 0.378 
                 0.419 
                 185 
                 87 
                 85 
               
               
                 Example 12 
                 1.8 
                 0.840 
                 0.208 
                 0.639 
                 0.326 
                 186 
                 88 
                 84 
               
               
                 Example 13 
                 1.6 
                 0.900 
                 0.209 
                 0.691 
                 0.303 
                 187 
                 85 
                 82 
               
               
                 Example 14 
                 1.6 
                 0.581 
                 0.249 
                 0.332 
                 0.750 
                 180 
                 88 
                 83 
               
               
                 Example 15 
                 1.7 
                 1.200 
                 0.450 
                 0.750 
                 0.600 
                 185 
                 87 
                 85 
               
               
                 Example 16 
                 1.8 
                 0.123 
                 0.012 
                 0.111 
                 0.108 
                 153 
                 90 
                 87 
               
               
                 Example 17 
                 2 
                 0.132 
                 0.012 
                 0.12 
                 0.100 
                 151 
                 90 
                 86 
               
               
                 Example 18 
                 1.9 
                 0.135 
                 0.000 
                 0.135 
                 0.000 
                 156 
                 95 
                 93 
               
               
                 Example 19 
                 1.6 
                 0.620 
                 0.309 
                 0.311 
                 0.994 
                 185 
                 87 
                 87 
               
               
                 Comparative 
                 1.5 
                 0.178 
                 0.075 
                 0.103 
                 0.728 
                 153 
                 91 
                 85 
               
               
                 Example 1 
               
               
                 Comparative 
                 1.5 
                 0.151 
                 0.078 
                 0.073 
                 1.068 
                 165 
                 83 
                 78 
               
               
                 Example 2 
               
               
                 Comparative 
                 1.4 
                 0.248 
                 0.12 
                 0.168 
                 0.714 
                 180 
                 83 
                 82 
               
               
                 Example 3 
               
               
                 Comparative 
                 1.5 
                 0.800 
                 0.319 
                 0.481 
                 0.663 
                 170 
                 80 
                 78 
               
               
                 Example 4 
               
               
                 Comparative 
                 1.4 
                 1.210 
                 0.62 
                 0.59 
                 1.051 
                 178 
                 82 
                 80 
               
               
                 Example 5 
               
               
                 Comparative 
                 1.5 
                 0.600 
                 0.249 
                 0.351 
                 0.709 
                 171 
                 79 
                 74 
               
               
                 Example 6 
               
               
                   
               
             
          
         
       
     
     Evaluation 
     Examples 1 to 19 all exhibited satisfactory battery characteristics. Furthermore, Examples 1 to 15 and 18, which used nitrates as the metal salts for the raw material, exhibited particularly satisfactory battery characteristics. Moreover, Example 18 in which calcination was carried out under pressure instead of atmospheric pressure exhibited the most satisfactory battery characteristics. 
     In Comparative Examples 1 to 3, the compositions of metals used as the raw material contained oxygen in excess, similarly to the present invention. However, due to the cracking conditions, the battery characteristics were poor. In Comparative Examples 4 to 6, the compositions of metals used as the raw material were not included in the scope of the present invention, and also, due to the cracking conditions, the battery characteristics were poor.