Abstract:
In a secondary battery including a non-aqueous electrolyte and a positive electrode, the improvement disclosed is a positive electrode composed of a material that a positive electrode active material and is composed of LiX, where X represents a halogen atom; and Fe 2 O 3 . A method of manufacturing the positive electrode active material includes mixing first particles and second particles to provide a mixture, wherein the first particles comprise LiX, where X represents a halogen atom, and the second particles comprise Fe 2 O 3 . A positive electrode including the positive electrode active material is disclosed, as well as a battery including the positive electrode, a battery pack including the battery, and a vehicle including the battery.

Description:
CROSS-REFERENCE TO RELATED APPLICATION 
       [0001]    This non-provisional application for a U.S. patent claims priority from Japanese Application JP2016-105493 filed May 26, 2016, the entire contents of which are incorporated herein by reference. 
       BACKGROUND OF THE INVENTION 
     1. Field of the Invention 
       [0002]    The present invention relates to a positive electrode active material for a non-aqueous electrolyte secondary battery and a manufacturing method thereof, a positive electrode, a battery, a battery pack, and a vehicle. 
       2. Description of the Related Art 
       [0003]    Secondary batteries, such as lithium ion secondary batteries, are widely used in small mobile device applications (see, for example, Japanese Patent Application Laid-open No. 2006-134758). In recent years, there has been a demand for development of a low-cost secondary battery excellent in charge-discharge efficiency. 
       SUMMARY OF THE INVENTION 
       [0004]    The inventors of the present invention have found a novel low-cost positive electrode active material for a non-aqueous electrolyte secondary battery excellent in charge-discharge efficiency and a manufacturing method thereof. 
         [0005]    The present invention provides a positive electrode active material for a non-aqueous electrolyte secondary battery capable of being used in the manufacture of a low-cost battery excellent in charge-discharge efficiency and a manufacturing method thereof, a positive electrode containing the positive electrode active material for a non-aqueous electrolyte secondary battery, a battery including the positive electrode, and a battery pack and a vehicle each including the battery. 
         [0006]    1. A material that is a positive electrode active material for a non-aqueous electrolyte secondary battery according to one embodiment of the present invention includes LiX, where X represents a halogen atom; and Fe 2 O 3 . 
         [0007]    2. The positive electrode active material for a non-aqueous electrolyte secondary battery according to the above-mentioned item 1 may have a molar ratio of LiX to Fe 2 O 3  of 0.1 or more and 100 or less, i.e., a molar ratio ranging from about 0.1 up to about 100. 
         [0008]    3. The positive electrode active material for a non-aqueous electrolyte secondary battery according to the above-mentioned item 1 or 2 may have an average particle diameter ranging from greater than zero up to about 100 μm. 
         [0009]    4. In the positive electrode active material for a non-aqueous electrolyte secondary battery according to any one of the above-mentioned items 1 to 3, the positive electrode active material contains metal oxides having a ratio of Fe 2 O 3  that ranges from about 1 mol % to about 100 mol % based on a total Amount of metal oxides. 
         [0010]    5. A method of manufacturing a material that is a positive electrode active material for a non-aqueous electrolyte secondary battery according to one embodiment of the present invention includes mixing first particles and second particles to provide a mixture, wherein the first particles comprise LiX, where X represents a halogen atom; and the second particles comprise Fe 2 O 3 . 
         [0011]    6. In the method of manufacturing a positive electrode active material for a non-aqueous electrolyte secondary battery according to the above-mentioned item 5, the mixing may be performed at a number of rotations of about 100 rpm or more. 
         [0012]    7. In the method of manufacturing a positive electrode active material for a non-aqueous electrolyte secondary battery according to the above-mentioned item 5 or 6, the mixture of first particles and second particles has an average particle diameter ranging from greater than zero up to about 100 μm. 
         [0013]    8. In the method of manufacturing a positive electrode active material for a non-aqueous electrolyte secondary battery according to any one of the above-mentioned items 5 to 7, wherein the mixture of first particles and second particles has a molar ratio of the first particles to the second particles of about 0.1 up to about 100. 
         [0014]    9. A positive electrode according to one embodiment of the present invention includes the positive electrode active material for a non-aqueous electrolyte secondary battery of any one of the above-mentioned items 1 to 4. 
         [0015]    10. A battery according to one embodiment of the present invention includes the positive electrode of the above-mentioned item 9. 
         [0016]    11. A battery pack according to one embodiment of the present invention includes the battery of the above-mentioned item 10. 
         [0017]    12. A vehicle according to one embodiment of the present invention includes the battery of the above-mentioned item 10. 
         [0018]    Through the use of the positive electrode active material for a non-aqueous electrolyte secondary battery according to any one of the above-mentioned items 1 to 4, a low-cost battery having excellent charge-discharge efficiency can be obtained. 
         [0019]    According to the method of manufacturing a positive electrode active material for a non-aqueous electrolyte secondary battery according to any one of the above-mentioned items 5 to 8, the low-cost positive electrode active material can be obtained by a simple method. 
     
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         [0020]      FIG. 1  is a cross-sectional view for schematically illustrating a secondary battery according to one embodiment of the present invention; 
           [0021]      FIG. 2  is a graph for showing charge-discharge curves of a positive electrode active material according to Test No. 1 of Example 1 of the present invention; 
           [0022]      FIG. 3  is a graph for showing charge-discharge curves of a positive electrode active material according to Test No. 3 of Example 1 of the present invention; 
           [0023]      FIG. 4  is a graph for showing charge-discharge curves of a positive electrode active material according to Test No. 5 of Example 1 of the present invention (in the case where the upper limit voltage is 4.4 V); 
           [0024]      FIG. 5  is a graph for showing charge-discharge curves of the positive electrode active material according to Test No. 5 of Example 1 of the present invention (in the case where the upper limit voltage is 5 V; and 
           [0025]      FIG. 6  is a graph for showing charge-discharge curves of a positive electrode active material according to Test No. 6 of Example 1 of the present invention. 
       
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
       [0026]    The present invention is hereinafter described in detail with reference to the drawings. In the present invention, “part(s)” means “part(s) by mass” and “%” means “mass %” unless otherwise specified. 
       1. POSITIVE ELECTRODE ACTIVE MATERIAL 
       [0027]    A positive electrode active material according to one embodiment of the present invention is a positive electrode active material for a non-aqueous electrolyte secondary battery (hereinafter sometimes referred to simply as “positive electrode active material”), containing LiX, where X represents a halogen atom, and Fe 2 O 3 . 
         [0028]    It is presumed that the positive electrode active material according to this embodiment contains LiX, and hence, in a battery using the positive electrode active material for its positive electrode, a lithium ion (Li + ) and Fe 2 O 3  . . . X −  are generated during discharge and the lithium ion (Li + ) can bind to Fe 2 O 3  . . . X −  to generate Li +  . . . Fe 2 O 3  . . . X −  during charge, as shown in the reaction formula (2) to be described later. 
         [0029]    The positive electrode active material according to this embodiment contains LiX, which generates an anion of a halogen atom (X − ) having high electronegativity through ionization, and hence through the use of the positive electrode active material according to this embodiment, which contains inexpensive Fe 2 O 3  as its host material, as a positive electrode active material, a low-cost battery excellent in charge-discharge efficiency can be manufactured. 
         [0030]    More specifically, the positive electrode active material according to this embodiment contains LiX, where X represents a halogen atom, and Fe 2 O 3 . 
         [0031]    The positive electrode active material according to this embodiment contains a mixture obtained by the mixing of first particles each formed of LiX, where X represents a halogen atom, and second particles each containing Fe 2 O 3 . A method of mixing the first particles and the second particles is described later. 
         [0032]    The positive electrode active material according to this embodiment can be suitably used as a positive electrode active material for a secondary battery, and can be particularly suitably used as a positive electrode active material for a non-aqueous electrolyte secondary battery. 
         [0033]    1.1. Charge-Discharge Mechanism of Battery 
         [0034]    The inventors of the present invention have presumed that a battery (secondary battery, for example, non-aqueous electrolyte secondary battery) using the positive electrode active material according to this embodiment in its positive electrode may be charged and discharged by the following reaction mechanism. 
         [0035]    LiX and Fe 2 O 3  bind to each other to form Li +  . . . Fe 2 O 3  . . . X − . In this case, it is presumed that the presence of LiX allows charge migration in Fe 2 O 3  containing Fe 3+  (that is, a trivalent iron ion), to thereby allow an electrode reaction to occur. 
         [0036]    More specifically, as shown in the following reaction formulae (1) and (2), it is presumed that part of LiX dissociates into Li +  and X − , whereby a dissociated lithium ion (Li + ) locally binds to oxygen (and/or iron) of one molecule of Fe 2 O 3 , and one dissociated anion (X − ) binds to oxygen (and/or iron) of Fe 2 O 3 , with the result that Li +  . . . Fe 2 O 3  . . . X −  is stably present. A charge-discharge reaction represented by the reaction formula (2) is repeated. 
         [0000]      (Reaction formulae)LiX→Li + +X −  . . .  (1), and
 
         [0000]      Li +  . . . Fe 2 O 3  . . . X −           Li + +Fe 2 O 3  . . . X+ e   −  . . .  (2).
 
         [0037]    In this case, LiX is preferably LiF (that is, the anion is preferably a fluorine ion (F − )) from the viewpoint of having high electronegativity and stably binding to oxygen (and/or iron) with ease. 
         [0038]    In the positive electrode active material according to this embodiment, from the view point of enabling the manufacture of a battery having higher charge-discharge efficiency, the molar ratio of LiX to Fe 2 O 3  in the mixture may be 0.1 or more and 100 or less, is preferably 10 or less, and is generally 0.5 or more and 10 or less. 
         [0039]    In addition, from the view point of enabling the conversion from LiX to Li +  and X −  to proceed uniformly and smoothly in a battery manufactured using the positive electrode active material according to this embodiment, the average particle diameter (primary particle diameter) of the positive electrode active material according to this embodiment (the mixture) is preferably 100 μm or less, and for example, may be 100 nm or more and 100 μm or less, or may be less than 500 nm. In addition, from the viewpoint of shortening the distance between LiX and Fe 2 O 3  to enable X −  to bind to Fe 2 O 3  more stably, the average particle diameter (primary particle diameter) of the mixture is preferably less than 10 μm, more preferably less than 1 μm, still more preferably less than 500 nm. For example, through the adjustment of the diameters of balls to be used for a ball mill, the mixture having an average particle diameter of less than 1 μm may be obtained. 
         [0040]    1.2. LiX Examples of the halogen atom contained in LiX include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The anion of the halogen atom has high electronegativity, and hence can stably bind to oxygen (and/or iron) contained in Fe 2 O 3 . Accordingly, at the time of the operation of a battery using the positive electrode active material according to this embodiment for its electrode (positive electrode), when the anion of the halogen atom binds to Fe 2 O 3  in the positive electrode, the anion of the halogen atom can be stably retained in the positive electrode. In particular, X preferably represents a fluorine atom from the viewpoint of having higher electronegativity, and hence being able to form more stable binding to oxygen (and/or iron). 
         [0041]    1.3. Fe 2 O 3    
         [0042]    Fe 2 O 3  (iron(III) oxide, ferric oxide) is so-called red rust, and is a reddish brown solid. The inventors of the present invention have found that when Fe 2 O 3 , which contains a trivalent iron ion, is used in combination with LiX, Fe 2 O 3  can be used as a positive electrode active material capable of releasing an electron. 
         [0043]    There is known a battery using, as a positive electrode active material, FeO or Fe 3 O 4 , which is an iron oxide containing a divalent iron ion (see Japanese Patent Application Laid-open No. 2015-128023). In this battery, through the use of FeO or Fe 3 O 4  as the positive electrode active material, an electron is released upon conversion of the divalent iron ion to a trivalent iron ion. As apparent from the foregoing, the trivalent iron ion has generally been considered not to cause charge-discharge. 
         [0044]    Under such circumstances, the inventors of the present invention have found for the first time that Fe 2 O 3  and LiX function as a positive electrode active material through the utilization of Fe 2 O 3 , which is an iron oxide containing only trivalent iron ions, and have created a battery utilizing LiX and Fe 2 O 3  as a positive electrode active material. 
         [0045]    In the positive electrode active material according to this embodiment, for example, the ratio of Fe 2 O 3  in metal oxides contained in the positive electrode active material is preferably 1 mol % or more and 100 mol % or less, for example, 50 mol % or more and 100 mol % or less. 
         [0046]    For example, red rust may be used as Fe 2 O 3 . Red rust is widely present in nature, and is inexpensive. When red rust is used as Fe 2 O 3 , even lower cost can be achieved. 
         [0047]    1.4. Action and Effect 
         [0048]    The positive electrode active material according to this embodiment contains the mixture of LiX and Fe 2 O 3 , and hence when the positive electrode active material is used for, for example, a positive electrode, LiX and Fe 2 O 3  each function as a positive electrode active material. X −  (anion of a halogen atom) has high electronegativity. Accordingly, through the use of LiX in the positive electrode active material, X −  and Fe 2 O 3  can more stably bind to each other, and hence lower cost is achieved and an electrode excellent in charge-discharge efficiency can be formed. 
       2. METHOD OF MANUFACTURING POSITIVE ELECTRODE ACTIVE MATERIAL 
       [0049]    The positive electrode active material according to the above-mentioned embodiment may be obtained by the following manufacturing method. That is, a method of manufacturing a positive electrode active material according to one embodiment of the present invention (hereinafter sometimes referred to simply as “manufacturing method”) includes a step of mixing of first particles each formed of LiX, where X represents a halogen atom; and second particles each containing Fe 2 O 3 . 
         [0050]    More specifically, through the mixing step, a mixture (having an average particle diameter of 100 μm or less, preferably 100 nm or more and 100 μm or less) of the first particles and the second particles can be obtained. 
         [0051]    In the manufacturing method according to this embodiment, from the view point of enabling uniform dispersion of the first particles and the second particles, the mixing step is preferably performed at a number of rotations of 100 rpm or more, preferably 100 rpm or more and 1,500 rpm or less (more preferably 1,000 rpm or less). Through the mixing of the first particles and the second particles at the above-mentioned number of rotations, the first particles and the second particles can be pulverized. 
         [0052]    In the manufacturing method according to this embodiment, from the view point of enabling uniform dispersion of the first particles and the second particles, the molar ratio of the first particles to the second particles is preferably 0.1 or more and 100 or less, more preferably 0.1 or more and 10 or less, and is generally 0.1 or more and 10 or less. 
         [0053]    In the manufacturing method according to this embodiment, from the view point of enabling uniform dispersion the first particles in the mixture, the average particle diameter of the first particles is preferably 100 nm or more and 100 μm or less. 
         [0054]    In the manufacturing method according to this embodiment, from the view point of enabling uniform dispersion the second particles in the mixture, the average particle diameter of the second particles is preferably 100 nm or more and 100 μm or less. 
         [0055]    In addition, in the manufacturing method according to this embodiment, a mixing time in the mixing step is generally 1 hour or more and 500 hours or less, and a mixing temperature in the mixing step is generally 10° C. or more and 60° C. or less (in terms of ambient temperature) and is preferably 10° C. or more and 40° C. or less. 
         [0056]    The method of manufacturing a positive electrode active material according to this embodiment includes the mixing step, and hence lower cost is achieved and a positive electrode active material for forming an electrode excellent in charge-discharge efficiency can be obtained by a simple method. 
       3. BATTERY 
       [0057]      FIG. 1  is a view for schematically illustrating an example of a battery according to one embodiment of the present invention using the positive electrode active material according to the above-mentioned embodiment. As illustrated in  FIG. 1 , the battery according to this embodiment includes a positive electrode  2  and a negative electrode  3 , and the positive electrode  2  contains the positive electrode active material according to the above-mentioned embodiment. 
         [0058]    The battery according to this embodiment is preferably a secondary battery from the view point of being capable of being charged and discharged, and is more preferably a non-aqueous electrolyte secondary battery from the viewpoint of the positive electrode active material containing LiX. The battery according to this embodiment may contain the positive electrode active material according to the above-mentioned embodiment as a positive electrode active material in its positive electrode. 
         [0059]    As an example of the battery according to this embodiment, a lithium ion secondary battery is schematically illustrated in  FIG. 1 . As illustrated in  FIG. 1 , a lithium ion secondary battery (hereinafter referred to simply as “battery”)  1  includes a positive electrode layer (positive electrode)  2 , a negative electrode layer (negative electrode)  3 , a separator  4 , a positive electrode-side collector  5 , and a negative electrode-side collector  6 . 
         [0060]    3.1. Positive Electrode 
         [0061]    The positive electrode layer  2  includes an electrode material (positive electrode material)  21  containing the positive electrode active material according to the above-mentioned embodiment, and an electrolyte solution  7  filling gaps between particles of the positive electrode material  21 . 
         [0062]    The positive electrode layer  2  may contain a conductive material in addition to the positive electrode material  21 . A known substance is used as the conductive material. For example, as a carbon-based conductive material, carbon black (KB), acetylene black (AB), SP-270, UP-5-a, or vapor grown carbon fiber (VGCF) may be used. The positive electrode layer  2  may contain one kind or a plurality of kinds of conductive materials. 
         [0063]    The positive electrode layer  2  may further contain a binder. As the binder, various polymers that have heretofore been used as binders may be adopted. Specific examples of the polymer include polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, polyethylene terephthalate, polyacrylonitrile, and a styrene-butadiene rubber. The positive electrode layer  2  may contain one kind or a plurality of kinds of binders. 
         [0064]    3.2. Negative Electrode 
         [0065]    The negative electrode layer  3  includes an electrode material (negative electrode material)  31  containing the negative electrode active material, and the electrolyte solution  7  filling gaps between particles of the negative electrode material  31 . 
         [0066]    As the negative electrode active material, a substance that is known as a substance used for a lithium ion secondary battery may be adopted. Specific examples thereof include carbon (e.g., graphite), metal lithium, Sn, and SiO. 
         [0067]    The negative electrode layer  3  may further contain the binder described above as a material that may be used for the positive electrode layer  2 . 
         [0068]    The electrolyte solution  7  contains a solvent and an electrolyte dissolved in the solvent. 
         [0069]    As the solvent, a known solvent that is used for a lithium ion secondary battery may be adopted. A non-aqueous solvent, that is, an organic solvent, is used as the solvent. Examples of the non-aqueous solvent include carbonates, such as ethylene carbonate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, and propylene carbonate; acetonitrile, acetonitrile derivatives; ethers, such as ether, dimethoxyethane, and trimethoxyethane; fluorinated or chlorinated products thereof; and sulfones. Those solvents may be used alone or as a mixture thereof. 
         [0070]    For the electrolyte, a substance that has heretofore been used as an electrolyte of a lithium ion secondary battery may be adopted. More specific examples of the electrolyte include LiPF 6 , LiClO 4 , and LiBF 4 . The electrolyte solution  7  may contain one kind or a plurality of kinds of electrolytes. 
         [0071]    In order to improve the stability of the performance of the battery and its electrical characteristics, any of various additives, such as overcharge inhibitors, may be added to the electrolyte solution  7 . 
         [0072]    3.3. Separator 
         [0073]    The separator  4  is arranged between the positive electrode layer  2  and the negative electrode layer  3 . The arrangement of the separator  4  between the positive electrode layer  2  and the negative electrode layer  3  can prevent a short circuit between the positive electrode and the negative electrode. In addition, when the separator  4  is porous, the electrolyte solution  7  and lithium ions can be allowed to permeate therethrough. As a material for the separator  4 , for example, there are given resins (specifically, polyolefin-based polymers, such as polyethylene, polypropylene, and polystyrene). 
         [0074]    For the positive electrode-side collector  5 , for example, a metal foil of aluminum, an aluminum alloy, or the like may be used. In addition, as the negative electrode-side collector  6 , for example, a metal foil of copper, a copper alloy, or the like may be used. 
         [0075]    The battery  1  may include, in addition to the above-mentioned components, components such as a battery case, a positive electrode-side terminal, and a negative electrode-side terminal (none of which is shown). For example, a roll body formed by rolling the stack structure illustrated in  FIG. 1  in many layers may be housed in a battery case. In addition, the positive electrode-side terminal is connected to the positive electrode-side collector  5 , and the negative electrode-side terminal is connected to the negative electrode-side collector  6 . 
         [0076]    3.4. Applications 
         [0077]    The battery according to this embodiment is low cost and excellent in charge-discharge efficiency, and hence can be suitably used as, for example, not only a battery for a battery pack or a small mobile device, but also a battery for a large machine, for example, a vehicle, such as an electric bicycle, a two-wheeler, a three-wheeler, or a four-wheeler, or a ship. 
       4. EXAMPLES 
       [0078]    The present invention is hereinafter described in more detail by way of Examples with reference to the drawings. However, the present invention is by no means limited to the Examples. 
       4.1. Example 1 
       [0079]    Preparation of Positive Electrode Active Material 
         [0080]    LiF and Fe 2 O 3  were used as raw materials. While the molar ratio of LiF and Fe 2 O 3  (LiF:Fe 2 O 3 ) was adjusted to 2:1, LiF and Fe 2 O 3  were mixed with a planetary ball mill for 24 hours to prepare a mixture of Test No. 1. In this case, the mixing was performed under the condition of 600 rpm at an external environmental temperature of 25° C. 
         [0081]    The resultant mixture was evaluated by charge-discharge measurement. In the charge-discharge measurement, the resultant mixture (90 g) was composited with acetylene black (AB) (5 g) at 600 rpm, and then the resultant was mixed with polyvinylidene difluoride (PVDF) to prepare a positive electrode active material (mixture:AB:PVDF=70:25:5 (mass ratio)). The positive electrode active material was applied onto an aluminum foil to prepare a working electrode (positive electrode). 
         [0082]    The Fe 2 O 3  used in Test No. 1 had been pulverized at 650 rpm for 24 hours before being mixed with LiF, whereas the Fe 2 O 3  used in each of Test Nos. 2 to 6 was used without being pulverized. In addition, in Test Nos. 3 and 4, positive electrode active materials of Test Nos. 3 and 4 were each prepared by the same treatment as that of Test No. 1 except that LiF and Fe 2 O 3  were used with their molar ratio adjusted to a value shown in Table 1. 
         [0083]    Production of a Battery 
         [0084]    The positive electrode active material of each of Test Nos. 1 to 6 of Example 1 was applied onto an aluminum foil to prepare a working electrode (positive electrode). In addition, metal lithium was used for a counter electrode (negative electrode), 1 M LiPF 6 EC:DEC (1:1) was used for an electrolyte solution, and a cell was produced using a bipolar cell made of stainless steel. 
         [0085]    Charge-Discharge Test 
         [0086]    In this Example, a charge-discharge test was performed at a current density of 1 mA/cm 2 , in the voltage range of from 4.4 V to 1.9 V (in  FIG. 5 , measurement was performed also in the voltage range of from 5 V to 1.9 V), and at a measurement temperature of 25° C. In each of  FIG. 2  to  FIG. 6 , the charge-discharge test results (charge-discharge curves) of a battery using the positive electrode active material of Test No. 1, 3, 5, or 6 of Example 1 are shown (axis of abscissa: capacity, axis of ordinate: voltage, dashed line: first cycle, solid lines: second to tenth cycles (in  FIG. 6 , second and third cycles)). 
         [0087]    It can be understood from the results shown in Table 1 that the positive electrode active material of each of Test Nos. 1 to 6 enables the manufacture of a low-cost battery excellent in charge-discharge efficiency by virtue of containing LiX and Fe 2 O 3 . 
         [0000]    
       
         
               
               
               
               
               
             
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 1 
               
             
             
               
                   
               
               
                   
                 Raw  
                 Raw  
                   
                   
               
               
                   
                 material LiF 
                 material Fe 2 O 3   
                   
                 Mixture 
               
             
          
           
               
                   
                 Average 
                   
                 Average 
                   
                 LiF/ 
                 Average 
                 Current 
               
               
                   
                 particle 
                   
                 particle 
                   
                 Fe 2 O 3   
                 particle 
                 density 
               
               
                 Test  
                 diameter 
                 Purity  
                 diameter 
                 Purity  
                 (Molar 
                 diameter 
                 (mAh/ 
               
               
                 No. 
                 (μm) 
                 (%) 
                 (μm) 
                 (%) 
                 ratio) 
                 (nm) 
                 g) 
               
               
                   
               
               
                 1 
                 0.1 
                 99 
                 1   
                 95   
                 2/1 
                 250 
                 39 
               
               
                 2 
                 0.1 
                 99 
                 1   
                 95   
                 2/1 
                 250 
                 65 
               
               
                 3 
                 0.1 
                 99 
                 1   
                 95   
                 1/1 
                 250 
                 53 
               
               
                 4 
                 0.1 
                 99 
                 0.3 
                 99.9 
                 2/1 
                 250 
                 54 
               
               
                 5 
                 0.1 
                 99 
                 0.3 
                 99.9 
                 1/1 
                 250 
                 56 
               
               
                 6 
                 0.1 
                 99 
                 1   
                 99.9 
                 2/1 
                 250 
                 57 
               
               
                   
               
             
          
         
       
     
       4.2. Example 2 
       [0088]    A positive electrode active material was prepared in the same manner as in Test No. 1 of Example 1 except that red rust was used as Fe 2 O 3 , and a battery was manufactured using the positive electrode active material. 
         [0089]    The positive electrode active material for a non-aqueous electrolyte secondary battery of the present invention can be used in the manufacture of a low-cost battery excellent in charge-discharge efficiency. The battery can be suitably used, for example, as a battery for not only a small mobile device, but also a large machine, for example, a vehicle, such as an electric bicycle, a two-wheeler, a three-wheeler, or a four-wheeler, or a ship, and as a battery in a battery pack. 
         [0090]    Many other modifications will be apparent to and be readily practiced by those skilled in the art without departing from the scope and spirit of the invention. It should therefore be understood that the scope of the appended claims is not intended to be limited by the details of the description but should rather be broadly construed.