JPWO2017119411A1 - Lithium iron manganese complex oxide - Google Patents

Abstract

A novel compound useful as a positive electrode active material for a lithium ion secondary battery is provided.
Composition formula:
Li _{1 + m} Fe _x Mn _2-x O ₄
[Wherein m represents 0 <m ≦ 2. x represents 0 <x ≦ 1. ]
Lithium iron manganese complex oxide represented by

Description

  The present invention relates to a lithium iron manganese composite oxide.

  Lithium ion secondary batteries occupy the most important position among energy storage devices, and in recent years, their uses such as automobile batteries for plug-in hybrids are expanding.

Currently, positive electrode active materials such as LiCoO ₂ and LiNi _1/3 Co _1/3 Mn _1/3 O ₂ are mainly used for positive electrodes of lithium ion secondary batteries (Non-patent Documents 1 and 2). However, the positive electrode material containing these positive electrode active materials is expensive because it contains a large amount of rare metals such as cobalt and nickel, and is also a factor causing a heat generation accident and the like because of its strong combustion resistance. .

Therefore, as a positive electrode active material that can solve these problems, iron-based poly (oxo) that uses iron, which is an element abundant in nature, and has a strong polyanionic acid skeleton to significantly reduce the combustion resistance. ) Anionic materials, especially LiFePO _4, are attracting attention (Non-patent Document 3).

Solid State Ionics, 3-4, 171-174, 1981 J. et al. Electrochem. Soc. , 151 (6), A914-A921,2004 J. et al. Electrochem. Soc. 144 (4), 1188-1194, 1997

However, since LiFePO ₄ can reversibly insert and desorb only 1 Li ⁺ per molecule, its charge / discharge capacity is low, and in order to achieve a high charge / discharge capacity, desorption and insertion of 1 Li ⁺ or more are necessary. There is a need for possible positive electrode active materials.

  This invention is made | formed in view of such the present condition, and it aims at providing a novel compound useful as a positive electrode active material for lithium ion secondary batteries.

  The present inventors have intensively studied to solve the above-described problems of the present invention. As a result, we succeeded in synthesizing lithium iron manganese composite oxides with specific composition. Further, it has been found that the lithium iron manganese based composite oxide can insert and desorb lithium ions, and exhibits a theoretical charge / discharge capacity that is high enough to be used as a positive electrode active material for a lithium ion secondary battery. The present inventors have completed the present invention by conducting further research based on these findings.

That is, the present invention typically includes the subject matters described in the following sections.
Item 1.
Composition formula:
Li _{1 + m} Fe _x Mn _2-x O ₄
[Wherein m represents 0 <m ≦ 2. x represents 0 <x ≦ 1. ]
Lithium iron manganese complex oxide represented by
Item 2.
Item 2. The lithium iron manganese composite oxide according to Item 1, which has a tetragonal structure or a cubic structure.
Item 3.
Item 3. The lithium iron manganese based composite oxide according to Item 1 or 2 having a rock salt structure.
Item 4.
Item 4. The lithium iron manganese composite oxide according to any one of Items 1 to 3, wherein the average particle size is 0.01 to 50 µm.
Item 5.
Item 5. The method for producing a lithium iron manganese-based composite oxide according to any one of Items 1 to 4, further comprising a step of heating a mixture containing lithium, iron, manganese, and oxygen.
Item 6.
Item 6. The method according to Item 5, wherein the heating temperature is 600 ° C or higher.
Item 7.
The positive electrode active material for lithium ion secondary batteries containing the lithium iron manganese system complex oxide in any one of said claim | item 1-4.
Item 8.
The positive electrode for lithium ion secondary batteries containing the positive electrode active material for lithium ion secondary batteries of said claim | item 7.
Item 9.
Furthermore, the positive electrode for lithium ion secondary batteries of the said claim | item 8 containing a conductive support agent.
Item 10.
The lithium ion secondary battery containing the positive electrode for lithium ion secondary batteries of said claim | item 8 or 9.

  The lithium iron manganese based composite oxide of the present invention can be used as a positive electrode active material for a lithium ion secondary battery because it can desorb and insert one or more lithium ions. In particular, by using the lithium iron manganese based composite oxide of the present invention as a positive electrode active material, a lithium ion secondary battery exhibiting a high charge / discharge capacity can be obtained.

₂ is a diagram showing an X-ray diffraction pattern of Li ₂ FeMnO ₄ obtained in Example 1. FIG. The X-ray diffraction pattern of Li ₂ FeMnO ₄ obtained when the firing temperature was set to 800 ° C. in Example 1 and other lithium manganese-based composite oxides (Li ₂ NiMnO ₄ , Li ₂ CoMnO ₄ , and Li ₂ Mn it is a diagram showing the result of comparison with the X-ray diffraction pattern of the _{2 O 4).} Is a diagram showing the observation results by the scanning electron microscope of Example 1 _Li 2 FeMnO ₄ that the firing temperature was obtained when the 800 ° C. In (SEM). 3 is a cross-sectional view of a test cell used in Example 2. FIG. It is a figure which shows the measurement result (0.05C rate; 55 degreeC) of the charging / discharging characteristic performed in Example 2. FIG. It is a figure which shows the measurement result (0.05C rate; 25 degreeC) of the charging / discharging characteristic performed in Example 2. FIG. It is a figure which shows the measurement result (0.1C rate) of the charging / discharging characteristic performed in Example 2. FIG. The measurement result of the charge / discharge characteristic of the electrode of only carbon and PVDF performed in Example 2 is shown. It is a figure which shows the measurement result of the rate characteristic performed in Example 2. FIG. It is a figure which shows the measurement result (0.05C rate) of the charging / discharging characteristic performed in Example 2. FIG. In addition, it is the result which started from discharge. ₄ is a diagram showing an X-ray diffraction pattern of LiFeMnO ₄ obtained in Comparative Example 1. FIG. It is a diagram showing the observation results by the scanning electron microscope LiFeMnO ₄ obtained when the firing temperature was 800 ° C. (SEM) in Comparative Example 1. The measurement result (0.05C rate; 55 degreeC) of the initial stage charge / discharge characteristic performed by the comparative example 2 is shown. The measurement result (0.05C rate; 55 degreeC) of the charging / discharging characteristic in the high order cycle performed by the comparative example 2 is shown.

  Hereinafter, the present invention will be described in detail. In the present specification, when a numerical range is indicated, the numerical range includes both numerical values.

1. Lithium iron manganese composite oxide The lithium iron manganese composite oxide of the present invention has a composition formula:
Li _{1 + m} Fe _x Mn _2-x O ₄
[Wherein m represents 0 <m ≦ 2. x represents 0 <x ≦ 1. ]
It is a compound represented by these. Hereinafter, the compound may be referred to as “the compound of the present invention”.

  In the above composition formula, m is 0 <m ≦ 2, and 0 <m ≦ 1.5 is preferable from the viewpoint of easy insertion and desorption of lithium ions, capacity and potential, and 0.5 ≦ m ≦ 1.5 is more preferable, and 0.75 ≦ m ≦ 1.25 is more preferable. x is 0 <x ≦ 1, and 0.25 ≦ x ≦ 1 is preferable and 0.5 ≦ x ≦ 1 from the viewpoint of easy insertion and desorption of lithium ions, capacity and potential. More preferably, 0.75 ≦ x ≦ 1 is more preferable.

The compound of the present invention, _{specifically,} include Li 2 FeMnO _4.

  The crystal structure of the compound of the present invention is preferably a tetragonal structure or a cubic structure, and more preferably a tetragonal structure. In particular, the compound of the present invention preferably has a tetragonal or cubic structure as the main phase, and more preferably has a tetragonal structure as the main phase. In the compound of the present invention, the abundance of the crystal structure as the main phase is not particularly limited, and is preferably 80 mol% or more, more preferably 90 mol% or more based on the whole compound of the present invention. For this reason, the compound of this invention can also be used as the material which consists of a single phase crystal structure, and can also be used as the material which has another crystal structure in the range which does not impair the effect of this invention. The crystal structure of the compound of the present invention can be confirmed by X-ray diffraction measurement. Moreover, when the compound of this invention is a tetragonal structure, it is preferable that it is a rock salt type structure.

  The compound of the present invention has peaks at various positions in the X-ray diffraction pattern by CuKα rays. For example, the diffraction angle 2θ preferably has a peak at 18 to 20 °, 37 to 39 °, 43 to 45 °, 61 to 68 °, 70 to 77 °, 78 to 82 °, and the like. Especially, it is preferable to have the highest peak at 43 to 45 ° and the second highest peak at 61 to 68 °.

  The average particle size of the compound of the present invention is not particularly limited, and is preferably 0.01 to 50 μm, more preferably 0.1 to 50 μm, and more preferably 0.5 to 25 μm from the viewpoint of improving performance. More preferably. In addition, the average particle diameter of the compound of this invention can be confirmed with a scanning electron microscope (SEM).

2. Method for Producing Lithium Iron Manganese Complex Oxide The method for producing the compound of the present invention includes a step of heating a mixture containing lithium, iron, manganese and oxygen. Hereinafter, the method for producing the compound of the present invention may be referred to as “the method for producing the present invention”.

  In the production method of the present invention, as a raw material compound for obtaining a mixture containing lithium, iron, manganese, and oxygen, finally lithium, iron, manganese, and oxygen are contained in the mixture. For example, a lithium-containing compound, an iron-containing compound, a manganese-containing compound, an oxygen-containing compound, or the like can be used.

  The type of each compound such as a lithium-containing compound, an iron-containing compound, a manganese-containing compound, and an oxygen-containing compound is not particularly limited, and four or more types including one element each of lithium, iron, manganese, and oxygen These compounds can also be used as a mixture, and a compound containing two or more elements at the same time among lithium, iron, manganese and oxygen is used as a part of the raw material, and less than four compounds are mixed. Can also be used.

  As these raw material compounds, compounds containing no metal elements other than lithium, iron, manganese, and oxygen (particularly rare metal elements) are preferable. Moreover, it is preferable that elements other than each element of lithium, iron, manganese, and oxygen contained in the raw material compound are separated or volatilized by a heat treatment described later.

  Specific examples of such raw material compounds include the following compounds.

Examples of the lithium-containing compound include metallic lithium (Li); lithium oxide (Li ₂ O); lithium bromide (LiBr); lithium fluoride (LiF); lithium iodide (LiI); lithium oxalate (Li ₂ C ₂ O). ₄ ); lithium hydroxide (LiOH); lithium nitrate (LiNO ₃ ); lithium chloride (LiCl); lithium carbonate (Li ₂ CO ₃ ) and the like.

Examples of the iron-containing compound include metallic iron (Fe); iron oxides such as iron oxide (II) (FeO) and iron oxide (III) (Fe ₂ O ₃ ); iron bromide (II) (FeBr ₂ ), chloride Iron (II) (FeCl ₂ ); Iron hydroxide (II) (Fe (OH) ₂ ), Iron hydroxide (III) (Fe (OH) ₃ ), etc .; Iron carbonate (II) (FeCO ₃ ), iron carbonates such as iron (III) carbonate (Fe ₂ (CO ₃ ) ₃ ); iron (II) oxalate (FeC ₂ O ₄ ) and the like.

Examples of manganese-containing compounds include manganese metal (Mn); manganese oxides such as manganese oxide (II) (MnO) and manganese oxide (IV) (MnO ₂ ); manganese hydroxide (II) (Mn (OH) ₂ ), Manganese hydroxides such as manganese hydroxide (IV) (Mn (OH) ₄ ); manganese carbonates such as manganese carbonate (II) (MnCO ₃ ); manganese (II) oxalate (MnC ₂ O ₄ ) and the like It is done.

Examples of the oxygen-containing compound include lithium hydroxide (LiOH); lithium carbonate (Li ₂ CO ₃ ); iron oxides such as iron (II) oxide (FeO) and iron (III) oxide (Fe ₂ O ₃ ); Iron hydroxides such as iron (II) (Fe (OH) ₂ ), iron hydroxide (III) (Fe (OH) ₃ ); iron carbonate (II) (FeCO ₃ ), iron carbonate (III) (Fe ₂ Iron carbonates such as (CO ₃ ) ₃ ); iron (II) oxalate (FeC ₂ O ₄ ); manganese oxides such as manganese (II) oxide (MnO) and manganese (IV) oxide (MnO ₂ ); water Manganese hydroxides such as manganese (II) oxide (Mn (OH) ₂ ) and manganese hydroxide (IV) (Mn (OH) ₄ ); manganese carbonates such as manganese (II) carbonate (MnCO ₃ ); oxalic acid manganese _{(II) (MnC 2 O 4} ) , etc. And the like.

  In addition, a hydrate can also be used for these raw material compounds.

  Moreover, the raw material compound used in the production method of the present invention can be a commercially available product, or can be appropriately synthesized and used. The synthesis method in the case of synthesizing each raw material compound is not particularly limited, and can be carried out according to a known method.

  The shape of these raw material compounds is not particularly limited. From the viewpoint of ease of handling and the like, a powder form is preferable. Further, from the viewpoint of reactivity, it is preferable that the particles are fine, and it is more preferable that the particles have a mean particle size of 1 μm or less (preferably about 10 to 200 nm, particularly preferably about 60 to 80 nm). . In addition, the average particle diameter of a raw material compound can be measured with a scanning electron microscope (SEM).

  A mixture containing lithium, iron, manganese, and oxygen can be obtained by mixing necessary materials among the raw material compounds described above.

  The mixing ratio of each raw material compound is not particularly limited, and it is preferable to mix so that the composition of the compound of the present invention as the final product is obtained. The mixing ratio of the raw material compounds is preferably such that the ratio of each element contained in the raw material compound is the same as the ratio of each element in the compound of the present invention to be produced.

  The method for preparing a mixture containing lithium, iron, manganese, and oxygen is not particularly limited, and a method that can uniformly mix each raw material compound can be employed. For example, mortar mixing, mechanical milling treatment, coprecipitation method, a method of mixing after each raw material compound is dispersed in a solvent, a method of dispersing each raw material compound at once in a solvent and mixing, etc. can be adopted. . Among these, a mixture can be obtained by a simple method by employing mortar mixing, and a uniform mixture can be obtained by employing a coprecipitation method.

  Moreover, when performing a mechanical milling process as a mixing means, as a mechanical milling apparatus, a ball mill, a vibration mill, a turbo mill, a disk mill etc. can be used, for example, A ball mill is especially preferable. Moreover, when performing a mechanical milling process, it is preferable to perform mixing and a heating simultaneously.

  The atmosphere during mixing and heating is not particularly limited as long as it is an inert atmosphere. For example, an inert gas atmosphere such as argon or nitrogen, a hydrogen gas atmosphere, or the like can be employed. Further, mixing and heating may be performed under reduced pressure such as vacuum.

  When heating a mixture containing lithium, iron, manganese and oxygen, the heating temperature is not particularly limited, and the crystallinity and electrode characteristics (capacity and potential) of the resulting compound of the present invention are further improved. In view of the above, it is preferably 600 ° C. or higher, more preferably 700 ° C. or higher, further preferably 800 ° C. or higher, and particularly preferably 900 ° C. or higher. The upper limit of the heating temperature is not particularly limited as long as it is a temperature at which the compound of the present invention can be easily produced (for example, about 1500 ° C.). In other words, the heating temperature is preferably 600 to 1500 ° C, more preferably 700 to 1500 ° C, still more preferably 800 to 1500 ° C, and particularly preferably 900 to 1500 ° C. .

3. Positive electrode active material for lithium ion secondary battery Since the compound of the present invention has the composition and crystal structure described above, lithium ions can be inserted and desorbed. Therefore, the positive electrode active material for lithium ion secondary battery should be used. Can do. Therefore, this invention includes the positive electrode active material for lithium ion secondary batteries containing the compound of this invention mentioned above. In the following, the positive electrode active material for a lithium ion secondary battery containing the compound of the present invention may be referred to as “the positive electrode active material of the present invention”.

  In the positive electrode active material of the present invention, the above-described compound of the present invention and a carbon material (for example, a material such as carbon black such as acetylene black) may form a composite. Thus, since the carbon material suppresses particle growth during firing, it is possible to obtain a fine electrode positive electrode active material for a lithium ion secondary battery having excellent electrode characteristics. In this case, the content of the carbon material is preferably 1 to 30% by mass, more preferably 3 to 20% by mass, and particularly preferably 5 to 15% by mass in the positive electrode active material for a lithium ion secondary battery of the present invention. is there.

  The positive electrode active material of the present invention contains the above-described compound of the present invention. The positive electrode active material of the present invention may be composed of only the compound of the present invention described above, or may contain inevitable impurities in addition to the compound of the present invention. Examples of such inevitable impurities include the raw material compounds described above. The content of inevitable impurities is 10 mol% or less, preferably 5 mol% or less, more preferably 2 mol% or less, as long as the effects of the present invention are not impaired.

4). Positive electrode for lithium ion secondary battery and lithium ion secondary battery The positive electrode for lithium ion secondary battery and lithium ion secondary battery of the present invention are basically the same except that the above-described compound of the present invention is used as a positive electrode active material. Such a structure can employ the same structure as a known positive electrode for a non-aqueous electrolyte (non-aqueous) lithium ion secondary battery and a non-aqueous electrolyte (non-aqueous) lithium ion secondary battery. For example, the positive electrode, the negative electrode, and the separator can be disposed in the battery container such that the positive electrode and the negative electrode are separated from each other by the separator. Thereafter, the lithium ion secondary battery of the present invention can be manufactured by, for example, sealing the battery container after filling the battery container with the nonaqueous electrolytic solution. The lithium ion secondary battery of the present invention may be a lithium secondary battery. In the present specification, “lithium ion secondary battery” means a secondary battery using lithium ions as carrier ions, and “lithium secondary battery” means a secondary that uses lithium metal or a lithium alloy as a negative electrode active material. Means battery.

  The positive electrode for a lithium ion secondary battery of the present invention can employ a structure in which a positive electrode active material containing the above-described compound of the present invention is supported on a positive electrode current collector. For example, the positive electrode material containing the above-described compound of the present invention, a conductive additive, and, if necessary, a binder can be produced by applying to a positive electrode current collector.

  As the conductive aid, for example, a carbon material such as acetylene black, ketjen black, carbon nanotube, vapor grown carbon fiber, carbon nanofiber, graphite, coke or the like can be used. The shape of the conductive auxiliary agent is not particularly limited, and for example, a powder form can be adopted.

  As the binder, for example, a fluororesin such as polyvinylidene fluoride resin or polytetrafluoroethylene can be used.

  The content of various components in the positive electrode material is not particularly limited, and can be appropriately determined from a wide range. For example, 50 to 95% by volume (particularly 70 to 90% by volume) of the above-described compound of the present invention, 2.5 to 25% by volume (particularly 5 to 15% by volume) of a conductive auxiliary agent, and a binder. It is preferable to contain 2.5-25 volume% (especially 5-15 volume%).

  Examples of the material constituting the positive electrode current collector include aluminum, platinum, molybdenum, and stainless steel. Examples of the shape of the positive electrode current collector include a porous body, a foil, a plate, and a mesh made of fibers.

  Note that the amount of the positive electrode material applied to the positive electrode current collector is not particularly limited, and is preferably determined as appropriate according to the use of the lithium ion secondary battery.

Examples of the negative electrode active material constituting the negative electrode include lithium metal; silicon; silicon-containing acrylate compound; lithium alloy; M ¹ M ² ₂ O ₄ (M ¹ : Co, Ni, Mn, Sn, etc., M ² : Mn, Ternary or quaternary oxides represented by Fe, Zn, etc .; M ³ ₃ O ₄ (M ³ : Fe, Co, Ni, Mn, etc.), M ⁴ ₂ O ₃ (M ⁴ : Fe, Co, Ni) , Mn, etc.), MnV ₂ O ₆ , M ⁵ O ₂ (M ⁵ : Sn, Ti etc.), M ⁶ O (M ⁶ : Fe, Co, Ni, Mn, Sn, Cu etc.) Oxides; graphite, hard carbon, soft carbon, graphene; carbon materials described above; organic systems such as Li ₂ C ₆ H ₄ O ₄ , Li ₂ C ₈ H ₄ O ₄ , Li ₂ C ₁₆ H ₈ O ₄ Compounds and the like.

Examples of lithium alloys include alloys containing lithium and aluminum as constituent elements, alloys containing lithium and zinc as constituent elements, alloys containing lithium and lead as constituent elements, alloys containing lithium and manganese as constituent elements, lithium and bismuth. Alloys containing lithium and nickel as constituent elements, alloys containing lithium and antimony as constituent elements, alloys containing lithium and tin as constituent elements, alloys containing lithium and indium as constituent elements; metal (scandium) , Titanium, vanadium, chromium, zirconium, niobium, molybdenum, hafnium, tantalum, and the like) and carbon containing MXene alloy, M ⁷ _x BC ₃ alloy (M ⁷ : Sc, Ti, V, Cr, Zr, Nb, Mo, Hf Ta, etc.) quaternary layered carbide or nitride compounds such like.

  The negative electrode can be composed of a negative electrode active material, and a configuration in which a negative electrode material containing a negative electrode active material, a conductive additive, and a binder as required is supported on the negative electrode current collector is adopted. You can also. When adopting a configuration in which the negative electrode material is supported on the negative electrode current collector, a negative electrode mixture containing a negative electrode active material, a conductive additive, and a binder as necessary is applied to the negative electrode current collector. Can be manufactured.

When the negative electrode is composed of a negative electrode active material, the above negative electrode active material has a shape suitable for an electrode (plate shape, etc.)
It can be obtained by molding.

  In addition, when adopting a configuration in which the negative electrode material is supported on the negative electrode current collector, the types of the conductive auxiliary agent and the binder, and the negative electrode active material, the conductive auxiliary agent, and the binder content are those of the positive electrode described above. Can be applied. Examples of the material constituting the negative electrode current collector include aluminum, copper, nickel, and stainless steel. Examples of the shape of the negative electrode current collector include a porous body, a foil, a plate, and a mesh made of fibers. In addition, it is preferable to determine suitably the application quantity of the negative electrode material with respect to a negative electrode collector according to the use etc. of a lithium ion secondary battery.

  The separator is not limited as long as it is made of a material that can separate the positive electrode and the negative electrode in the battery and can hold the electrolytic solution to ensure the ionic conductivity between the positive electrode and the negative electrode. For example, polyolefin resin such as polyethylene, polypropylene, polyimide, polyvinyl alcohol, terminal aminated polyethylene oxide; fluorine resin such as polytetrafluoroethylene; acrylic resin; nylon; aromatic aramid; inorganic glass; Materials in the form of a membrane, nonwoven fabric, woven fabric, etc. can be used.

  The nonaqueous electrolytic solution is preferably an electrolytic solution containing lithium ions. Examples of such an electrolytic solution include a lithium salt solution, an ionic liquid composed of an inorganic material containing lithium, and the like.

  Examples of lithium salts include lithium halides such as lithium chloride, lithium bromide, and lithium iodide; lithium inorganic salts such as lithium perchlorate, lithium tetrafluoroborate, lithium hexafluorophosphate, and lithium hexafluoroarsenate. Compound: Lithium organic salt compounds such as bis (trifluoromethylsulfonyl) imide lithium, bis (perfluoroethanesulfonyl) imide lithium, lithium benzoate, lithium salicylate, lithium phthalate, lithium acetate, lithium propionate, Grignard reagent, etc. Can be mentioned.

  Examples of the solvent include carbonate compounds such as propylene carbonate, ethylene carbonate, dimethol carbonate, ethyl methyl carbonate, and diethyl carbonate; lactone compounds such as γ-butyrolactone and γ-valerolactone; tetrahydrofuran, 2-methyltetrahydrofuran, diethyl Ether compounds such as ether, diisopropyl ether, dibutyl ether, methoxymethane, glyme, dimethoxyethane, dimethoxymethane, dietoxmethane, dietochiethane, propylene glycol dimethyl ether; acetonitrile; N, N-dimethylformamide; N-propyl-N-methylpyrrolidinium bis (Trifluoromethanesulfonyl) imide etc. are mentioned.

Further, a solid electrolyte can be used instead of the non-aqueous electrolyte. Examples of the solid electrolyte include lithium ion conductors such as Li ₁₀ GeP ₂ S ₁₂ , Li ₇ P ₃ S ₁₁ , Li ₇ La ₃ Zr ₂ O ₁₂ , La _0.51 Li _0.34 TiO _{2.94, and the} like. Enumerated.

  In such a lithium ion secondary battery of the present invention, since the compound of the present invention is used, a higher potential and energy density can be ensured in the oxidation-reduction reaction (charge / discharge reaction), and safety is ensured. Excellent (polyanion skeleton) and practicality. Therefore, the lithium ion secondary battery of the present invention can be suitably used, for example, for devices that are required to be downsized and high performance.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further in detail, this invention is not limited to the following example.

Example 1: As a synthetic raw material powder of Li ₂ FeMnO ₄ , Li ₂ CO ₃ (manufactured by Rare Metallic; 99.9% (3N)), Fe ₂ C ₂ O ₄ .2H ₂ O (manufactured by Junsei Kagaku); 99.9% (3N)) and MnO ₂ (Rare Metallic; 99.99% (4N)) were used. Li ₂ CO ₃ , Fe ₂ C ₂ O ₄ .2H ₂ O, and MnO ₂ were weighed so that lithium: iron: manganese (molar ratio) was 2: 1: 1, and zirconia balls (15 mmΦ × 10) The mixture was placed in a chrome steel container, added with acetone, and pulverized and mixed at 400 rpm for 24 hours in a planetary ball mill (manufactured by Fritsch, trade name: P-6). Then, after removing acetone under reduced pressure, the recovered powder was pelleted by hand pressing and calcined at 600 ° C., 700 ° C., 800 ° C., 900 ° C., or 1000 ° C. for 1 hour under an argon stream. At this time, the temperature rising rate was 400 ° C./h. The cooling rate was set to 100 ° C./h up to 300 ° C., and thereafter, the mixture was naturally cooled to room temperature. Each obtained product (Li ₂ FeMnO ₄ ) was confirmed by powder X-ray diffraction (XRD). The results are shown in FIG.

  In addition, for powder X-ray diffraction (XRD) measurement, an X-ray diffraction measurement apparatus (manufactured by Rigaku Corporation, trade name: RINT2200) was used, and an X-ray source was CuKα monochromatized with a monochromator. Data were collected under the measurement conditions of a tube voltage of 5 kV and a tube current of 300 mA. At this time, the scanning speed was set so that the intensity was about 10,000 counts. The sample used for measurement was sufficiently pulverized so that the particles were uniform. Rietveld analysis was performed for the structural analysis, and JANA-2006 was used as the analysis program.

From FIG. 1, it was confirmed that when the firing temperature was 600 ° C. or higher, a plurality of main peaks were observed at least at 2θ values of 30 to 65 °. These peaks, since it corresponds to the _Li 2 FeMnO ₄ single-phase, _Li 2 FeMnO ₄ single-phase is found to be obtained as a product. Moreover, since the peak seen in the said 2 (theta) value 35-65 degree becomes a strong peak, so that baking temperature is high, it turned out that the one where baking temperature is higher is preferable.

Also, from FIG. 1, the obtained Li ₂ FeMnO ₄ crystal has a diffraction angle represented by 2θ of 18 to 20 °, 37 to 39 °, and 43 to 45 ° in an X-ray diffraction pattern by powder X-ray diffraction. , 61-68 °, 70-77 °, and 78-82 °. From the results, the obtained crystal of Li ₂ FeMnO ₄ has a tetragonal structure (space group P4 / nbm), and the lattice constants are a = b = 3.596 to 3.610Å, c = 14.366 to 14.498A, an α = β = γ = 90 ° , the unit cell volume (V) was found to be crystalline is 187.2~187.5Å ^3. Further, since it is c / a = 3.9950, the resulting _Li 2 FeMnO ₄ crystal was found to have a rock-salt structure.

Furthermore, Li ₂ FeMnO ₄ obtained when the firing temperature is 800 ° C., and other known lithium manganese based composite oxides (Li ₂ NiMnO ₄ , Li ₂ CoMnO ₄ , and Li ₂ Mn ₂ O ₄ ) The result of comparing the X-ray diffraction patterns is shown in FIG. _{Incidentally, Li 2 NiMnO 4, Li 2} CoMnO 4, and _Li 2 _Mn 2 _{O 4,} except that changing the starting compound is a sample synthesized in the same manner as described above. In addition, Li ₂ FeMnO ₄ , Li ₂ NiMnO ₄ , Li ₂ CoMnO ₄ , and Li ₂ Mn ₂ O ₄ , and other iron-manganese composite oxides (K ₂ FeMnO ₄ , Na ₂ FeMnO ₄ , MgFeMnO ₄ , LiFeMnO ₄₎ Table 1 below shows a comparison of the lattice constants.

From FIG. 2, it can be seen that Li ₂ FeMnO ₄ and other lithium manganese based composite oxides (Li ₂ NiMnO ₄ , Li ₂ CoMnO ₄ , and Li ₂ Mn ₂ O ₄ ) exhibit completely different X-ray diffraction patterns. confirmed.

Furthermore, Li ₂ FeMnO ₄ obtained when the firing temperature was 800 ° C. was observed with a scanning electron microscope (SEM). The results are shown in FIG. In FIG. 3, the scale bar indicates 7.69 μm. From FIG. 3, it was found that Li ₂ FeMnO ₄ having a particle diameter of about 1 to 20 μm was obtained.

Example 2: Measurement of charge / discharge characteristics In order to perform charge / discharge characteristics, Li ₂ FeMnO ₄ , polyvinylidene fluoride (PVDF), and acetylene black (AB) obtained at the firing temperature of 800 ° C in Example 1 above. Were mixed in an agate mortar so that the volume ratio was 85: 7.5: 7.5, and the resulting slurry was applied onto an aluminum foil (thickness 20 μm) as a positive electrode current collector, It was punched into a circle and used as a positive electrode. Moreover, in order to prevent a sample from peeling from a positive electrode electrical power collector, it crimped | bonded by 30-40 mPa.

Metal lithium punched out at 14 mmφ was used for the negative electrode, and two porous membranes (trade name: celgard 2500) cut out at 18 mmφ were used as the separator. The electrolytic solution is an electrolytic solution (manufactured by Kishida Chemical Co., Ltd.) in which LiPF ₆ is dissolved at a concentration of 1 mol / dm ³ as a supporting electrolyte in a solvent in which ethylene carbonate (EC) and diethyl carbonate (DEC) are mixed at a volume ratio of 1: 2. used. The battery was produced in Globe Books under an argon atmosphere because of the use of metallic lithium and the cause of increased resistance when water was mixed in the electrolyte. As the cell, a CR2032-type coin cell shown in FIG. 4 was used. The measurement of the constant current charge / discharge characteristics was started from charging at a 0.05C rate or a 0.1C rate, using a voltage switch, setting a current of 10 mA / g, an upper limit voltage of 4.8 V, and a lower limit voltage of 1.5 V. . The charge / discharge measurement was performed in a state where the cell was placed in a 55 ° C. constant temperature bath or at room temperature (25 ° C.). Fig. 5 shows the measurement results of charge / discharge characteristics at 0.05C rate (55 ° C) (relationship between each cycle and discharge capacity), and the measurement results of charge / discharge characteristics at 0.05C rate (25 ° C) (each cycle). 6 shows the relationship between the discharge capacity and the discharge capacity, and FIG. 7 shows the measurement results of the charge / discharge characteristics at the 0.1 C rate (55 ° C.) (the relation between each cycle and the discharge capacity). The C rate refers to the current density required to charge / discharge the theoretical capacity from the electrode active material in one hour.

As shown in FIG. 5, the initial charge capacity is 280 mAh / g (about 1.9 Li ⁺ min) at a 0.05 C rate (55 ° C.), and the theoretical capacity of Li ₂ FeMnO ₄ is about 285 mAh / g. It was found that a value very close to the theoretical capacity was obtained. The average operating voltage is 2.8 V, and the charge / discharge capacity that can be reversibly extracted is about 250 mAh / g (about 1.8 Li ⁺ min). This is an energy density corresponding to 700 Wh / kg, and Li ₂ FeMnO ₄ is highly expected as a positive electrode active material having a high capacity and a high energy density. Further, from FIG. 6, it was confirmed that at room temperature, only a capacity of 1 Li ⁺ was reversibly removed / inserted at most. From the results, it was found that Li ₂ FeMnO ₄ can maximize the performance by raising the operating temperature. Further, FIG. 7 shows that good cycle characteristics can be obtained for the initial discharge and the high-order cycle at the 0.1 C rate. Moreover, it turned out that the capacity | capacitance which can be pulled out at 0.1 C rate is about 200 mAh / g.

A positive electrode was prepared in the same manner as described above except that Li ₂ FeMnO ₄ was not used, and a charge / discharge test was performed at a C / 20 rate (55 ° C.) under the same conditions as described above. The results are shown in FIG.

From FIG. 8, it was confirmed that a charge / discharge capacity could not be obtained with an electrode not using Li ₂ FeMnO ₄ . By comparing FIG. 5 with FIG. 8, it was found that the high charge / discharge capacity shown in FIG. 5 was derived from Li ₂ FeMnO ₄ .

Furthermore, the rate characteristics of Li ₂ FeMnO ₄ were examined. Specifically, after charging at a 0.05 C rate, the initial discharge capacity at a 0.05 C rate, a 0.1 C rate, or a 0.2 C rate was measured. The results are shown in FIG.

From FIG. 9, the capacity obtained at the 0.1 C rate was 225 mAh / g, and the capacity obtained at the 0.2 C rate was 100 mAh / g. From these results, it was found that Li ₂ FeMnO ₄ exhibits good rate characteristics.

  Further, the current charge / discharge characteristics were measured in the same manner as described above except that the discharge was started at 0.05 C rate. The results are shown in FIG.

From FIG. 10, the capacity that can be extracted from Li ₂ FeMnO ₄ after the initial discharge was about 360 mAh / g. From the result, it was found that when Li ₂ FeMnO ₄ is discharged for the first time, that is, when lithium is further inserted, a higher capacity can be obtained. Therefore, Li ₂ FeMnO ₄ is highly expected as a high capacity positive electrode active material.

Comparative Example 1: Li ₂ CO ₃ (manufactured by Rare Metallic; 99.9% (3N)), Fe ₂ O ₃ (pure chemistry, 99.9% (3N)), and MnO as synthetic raw material powders of LiFeMnO _{4 2} (rare metallic, 99.99% (4N)) was used. Li ₂ CO ₃ , Fe ₂ O ₃ and MnO ₂ were weighed so that lithium: iron: manganese (molar ratio) was 1: 1: 2, and mixed in an agate mortar for about 30 minutes to obtain a raw material mixture. Then, the raw material mixture was put into a chrome steel container together with zirconia balls (15 mmΦ × 10), added with acetone, and pulverized and mixed at 400 rpm for 6 hours in a planetary ball mill (Fritsch; P-6). Then, after distilling off acetone under reduced pressure, the recovered powder is pellet-molded at 40 MPa, and in air at 550 ° C., 600 ° C., 650 ° C., 700 ° C., 750 ° C., 800 ° C., 850 ° C., or 900 ° C. Baked for 3 hours. Thereafter, it was allowed to cool to room temperature by natural cooling. Each obtained product was confirmed by powder X-ray diffraction (XRD) in the same manner as in Example 1. The results are shown in FIG.

From FIG. 11, the obtained LiFeMnO ₄ crystal has cubic crystals (space group Fd-3m), the lattice constant is a = b = c = 8.286 to 8.306Å, and α = β = γ = 90. a °, the unit cell volume (V) was found to be crystalline is 568.9~573.0Å ^3. Since c / a = 1, it was found that the obtained LiFeMnO ₄ crystal had a spinel structure.

Furthermore, LiFeMnO ₄ obtained when the firing temperature was 800 ° C. was observed with a scanning electron microscope (SEM). The results are shown in FIG. In FIG. 12, the scale bar indicates 1.53 μm. From FIG. 12, it was found that LiFeMnO ₄ having a particle size of about 0.3 to 3 μm was obtained.

Comparative Example 2: Measurement of charge / discharge characteristics In order to perform charge / discharge characteristics, the volume of LiFeMnO ₄ , polyvinylidene fluoride (PVDF), and acetylene black (AB) obtained in the case of the firing temperature of 800 ° C. in Comparative Example 1 described above was volume. The mixture was mixed in an agate mortar so that the ratio was 85: 7.5: 7.5, and the resulting slurry was applied onto an aluminum foil (thickness 20 μm) as a positive electrode current collector, and this was formed into a circle having a diameter of 8 mm. Punched into a positive electrode. Moreover, in order to prevent a sample from peeling from a positive electrode electrical power collector, it crimped | bonded by 30-40 mPa.

Metal lithium punched out at 14 mmφ was used for the negative electrode, and two porous membranes (trade name: celgard 2500) cut out at 18 mmφ were used as the separator. The electrolytic solution is an electrolytic solution (manufactured by Kishida Chemical Co., Ltd.) in which LiPF ₆ is dissolved at a concentration of 1 mol / dm ³ as a supporting electrolyte in a solvent in which ethylene carbonate (EC) and diethyl carbonate (DEC) are mixed at a volume ratio of 1: 2. used. The battery was produced in Globe Books under an argon atmosphere because of the use of metallic lithium and the cause of increased resistance when water was mixed in the electrolyte. As the cell, a CR2032-type coin cell shown in FIG. 4 was used. The measurement of the constant current charge / discharge characteristics was started from charging at a rate of 0.05 C, using a voltage switch, setting a current of 10 mA / g, an upper limit voltage of 4.8 V, and a lower limit voltage of 1.5 V. Moreover, the charge / discharge measurement was performed in a state where the cell was placed in a 55 ° C. constant temperature bath. FIG. 13 shows the measurement results (relationship between each cycle and discharge capacity) of the initial charge / discharge characteristics at the 0.05C rate (55 ° C.), and the charge / discharge characteristics at the higher cycle at the 0.05C rate (55 ° C.). The measurement results (relationship between each cycle and the discharge capacity) are shown in FIG. The C rate refers to the current density required to charge / discharge the theoretical capacity from the electrode active material in one hour.

As shown in FIG. 13, it was confirmed that the initial charge / discharge capacity of spinel-type LiFeMnO _{4 at} a 0.05C rate was 130 mAh / g. When compared with the rock salt type Li ₂ FeMnO ₄ obtained in Example 1, it was found that the initial charge / discharge capacity of the spinel type LiFeMnO ₄ was significantly inferior to the rock salt type Li ₂ FeMnO ₄ .

Furthermore, FIG. 14 shows that spinel-type LiFeMnO ₄ has relatively stable operating characteristics, but the extractable capacity is greatly inferior to that of the rock-salt-type rock-salt-type Li ₂ FeMnO ₄ .

DESCRIPTION OF SYMBOLS 1 Lithium ion secondary battery 2 Negative electrode terminal 3 Negative electrode 4 Separator impregnated with electrolyte 5 Insulation packing 6 Positive electrode 7 Positive electrode can

Claims (10)

Composition formula:
Li _{1 + m} Fe _x Mn _2-x O ₄
[Wherein m represents 0 <m ≦ 2. x represents 0 <x ≦ 1. ]
Lithium iron manganese complex oxide represented by The lithium iron manganese composite oxide according to claim 1, which has a tetragonal structure or a cubic structure. The lithium iron manganese complex oxide according to claim 1 or 2, having a rock salt structure. The lithium iron manganese composite oxide according to any one of claims 1 to 3, wherein an average particle diameter is 0.01 to 50 µm. The manufacturing method of the lithium iron manganese system complex oxide in any one of Claims 1-4 including the process of heating the mixture containing lithium, iron, manganese, and oxygen. The method according to claim 5, wherein the heating temperature is 600 ° C. or higher. The positive electrode active material for lithium ion secondary batteries containing the lithium iron manganese system complex oxide in any one of Claims 1-4. The positive electrode for lithium ion secondary batteries containing the positive electrode active material for lithium ion secondary batteries of Claim 7. Furthermore, the positive electrode for lithium ion secondary batteries of Claim 8 containing a conductive support agent. The lithium ion secondary battery containing the positive electrode for lithium ion secondary batteries of Claim 8 or 9.

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