JP5673932B2 - Lithium manganese composite oxide having cubic rock salt structure and method for producing the same - Google Patents

Description

  The present invention relates to a lithium manganese composite oxide having a cubic rock salt structure useful as a positive electrode material for a next-generation low-cost lithium ion secondary battery and a method for producing the same.

  Currently, in Japan, most of secondary batteries installed in portable devices such as mobile phones and notebook computers are lithium ion secondary batteries. In addition, lithium ion secondary batteries are expected to be put into practical use as large batteries for electric vehicles, power load leveling systems, and the like, and their importance is increasing.

Currently, in lithium ion secondary batteries, a lithium cobalt oxide (LiCoO ₂ ) material is mainly used as a positive electrode material, and a carbon material such as graphite is used as a negative electrode material. In the secondary battery having such a configuration, the lithium in the lithium cobalt oxide is oxidized from trivalent to tetravalent by charging and Li is desorbed to supply Li to the negative electrode. It operates as a battery by desorbing and inserting Li into the positive electrode side by reducing tetravalent cobalt to trivalent.

In such a lithium ion secondary battery, the amount of lithium ions reversibly desorbed (equivalent to charging) and inserted (equivalent to discharging) in the positive electrode material determines the capacity of the battery, and the voltage at the time of desorption / insertion is the battery LiCoO ₂ as a positive electrode material is an important battery constituent material related to battery performance. For this reason, the demand for lithium cobalt oxide is expected to increase further with the future expansion and enlargement of lithium ion secondary batteries.

However, since lithium cobalt oxide contains a large amount of cobalt, which is a rare metal, it is one of the factors that increase the material cost of lithium ion secondary batteries. Furthermore, considering that about 20% of cobalt resources are currently used in the battery industry, it is considered difficult to meet future demand growth with only the cathode material made of LiCoO ₂ .

Currently, lithium nickel oxide (LiNiO ₂ ) and lithium manganese oxide (LiMn ₂ O ₄ ) have been reported as cheaper and less resource-constrained positive electrode materials, and some have been put into practical use as alternative materials. Yes. However, lithium nickel oxide has the problem of reducing the safety of the battery during charging, and lithium manganese oxide has trivalent manganese eluted into the electrolyte during charge and discharge at high temperature (about 60 ° C), It has the problem of significantly degrading battery performance, and alternatives to these materials are less advanced. Among the lithium manganese oxides, a positive electrode material called LiMnO ₂ has also been proposed, but this material gradually has a spinel crystal structure typified by LiMn ₂ O ₄ from its original structure due to charge and discharge. In order to change, there exists a problem that the shape of a charging / discharging curve changes large with progress of a charging / discharging cycle, and it has not reached practical use.

In addition, lithium ferrite (LiFeO ₂ ) containing iron, which is more abundant in resources than manganese and nickel, is less toxic, and contains less expensive iron, is being investigated as a potential electrode material. However, since lithium ferrite obtained by a normal manufacturing method, that is, by mixing an iron source and a lithium source and firing at high temperature, hardly charges or discharges, it cannot be used as a positive electrode material for a lithium ion secondary battery.

On the other hand, LiFeO ₂ obtained by the ion exchange method has been reported to be chargeable / dischargeable (see Patent Documents 1 and 2 below), but the average discharge voltage of these materials is 2.5 V or less and the value of LiCoO ₂ Since it is significantly lower than (approximately 3.7V), it is difficult to replace LiCoO ₂ .

The present inventors have already described a layered rock salt type solid solution (Li _{1 + x} (Fe _y Mn ₁ ) composed of lithium manganese oxide (Li ₂ MnO ₃ ) and lithium ferrite, which are cheaper and resource-rich after iron. _-y ) _1-x O ₂ (0 <x <1/3, 0 <y <1), hereinafter referred to as “iron-containing Li ₂ MnO ₃ ”) is a lithium cobalt oxide in the charge / discharge test at room temperature. It has been found that it has an average discharge voltage close to 4V (see Patent Documents 3 and 4 below).

Furthermore, the present inventors show that a lithium-iron-manganese composite oxide satisfying specific conditions exhibits a higher capacity (150 mAh / g) and stable charge / discharge cycle characteristics than LiMn ₂ O ₄ during a high-temperature cycle test. (See Patent Document 5 below).

In addition, the present inventors have shown that lithium manganese oxides (titanium-containing Li ₂ MnO ₃ and iron and titanium-containing Li ₂ MnO ₃ ) containing titanium that is resource-rich and inexpensive with iron exhibit high capacity, In particular, it has been found that a specific chemical composition and transition metal ion distribution are excellent in discharge characteristics under high current density at room temperature and discharge characteristics at low temperature (see Patent Document 6-8 below). In addition, lithium titanium oxide (iron-containing Li ₂ TiO ₃ and iron- and nickel-containing Li ₂ TiO ₃ ) having a cubic rock salt type crystal structure, which has been difficult to use as a positive electrode material for lithium secondary batteries, It has been clarified that it can be used as a positive electrode material for ion secondary batteries. (See Patent Documents 9 and 10 below)
As described above, various reports have been made on lithium manganese-based positive electrode materials that can replace lithium-cobalt-based positive electrode materials. For further improvement of charge / discharge characteristics, the chemical composition of the positive electrode materials including control of the crystal structure. And optimization of manufacturing conditions is desired.

Japanese Patent Laid-Open No. 10-120421 JP-A-8-295518 JP 2002-68748 A Japanese Patent Laid-Open No. 2002-121026 JP 2005-154256 A JP 2008-63211 A JP 2009-179501 A JP 2009-274940 A JP2003-48717 JP 2003-306322 A

  The present invention has been made in view of the current state of the prior art described above, and its main object is to maintain an average discharge voltage of 3 V or more in a long-term charge / discharge cycle and to provide a lithium cobalt oxide-based positive electrode material. Is a material having a discharge capacity equivalent to or higher than that, can be obtained by using raw materials with less resource restrictions and cheaper, and more excellent than known low-cost positive electrode materials. It is another object of the present invention to provide a novel material capable of exhibiting excellent charge / discharge characteristics.

The present inventor has intensively studied to achieve the above-described object. As a result, in the manganese-based oxide solid solution containing iron and / or titanium, the main crystal phase can be controlled to the crystal phase of the cubic rock salt structure by devising the chemical composition and the production method. The obtained oxide has excellent discharge characteristics as compared with the oxide obtained by the conventional method, and it has been found that the initial charge / discharge efficiency is particularly high. As a result, by using the oxide as a positive electrode material for a lithium ion secondary battery, the amount of negative electrode material required for initial charging can be reduced, and as a result, a battery having a high energy density can be manufactured. The present invention was completed here.

  That is, the present invention provides the following lithium manganese composite oxide, a production method thereof, a lithium ion secondary battery positive electrode material comprising the lithium manganese composite oxide, and a lithium ion secondary battery.

Item 1. Composition formula: Li _{1 + x} (Mn _1-mn Fe _m Ti _n ) _1-x O ₂ (0 <x <1/3, 0 ≦ m ≦ 0.70, 0 ≦ n ≦ 0.70, 0.55 ≦ m + n <1 ) is represented by, it a lithium-manganese-based composite oxide, wherein the main crystal phase is a crystal phase of cubic rock-salt type structure,
Lithium manganese in which the ratio of the crystal phase of the cubic rock salt type structure to the crystal phase of the layered rock salt type structure is cubic rock salt type structural crystal phase: layered rock salt type structural crystal phase (weight ratio) = 100: 0 to 93: 7 Complex oxides.
Item 2. And at least one compound selected from the group consisting of titanium compounds and iron compounds, a mixed aqueous solution containing a manganese compound to form a precipitate as an alkaline, a precipitate obtained with water-soluble lithium compound, a non-oxidizing agent 2. The method for producing a lithium manganese composite oxide according to item 1 , wherein hydrothermal treatment is performed under alkaline conditions in the presence.
Item 3 . Item 3. The method for producing a lithium manganese composite oxide according to Item 2 , wherein the aqueous solution used for the hydrothermal treatment further contains a reducing agent.
Item 4 . Item 4. The method for producing a lithium manganese composite oxide according to Item 1, wherein after the hydrothermal treatment is performed by the method according to Item 2 or 3 , firing treatment is performed in the presence of a lithium compound.
Item 5 . At least one compound selected from the group consisting of a titanium compound and an iron compound, and a mixed aqueous solution containing a manganese compound is made alkaline to form a precipitate, and the obtained precipitate together with a water-soluble lithium compound and an oxidizing agent is subjected to alkaline conditions. 2. The method for producing a lithium manganese oxide according to item 1 , wherein the hydrothermal treatment is performed, and the product after the hydrothermal treatment is baked together with the lithium compound in a reducing atmosphere.
Item 6. Lithium ion secondary battery positive electrode material made of lithium-manganese-based composite oxide according to above climate 1.
Item 7 . The lithium ion secondary battery which uses the positive electrode material for lithium ion secondary batteries of said item 6 as a component.

  Hereinafter, the lithium manganese composite oxide and the method for producing the same of the present invention will be specifically described.

(1) The lithium-manganese-based composite oxide of lithium manganese-based composite oxide of the present invention, the composition formula _{Li 1 + x (Mn 1-} mn Fe m Ti n) 1-x O 2 (0 <x <1/3, 0 ≦ m ≦ 0.70, 0 ≦ n ≦ 0.70, 0.55 ≦ m + n <1), based on cubic rock salt type (NaCl type) structure, which is a general crystal structure of oxide As the main crystal phase, the same cubic crystal as α-LiFeO ₂ and Li ₂ TiO ₃ which are known substances

It includes a crystal phase with a rock salt structure. FIG. 1 is a drawing schematically showing a crystal structure of a crystal phase (LiFeO ₂ ) having a cubic rock salt (NaCl) type structure. Oxide ions form a face-centered cubic lattice, and Li and Fe occupy the octahedral position at a ratio of 1: 1. The lithium manganese composite oxide of the present invention has a structure in which at least one element selected from the group consisting of Li and Mn and Fe and Ti is present at the octahedral position.

  The lithium manganese composite oxide of the present invention includes a crystal phase having a cubic rock salt structure as a main crystal phase, and may be a single phase of a crystal phase having a cubic rock salt structure, or A crystal phase of a layered rock salt structure having a different cation distribution, for example, a mixed phase containing a small amount of a crystal phase of a monoclinic layered rock salt structure, a crystal phase of a hexagonal layered rock salt structure, or the like may be used. In this case, the ratio of the crystal phase of the cubic rock salt type structure to the crystal phase of the layered rock salt type structure is usually cubic crystal salt type structure crystal phase: layered rock salt type structure crystal phase (weight ratio) = 100: 0 to 93: It may be within a range of about 7.

In conventionally known lithium manganese composite oxides, manganese atoms basically exist as a component constituting Li ₂ MnO ₃ having a monoclinic layered rock salt structure as a tetravalent element. Regarding Li ₂ MnO ₃ , “CS Johnson, JS Kim, C. Lefief, JT Vaughey and MM Thackeray, Electrochemistry Communication, vol.6 p.1085-1091 (2004)” (hereinafter referred to as “Reference 1”). In the initial charge, a potential flat portion due to Li ₂ O desorption appears in the vicinity of 4.5 V, but the charge capacity up to 5.0 V is 383 mAh / g, whereas the discharge capacity is 208 mAh / g, It is described that the initial charge / discharge efficiency is a low value of 54%.

On the other hand, the lithium manganese based composite oxide of the present invention is obtained by devising a manufacturing method as described later, and is a novel that can maintain a cubic rock salt structure despite containing manganese. It is a substance. The lithium-manganese composite oxide of the present invention having such a feature is a lithium-containing lithium oxide containing Li ₂ MnO ₃ having a monoclinic layered rock salt structure or a hexagonal layered rock salt structure as a main component. Compared with a manganese-based composite oxide, it has excellent charge / discharge characteristics, and in particular has a high initial charge efficiency. Although the reason for this is not clear, lithium manganese composite oxides having a cubic rock salt structure can desorb Li at a voltage as low as 4.5 V or less, which improves initial charge and discharge efficiency. it is conceivable that.

  The lithium manganese based composite oxide of the present invention is an oxide containing Li and Mn as essential elements as shown in the above composition formula, and further contains at least one element selected from the group consisting of Fe and Ti. It is a solid solution.

  The amount of Fe to be dissolved (m value: Fe / (Fe + Mn + Ti)) is about 70 mol% or less of the amount of metal other than Li (0 ≦ Fe / (Fe + Mn + Ti) ≦ 0.70), Preferably, it is 10 mol% or more and 65 mol% or less (0.1 ≦ Fe / (Fe + Mn + Ti) ≦ 0.65). By including iron which is abundant in resources within such a range, it is possible to obtain a positive electrode material which is inexpensive and has excellent charge / discharge performance. However, when the Fe solid solution amount becomes excessive, the Fe dilution by Mn becomes insufficient, resulting in an increase in Fe that does not participate in charge and discharge, resulting in a decrease in the Li content contained per composition formula. It is not preferable in terms of characteristics.

  Ti, which is solid-solved in the lithium manganese composite oxide of the present invention, is basically present in the cubic rock salt structure in the form of replacing Mn and Li, similarly to Fe. Ti exists in a tetravalent state, and is thought to contribute to the suppression of Li deficiency and changes in powder properties as described in Patent Document 6. The amount of Ti dissolved in the composite oxide of the present invention (n value: Ti / (Fe + Mn + Ti)) is about 70 mol% or less of the amount of metal other than Li (0 ≦ Ti / (Fe + Mn + Ti)) ≦ 0.70), preferably about 10 mol% or more and about 65 mol% or less (0.1 ≦ Ti / (Fe + Mn + Ti) ≦ 0.65). It is not preferable to use a large amount of Ti, which is more difficult to be involved in charge / discharge than Mn, because it causes a decrease in charge / discharge capacity. On the other hand, when the solid solution amount of Ti is too small, effects such as suppression of Li deficiency are not sufficiently exhibited, which is also not preferable.

  The total amount of Fe and Ti to be dissolved in the lithium manganese composite oxide of the present invention is in the range of about 0.55 ≦ m + n <1 in the composition formula, preferably in the range of about 0.6 ≦ m + n ≦ 0.9. Is within. Lithium-manganese composite oxides with the crystal phase of the target cubic rock salt structure as the main crystal phase by devising the manufacturing method as described later, with the total amount of Fe and Ti within this range Can be obtained.

In the lithium manganese composite oxide of the present invention, as long as the cubic rock salt type crystal structure can be maintained, _{x of} Li _{1 + x} (Mn _1-mn Fe _m Ti _n ) _1-x O ₂ is a transition Depending on the average valence of the metal, it can take values between 0 and 1/3. Preferably it is the range of 0.05-0.30.

  Further, the composite oxide of the present invention has a lithium hydroxide, lithium carbonate, titanium compound, iron compound, manganese compound (including hydrates and composite compounds thereof) in a range that does not significantly affect the charge / discharge characteristics. An impurity phase may be included. In addition, when performing a baking treatment in the presence of an organic substance to be described later, an impurity phase such as amorphous or crystalline carbon that may remain at the time of baking may be included in the product. Such an impurity phase may also be present in the composite oxide of the present invention. About the amount of impurity phases other than the crystal phase of the rock salt type structure consisting of the crystal phase of the cubic rock salt type structure and the layered rock salt type structure, it may be present up to about 10% by weight in the lithium manganese composite oxide.

Method for Producing Lithium Manganese Composite Oxide There is no particular limitation on the method for producing lithium manganese composite oxide of the present invention. For example, according to a method utilizing hydrothermal reaction, a composite having excellent charge / discharge performance An oxide can be easily formed. Hereinafter, this method will be specifically described.

  (I) Among the production methods using a hydrothermal reaction, first, the first method is to dissolve a metal compound that is a generation source of iron ions, manganese ions, and titanium ions in water, a water / alcohol mixture, or the like. This is a method in which the mixed solution is made alkaline to form a precipitate, and then a water-soluble lithium compound is added thereto and hydrothermal treatment is performed under alkaline conditions. At this time, by performing a hydrothermal treatment without adding an oxidizing agent, a lithium manganese composite oxide having a crystal phase of a target cubic rock salt structure as a main crystal phase can be obtained.

  As an iron compound, a manganese compound, and a titanium compound, if it is a component which can form the mixed aqueous solution containing these compounds, it can be used without limitation. Usually, a water-soluble compound may be used. Specific examples of such water-soluble compounds include chlorides, nitrates, sulfates, oxalates and acetates. Moreover, water-soluble salts, such as permanganate, can also be used as a manganese compound. These water-soluble compounds may be either anhydrides or hydrates. Further, even water-insoluble compounds such as oxides and hydroxides can be used as an aqueous solution after being dissolved using an acid such as hydrochloric acid. Each of these raw material compounds may be used alone or in combination of two or more for each metal source.

  The mixing ratio of the iron compound, manganese compound, and titanium compound in the mixed aqueous solution may be set to the same element ratio as each element ratio in the target composite oxide. Accordingly, at least one of these iron compounds and titanium compounds is used depending on the composition of the target composite oxide.

  The concentration of each compound in the mixed aqueous solution is not particularly limited, and may be determined as appropriate so that a uniform mixed aqueous solution can be formed and a coprecipitate can be smoothly formed. Usually, the total concentration of the iron compound, manganese compound and titanium compound may be about 0.01 to 5 mol / l, preferably about 0.1 to 2 mol / l.

  As a solvent for the mixed aqueous solution, water may be used alone, or a water-alcohol mixed solvent containing a water-soluble alcohol such as methanol or ethanol may be used. By using a water-alcohol mixed solvent, it is possible to form a precipitate at a temperature lower than 0 ° C. or to form a precipitate when potassium permanganate is used as the manganese source. The amount of alcohol used may be appropriately determined according to the target precipitation temperature, but it is usually appropriate to use about 50 parts by weight or less with respect to 100 parts by weight of water.

  In order to generate a precipitate (coprecipitate) from the mixed aqueous solution, the mixed aqueous solution may be made alkaline. Conditions for forming a good precipitate vary depending on the type and concentration of each compound contained in the mixed aqueous solution, and thus cannot be defined unconditionally. However, it is usually preferable to set the pH to about 8 or more, and to about pH 11 or more. More preferred.

  The method for making the mixed aqueous solution alkaline is not particularly limited, and usually an alkali or an aqueous solution containing an alkali may be added to the mixed aqueous solution. Moreover, a coprecipitate can be formed also by the method of adding this mixed aqueous solution to the aqueous solution containing an alkali. Examples of the alkali used to make the mixed aqueous solution alkaline include alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, and lithium hydroxide, ammonia, and the like. When these alkalis are used as an aqueous solution, for example, they can be used as an aqueous solution having a concentration of about 0.1 to 20 mol / l, preferably about 0.3 to 10 mol / l. Further, the alkali may be dissolved in a water-alcohol mixed solvent containing a water-soluble alcohol, similarly to the mixed aqueous solution of the metal compound described above.

  During precipitation, the temperature of the mixed aqueous solution is set to about -50 ° C to + 40 ° C, preferably about -20 ° C to + 30 ° C, so that spinel ferrite is generated due to the generation of heat of neutralization during the reaction. A fine and homogeneous coprecipitate is easily formed.

  After making the mixed aqueous solution alkaline, the reaction solution is further blown with air at about 0 to 150 ° C. (preferably about 10 to 100 ° C.) for about 0.5 to 7 days (preferably about 1 to 4 days). In addition, it is preferable to oxidize and age the precipitate.

  The precipitate can be purified by washing the resulting precipitate with distilled water or the like to remove excess alkali components, residual raw materials, and the like, followed by filtration. Next, the precipitate obtained by the above method is subjected to hydrothermal treatment under alkaline conditions together with the water-soluble lithium compound. Hydrothermal treatment can be performed by heating the aqueous solution containing the precipitate and the water-soluble lithium compound under alkaline conditions. Heating is usually performed in a sealed container. In the first method, the hydrothermal treatment needs to be performed in the absence of an oxidizing agent. As a result, a lithium manganese composite oxide containing the crystal phase of the intended cubic rock salt structure as the main crystal phase can be obtained.

  In the aqueous solution used for the hydrothermal reaction, the content of the precipitate containing iron, manganese and titanium is preferably about 1 to 100 g, more preferably about 10 to 80 g per liter of water.

  As the water-soluble lithium compound, for example, a water-soluble lithium salt such as lithium chloride or lithium nitrate, lithium hydroxide, or the like can be used. These water-soluble lithium compounds can be used singly or in combination of two or more, and any of anhydrides and hydrates may be used.

  The amount of the water-soluble lithium compound used is preferably about Li / (Fe + Mn + Ti) = 1 to 10 as a molar ratio of lithium element to the total number of moles of Fe, Mn and Ti in the precipitation product, More preferably, it is about 3-7.

  The concentration of the water-soluble lithium compound is preferably about 0.1 to 10 mol / l, and more preferably about 1 to 8 mol / l.

  A reducing agent can be further added to the aqueous solution used for the hydrothermal reaction. By performing a hydrothermal synthesis reaction using an aqueous solution to which a reducing agent is added, the crystal structure of the lithium manganese composite oxide can be further stabilized to a cubic rock salt type. The reducing agent can be used without particular limitation as long as it decomposes and absorbs oxygen during a hydrothermal reaction, and specific examples thereof include sodium sulfite, potassium sulfite, ammonium sulfite and hydrates thereof. . These reducing agents can be used singly or in combination of two or more.

  The concentration of the reducing agent is preferably about 0.1 to 10 mol / l, more preferably about 0.5 to 5 mol / l.

  About pH of the aqueous solution at the time of performing a hydrothermal reaction, it is usually preferable to set it as about pH8 or more, and it is more preferable to set it as about pH11 or more.

When the aqueous solution containing the precipitate and the aqueous lithium compound is under alkaline conditions, it may be heated as it is, but when the pH value is low, for example, an alkali metal hydroxide such as potassium hydroxide or sodium hydroxide. In addition, ammonia may be added to increase the pH value.
Hydrothermal reaction can be performed using a normal hydrothermal reaction apparatus (for example, a commercially available autoclave).

  Hydrothermal reaction conditions are not particularly limited, but may be usually about 100 to 300 ° C. and about 0.1 to 150 hours, preferably about 150 to 250 ° C. and about 1 to 100 hours.

  After completion of the hydrothermal reaction, the reaction product is usually washed in order to remove the remaining lithium compound and the like. For washing, for example, water, a water-alcohol mixed solution, alcohol, acetone, or the like can be used. Next, the product is filtered and dried at a temperature of 80 ° C. or higher (usually about 100 ° C.) to obtain the target lithium manganese composite oxide.

  After obtaining the lithium manganese composite oxide by the above-described method, if necessary, the obtained lithium manganese composite oxide is calcined with a lithium compound to control the Li content and powder characteristics. be able to.

  The lithium compound used in the firing step can be used without particular limitation as long as it is a compound containing lithium element. Specific examples include lithium salts such as lithium chloride, lithium nitrate, and lithium acetate, lithium hydroxide, and hydrates thereof. Can be mentioned. These lithium compounds can be used singly or in combination of two or more. The usage-amount of a lithium compound should just be about 0.01-2 mol with respect to 1 mol of lithium manganese complex oxide obtained by the hydrothermal method.

  Usually, in order to improve the reactivity, it is preferable to disperse and stir the lithium manganese composite oxide obtained by the hydrothermal method in an aqueous solution in which a lithium compound is dissolved, dry it, pulverize it, and fire it. As for the degree of pulverization, it is sufficient that coarse particles are not included and the mixture has a uniform color tone.

  The lithium compound can be used in the form of a powder, an aqueous solution, or the like, but is preferably used in the form of an aqueous solution in order to ensure the uniformity of the reaction. In this case, the concentration of the aqueous solution is usually about 0.1 to 10 mol / l.

  Regarding the method of firing in the presence of a lithium compound, a relatively low temperature is preferable for stabilizing the cubic rock salt structure. Usually, after adding and mixing the above-mentioned lithium compound to the lithium manganese based composite oxide obtained by the hydrothermal method, it is heated and dried at a temperature of 80 ° C. or higher, preferably about 100 ° C., and pulverized. What is necessary is just to bake. The specific firing temperature range varies depending on the composition of the target composite oxide, but can usually be about 150 to 650 ° C. However, when obtaining a complex oxide having a high content of Mn element, a crystal phase having a layered rock-salt structure tends to occur when the firing temperature is increased. For this reason, when obtaining a complex oxide having a relatively high content of Mn element, it is preferable to set the firing temperature to about 550 ° C. or less in order to suppress the appearance of the crystal phase of the layered rock salt structure.

  The atmosphere during firing may be any of air, inert atmosphere, and oxidizing atmosphere. The firing time is preferably about 0.1 to 100 hours including the time to reach the firing temperature, and more preferably about 0.5 to 60 hours.

  By baking by the above-described method, it is possible to control the Li content, powder characteristics, and the like of the target lithium manganese composite oxide. For example, the lithium content in the lithium manganese composite oxide can be adjusted by appropriately setting the amount of the lithium compound added during firing. Moreover, the particle size of the lithium manganese composite oxide can be increased by increasing the firing temperature.

  (Ii) The second method of producing a lithium manganese composite oxide using a hydrothermal reaction is similar to the first method in that a metal compound that is a source of generation of iron ions, manganese ions, and titanium ions is used. The dissolved mixed solution is made alkaline to form a precipitate, and then a water-soluble lithium compound and an oxidizing agent are added thereto, hydrothermally treated under alkaline conditions, and then the obtained lithium manganese composite oxide is converted to lithium. It is a method including the process of baking in a reducing atmosphere with a compound.

This method is different from the first method in that hydrothermal treatment is performed in the presence of an oxidizing agent. When hydrothermal treatment is performed in the presence of an oxidizing agent, it is possible to suppress by-production of orthorhombic LiMnO ₂ , which is an undesirable impurity phase in terms of charge / discharge characteristics.

  The oxidizing agent can be used without particular limitation as long as it decomposes during hydrothermal reaction and generates oxygen. Specific examples include potassium chlorate, lithium chlorate, lithium perchlorate, sodium chlorate, hydrogen peroxide. Water etc. can be mentioned. An oxidizing agent can be used individually by 1 type or in mixture of 2 or more types. The concentration of the oxidizing agent is preferably about 0.1 to 10 mol / l, and more preferably about 0.5 to 5 mol / l.

  In the second method, except for conducting hydrothermal treatment using a precipitate containing iron, manganese, and titanium and using an aqueous solution in which an oxidizing agent and water-soluble lithium are added, the other conditions are the same as the water in the first method. Same as heat treatment.

  After the hydrothermal treatment by the method described above, the obtained lithium-manganese composite oxide is calcined together with the lithium compound in a reducing atmosphere, so that the crystal phase of the target cubic rock salt structure is obtained as a main crystal. A lithium manganese composite oxide as a phase can be obtained.

  In the second method, as the lithium compound, the same compound as in the first method can be used, and the amount used may be the same as in the first method.

  The method for firing in a reducing atmosphere is not particularly limited. For example, firing in a reducing atmosphere is possible by firing in an inert atmosphere in the presence of an organic substance, carbon powder, or the like.

  There are no particular limitations on the organic material, and any carbon-containing compound that can be decomposed into a reducing atmosphere at the firing temperature described below can be used. In particular, when a water-soluble organic substance is used, it is advantageous because it can be dispersed and mixed with the lithium manganese composite oxide powder in an aqueous solution state. Specific examples of such organic substances include sucrose, glucose, starch, acetic acid, citric acid, oxalic acid, benzoic acid, aminoacetic acid and the like. Further, an organic lithium salt such as lithium acetate and a hydrate thereof may be used.

  As the carbon powder, for example, carbon powder obtained by thermal decomposition of an organic substance, for example, graphite, acetylene black, or the like can be used.

  The above organic substances and carbon powders can be used singly or in combination of two or more.

  The amount of at least one component selected from the group consisting of organic matter and carbon powder (hereinafter sometimes referred to as “organic matter etc.”) is 0.001 times in terms of the molar amount of carbon relative to lithium manganese complex oxide. It is preferable to be about ˜5 times mole, and more preferably about 0.01 times to 1 times mole. When used as an aqueous solution, the concentration of the organic substance or the like may be appropriately determined so as to be within the above-mentioned range of use amount.

  The method for firing in the presence of an organic substance or the like is not particularly limited. For example, the lithium manganese-based composite oxide obtained by a hydrothermal method is mixed with the lithium compound and the organic substance described above, and then mixed at 80 ° C. Heat drying at the above temperature, preferably about 100 ° C., pulverization, and firing may be performed. The firing temperature is preferably about 150 to 1200 ° C, more preferably about 200 to 1000 ° C.

  The atmosphere at the time of firing may be an inert gas atmosphere such as in nitrogen gas so that a strong reducing atmosphere is obtained by decomposition of organic matter or the like. The firing time is preferably about 0.1 to 100 hours including the time to reach the firing temperature, and more preferably about 0.5 to 60 hours. By baking by the above-described method, it is possible to control the Li content, powder characteristics, and the like of the lithium manganese composite oxide while maintaining the cubic rock salt structure. For example, the lithium content in the lithium manganese composite oxide can be adjusted by appropriately setting the amount of the lithium compound added during firing. Moreover, the particle size of the lithium manganese composite oxide can be increased by increasing the firing temperature. Furthermore, it is possible to stabilize the cubic rock salt structure to a higher temperature by increasing the amount of organic matter added.

  The firing process described above may be a two-stage firing process in which a lithium compound is added to the lithium manganese composite oxide and fired, followed by firing in a reducing atmosphere. When performing a two-stage firing process, the Li content, Mn valence, powder characteristics, and the like can be controlled more precisely.

  In this case, with respect to the first stage baking treatment performed by adding the lithium compound to the lithium manganese composite oxide, the amount of the lithium compound used may be the same as the above baking treatment. As for the conditions for the first stage baking treatment, any atmosphere such as air, oxidizing atmosphere, inert atmosphere, reducing atmosphere, etc. can be selected as the firing atmosphere. The firing temperature is preferably about 200 to 1200 ° C, more preferably about 300 to 1000 ° C. The firing time is preferably about 0.1 to 100 hours including the time to reach the firing temperature, and more preferably about 0.5 to 60 hours.

  After the first stage baking process is performed by the above-described method, the second stage baking process may be performed in a reducing atmosphere. The conditions for the second stage baking treatment may be the same as those in the case where the above-described lithium compound is added and the baking treatment is performed in a reducing atmosphere.

  After obtaining the lithium manganese composite oxide by the first method or the second method described above, the fired product is usually subjected to a water washing treatment, a solvent washing treatment or the like in order to remove excess lithium compounds. Thereafter, filtration may be performed and, for example, heat drying may be performed at a temperature of 80 ° C. or higher, preferably about 100 ° C.

  Furthermore, if necessary, the heat-dried product is pulverized, added with a lithium compound, organic matter, etc., fired, washed, and dried to repeat the series of operations. The characteristics (stable charge / discharge characteristics in the operating voltage range as a positive electrode material for a lithium ion secondary battery, high capacity, etc.) can be further improved.

Lithium Ion Secondary Battery A lithium ion secondary battery using the lithium manganese composite oxide of the present invention can be produced by a known method. For example, the lithium manganese composite oxide of the present invention is used as a positive electrode active material, and a known metal lithium, carbon-based material (activated carbon, graphite), silicon, silicon oxide, or the like is used as a negative electrode material. Using a solution (organic electrolyte) in which a lithium salt such as lithium perchlorate or LiPF ₆ is dissolved in a mixed solvent of known ethylene carbonate, dimethyl carbonate, diethyl carbonate, etc., and other known battery components And a lithium ion secondary battery may be assembled according to a conventional method.

According to the present invention, by using inexpensive raw materials and elements, the average discharge voltage can be maintained at 3 V or higher, and the discharge capacity (180 mAh / g or higher) and weight equal to or higher than those of the lithium cobalt oxide-based positive electrode material. A novel composite oxide having an energy density (550 mWh / g or more) and useful as a positive electrode material can be obtained.

  Unlike the conventional positive electrode material, the lithium manganese composite oxide of the present invention has such a large capacity, and the discharge curve gradually decreases toward the end-of-discharge voltage (2.0 V or 1.5 V). This is due to the shape, and by reducing the discharge end voltage to about 2.0V or 1.5V, it is possible to easily realize a large capacity, and large lithium ions not only for small consumer use but also for automotive use. It is extremely useful as a positive electrode material for secondary batteries.

  In particular, the composite oxide of the present invention is characterized by high initial charge / discharge efficiency (70% or more) as compared with a conventional composite oxide having the same composition. For this reason, the amount of negative electrode material required to obtain a predetermined initial discharge amount can be reduced, and in addition to the contribution of the high energy density of the substance itself, the energy density of the battery can be improved by reducing the negative electrode amount. .

  The lithium manganese composite oxide according to the present invention has the above-described excellent performance, and is extremely useful as a positive electrode material for a lithium ion secondary battery having a high capacity and a low cost.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a drawing schematically showing a crystal structure of a crystal layer (α-LiFeO ₂ ) having a cubic rock salt structure, which is a main crystal structure of the lithium manganese composite oxide of the present invention. The X-ray diffraction pattern of the sample obtained in Example 1 and Comparative Example 1. The charging / discharging curve at room temperature (5 mg of active materials) of the lithium ion secondary battery which used the sample obtained in Example 1 or Comparative Example 1 as a positive electrode active material. The charge / discharge curve (active material amount 20 mg) at room temperature of the lithium ion secondary battery which used the sample obtained in Example 1 or Comparative Example 1 as a positive electrode active material. The discharge curve (active material amount 5 mg) in two different current densities about the lithium ion secondary battery which used the sample obtained in Example 1 or Comparative Example 1 as a positive electrode active material. The X-ray diffraction pattern of the sample obtained in Example 2 and Comparative Example 2. The charge-discharge curve at room temperature of the lithium ion secondary battery which used the sample obtained in Example 2 or Comparative Example 2 as a positive electrode active material (active material amount 5 mg). The X-ray diffraction pattern of the sample obtained in Example 3 and Comparative Example 3. The charge-discharge curve at room temperature of the lithium ion secondary battery which used the sample obtained in Example 3 or Comparative Example 3 as a positive electrode active material (active material amount 5 mg). The X-ray diffraction pattern of the sample obtained in Example 4 and Comparative Example 4. The charging / discharging curve at room temperature (5 mg of active materials) of the lithium ion secondary battery which used the sample obtained in Example 4 or Comparative Example 4 as a positive electrode active material. The X-ray diffraction pattern of the sample obtained in Example 5 and Comparative Example 5. The charge-discharge curve at room temperature (5 mg of active materials) of the lithium ion secondary battery which used the sample obtained in Example 5 or Comparative Example 5 as a positive electrode active material.

  Hereinafter, examples and comparative examples will be shown to further clarify the features of the present invention.

Example 1
Iron (II) chloride tetrahydrate 19.88 g, 30% titanium sulfate (IV) aqueous solution 80.00 g, and manganese (II) chloride tetrahydrate 9.90 g (total 0.25 mol, Fe: Ti: Mn molar ratio = 4: 4: 2) was added to 500 ml of distilled water and completely dissolved. An aqueous lithium hydroxide solution (a solution in which 60 g of anhydrous lithium hydroxide was dissolved in 1000 ml of distilled water) was prepared in another beaker. This lithium hydroxide aqueous solution was placed in a titanium beaker and stirred. While stirring this lithium hydroxide aqueous solution, the above metal salt aqueous solution was gradually added dropwise over 2 to 3 hours at room temperature to form an Fe—Ti—Mn precipitate. It was confirmed that the reaction solution was completely alkaline (pH 11 or more), and under stirring, air was blown into the reaction solution containing the coprecipitate at room temperature for 1 day to wet oxidize the precipitate. .

  The obtained precipitate was washed with distilled water and filtered, and this precipitated product was placed in a polytetrafluoroethylene beaker together with 50 g of lithium hydroxide monohydrate, 309 g of potassium hydroxide and 600 ml of distilled water. Stir. The pH of this aqueous solution was 11 or more. Thereafter, it was placed in a hydrothermal reactor (autoclave) and hydrothermally treated at 220 ° C. for 5 hours.

  After the hydrothermal treatment is completed, the reaction furnace is cooled to near room temperature, the beaker containing the hydrothermal treatment reaction solution is taken out of the autoclave, and the generated precipitate is washed with distilled water to remove excess lithium hydroxide and the like. Salts were removed. Next, the powder (lithium manganese composite oxide) obtained by filtration was added to a lithium hydroxide aqueous solution in which 5.25 g of lithium hydroxide monohydrate was dissolved in 100 ml of distilled water, and dispersed while stirring. After mixing and stirring, dried at 100 ° C. overnight and pulverized to produce a powder. Next, the temperature of the obtained powder is raised to 600 ° C. in an oxygen stream over one hour, then calcined in oxygen at that temperature for 20 hours, and then cooled to near room temperature in a furnace to remove excess lithium salt. The fired product was washed with distilled water, filtered, and dried to obtain a powdery product (lithium manganese composite oxide).

Comparative Example 1
In the same manner as in Example 1, it was carried out from precipitation preparation, hydrothermal treatment, addition of lithium hydroxide before firing, drying and pulverization, and then the temperature of the obtained powder was raised to 700 ° C. in oxygen for 1 hour, Baked in oxygen for 20 hours, cooled to near room temperature in a furnace, washed the baked product with distilled water to remove excess lithium salt, filtered and dried to obtain a powdered product .

Results of X-ray diffraction analysis FIG. 2 shows X-ray diffraction (XRD) diagrams of the powder products obtained in Example 1 and Comparative Example 1. Rietveld analysis was performed on these XRD patterns using the analysis program RIETAN-2000 (F. Izumi and T. Ikeda, Mater. Sci. Forum, vol.321-324 p.198-203 (2000).) The crystallographic parameters shown in Table 1 were calculated.

From FIG. 2, the sample obtained in Example 1 has only peaks derived from the crystal phase of cubic rock salt type (α-LiFeO ₂ type) structure, whereas the sample obtained in Comparative Example 1 A peak (▼) derived from the crystal phase of the monoclinic layered rock salt type (Li ₂ MnO ₃ type) structure was also observed. The broad peak observed in the vicinity of 2θ = 20 ° of the sample obtained in Example 1 is a short-range ordered arrangement in the cubic rock salt type crystal phase (111 superlattice lines corresponding to twice the lattice constant). (JM Cowley, Acta Cryst., A29 537-541 (1973).) And M. Tabuchi, K. Ado, H. Sakaebe, C. Masquelier, H. Kageyama and O. Nakamura , Solid State Ionics, 79, 220-226 (1995).).

From Table 1 above, the sample obtained in Example 1 consists only of a crystal phase having a cubic rock salt type (α-LiFeO ₂ ) structure, whereas the sample obtained in Comparative Example 1 is a cubic rock salt. It was confirmed that the crystal phase of the monoclinic layered rock salt type (Li ₂ MnO ₃ type) was included in addition to the crystal phase of the type structure.

Chemical composition and powder properties
The chemical composition of the powder products obtained in Example 1 and Comparative Example 1 was determined using ICP emission analysis, and the specific surface areas of these samples were determined using a BET specific surface area meter. The results are shown in Table 2 below.

As is clear from Table 2, the powder products obtained in Example 1 and Comparative Example 1 were within the range of the composite oxide of the present invention with respect to the x value, m value, and n value in the composition formula. In addition, about the primary particle size, it is thought that the sample obtained in Example 1 is smaller from the measured value of the specific surface area.

Evaluation of charge / discharge characteristics (Charge / discharge cycle characteristics at room temperature (active material amount 5mg))
Using the sample obtained in Example 1 or the sample obtained in Comparative Example 1 as a positive electrode active material, a lithium ion secondary battery having the following configuration was prepared, and a charge / discharge test was performed according to the following charge / discharge test conditions. went. The results are shown in FIG.
Battery configuration:
Positive electrode: Active material 5mg + AB5mg + PTFE0.5mg mixed and crimped on Al mesh,
Negative electrode: metallic lithium,
Electrolyte: LiPF ₆ dissolved in EC + DMC solvent.
AB: Acetylene black, PTFE: Polytetrafluoroethylene, EC: Ethylene carbonate, DMC: Dimethyl carbonate charge / discharge test conditions:
Test temperature: 30 ° C, current density (per active material): 40mA / g,
Potential range: 1.5-4.8V (constant current up to 5.0V only for initial charge-constant voltage charge (until it drops to 10mA / g))

  As apparent from FIG. 3 and Table 3, the sample obtained in Example 1 had a higher initial average discharge voltage than the sample obtained in Comparative Example 1, and further had an initial charge / discharge capacity and initial charge / discharge. It is clear that the efficiency, initial discharge energy density, and discharge capacity after 20 cycles are all large values and have excellent charge / discharge characteristics.

Evaluation of charge / discharge characteristics (Charge / discharge cycle characteristics at room temperature (active material amount 20mg))
Using the sample obtained in Example 1 and the sample obtained in Comparative Example 1 as the positive electrode active material, the active material amount was 20 mg, and a lithium ion secondary battery for testing having the following configuration was prepared. The charge / discharge test was conducted according to the charge / discharge test conditions shown. The results are shown in FIG.
Battery configuration:
Positive electrode: Active material 20mg + AB5mg + PTFE 0.5mg mixed and crimped on Al mesh Negative electrode: metallic lithium,
Electrolyte: LiPF ₆ dissolved in EC + DMC solvent.
Charging / discharging test conditions:
Test temperature: 30 ° C, current density (per active material): 40mA / g,
Potential range: 1.5-4.8V (constant current up to 5.0V only for initial charge-constant voltage charge (until it drops to 10mA / g))

  As is apparent from FIG. 4 and Table 4, the sample obtained in Example 1 has a slightly lower initial charge capacity and the same average discharge voltage when compared with the sample obtained in Comparative Example 1. However, the initial charge / discharge capacity, the initial charge / discharge efficiency, the initial discharge energy density, and the discharge capacity after 20 cycles were all large values. For this reason, even if it was a case where the amount of active materials corresponding to the energy density improvement of a battery was increased to 20 mg, it has confirmed that the sample obtained in Example 1 can exhibit the outstanding charging / discharging characteristic.

Evaluation of charge / discharge characteristics (discharge rate characteristics at room temperature (active material amount 5mg))
A secondary battery having the same structure as that in the case of the active material amount of 5 mg in the charge / discharge characteristic evaluation method described above was produced, and a charge / discharge test was performed under the following conditions. The results are shown in Table 5 below and FIG.
Charging / discharging test conditions:
Test temperature: 30 ℃
Current density (per active material): 40 mA / g (during charging), 120 mA / g or 600 mA / g (during discharging)
Potential range: 1.5-4.8V (constant current up to 5.0V only for initial charge-constant voltage charge (until it drops to 10mA / g))

  As apparent from FIG. 5 and Table 5, in the discharge test result at a high current density of 120 mA / g or 600 mA / g, the sample obtained in Example 1 is compared with the sample obtained in Comparative Example 1. It can be seen that the average discharge voltage is equal to or higher and the discharge capacity is increased.

  As is clear from this result, the sample obtained in Example 1 consisting only of the cubic rock salt type crystal phase is compared with that obtained in Comparative Example 1 containing about 30% by weight of monoclinic layered rock salt type crystal phase. Thus, it can be seen that the charge / discharge characteristics such as the initial charge / discharge efficiency are excellent.

Example 2
Add 120.00 g of 30% titanium sulfate (IV) aqueous solution and 19.79 g of manganese chloride (II) tetrahydrate (total amount 0.25 mol, Ti: Mn molar ratio = 6: 4) to 500 ml of distilled water and dissolve completely I let you. An aqueous lithium hydroxide solution (a solution in which 60 g of anhydrous lithium hydroxide was dissolved in 1000 ml of distilled water) was prepared in another beaker. This lithium hydroxide aqueous solution was placed in a titanium beaker and stirred. While stirring the lithium hydroxide aqueous solution, the metal salt aqueous solution was gradually dropped at room temperature over 2 to 3 hours to form a Ti-Mn precipitate. After confirming that the reaction solution was completely alkaline (pH 11 or more), the reaction solution containing the coprecipitate was blown with air at room temperature for 1 day with stirring to ripen the precipitate.

  The resulting precipitate was washed with distilled water and filtered, and the precipitated product was mixed with 50 g of lithium hydroxide monohydrate, 309 g of potassium hydroxide, 50 g of sodium sulfite heptahydrate, and 600 ml of distilled water. It put in the tetrafluoroethylene beaker and stirred well. The pH of this aqueous solution was 11 or more. Thereafter, it was placed in a hydrothermal reactor (autoclave) and hydrothermally treated at 220 ° C. for 5 hours.

  After the hydrothermal treatment is completed, the reaction furnace is cooled to near room temperature, the beaker containing the hydrothermal treatment reaction solution is taken out of the autoclave, and the generated precipitate is washed with distilled water to remove excess lithium hydroxide and the like. Salts were removed to obtain a powdery product (lithium manganese composite oxide).

Comparative Example 2
The steps from precipitation preparation, hydrothermal treatment, and subsequent water washing treatment and filtration were carried out in the same manner as in Example 2. Then, the powder (lithium manganese composite oxide) obtained by filtration was mixed with lithium hydroxide monohydrate 5.25. g was added to an aqueous lithium hydroxide solution dissolved in 100 ml of distilled water, dispersed and mixed with stirring, dried after stirring overnight at 100 ° C., and pulverized to prepare a powder.

  Next, the temperature of the obtained powder is raised to 600 ° C. in a nitrogen stream for 1 hour, then calcined in nitrogen at that temperature for 20 hours, cooled to near room temperature in the furnace, and then the excess lithium salt is removed. Therefore, the fired product was washed with distilled water, filtered and dried to obtain a powdery product (lithium manganese composite oxide).

Results by X-ray diffraction analysis FIG. 6 shows X-ray diffraction (XRD) diagrams of the powder products obtained in Example 2 and Comparative Example 2. Rietveld analysis was performed on these XRD patterns using the analysis program RIETAN-2000 (F. Izumi and T. Ikeda, Mater. Sci. Forum, vol. 321-324 p.198-203 (2000).) The crystallographic parameters shown in Table 6 below were calculated.

From FIG. 6, in the sample obtained in Example 2, only the peak derived from the crystal phase of the cubic rock salt type (Li ₂ TiO ₃ ) structure is observed, whereas the sample obtained in Comparative Example 1 is A peak (▼) derived from the crystal phase of the monoclinic layered rock salt type (Li ₂ MnO ₃ ) was also observed, confirming that it coexists with the crystal phase of the cubic rock salt type. The broad peak observed near 2θ = 20 ° of the sample obtained in Example 2 is a short-range order component derived from the cubic rock salt type crystal phase (twice the lattice constant) as in the sample of Example 1. (Corresponding to 111 planes).

From Table 6 above, the sample obtained in Example 2 consists only of a cubic rock salt type crystal phase, whereas the sample obtained in Comparative Example 2 is monoclinic in addition to the cubic rock salt type crystal phase. It was confirmed that it contained 47% by weight of crystal phase of crystal layered rock salt type (Li ₂ MnO ₃ type).

Evaluation of chemical composition and powder properties
The chemical composition of each powder product obtained in Example 2 and Comparative Example 2 was determined using ICP emission analysis, and the specific surface areas of these samples were determined using a BET specific surface area meter. The results are shown in Table 7.

  As is apparent from Table 7, the powder products obtained in Example 2 and Comparative Example 2 were within the range of the composite oxide of the present invention in terms of x value and n value in the composition formula. In addition, about a primary particle size, it is thought that the sample obtained in Example 2 is smaller from the measured value of a specific surface area.

Evaluation of charge / discharge characteristics (Charge / discharge cycle characteristics at room temperature (active material amount 5mg))
A lithium ion secondary battery was prepared in the same manner as in Example 1 except that the sample obtained in Example 2 or Comparative Example 2 was used as the positive electrode active material, and the amount of the positive electrode active material was 5 mg. A charge / discharge test was performed according to the test conditions. The results are shown in FIG.
Charging / discharging test conditions:
Test temperature: 30 ° C, current density (per active material): 40mA / g
Potential range: 1.5-4.8V (constant current up to 5.0V only for initial charge-constant voltage charge (until it drops to 10mA / g))

  As is apparent from FIG. 7 and Table 8, the sample obtained in Example 2 has the same initial average discharge voltage as compared with the sample obtained in Comparative Example 2, but the initial charge / discharge efficiency is large. It is clear that it has improved.

  From this result, the initial charge / discharge efficiency of the sample obtained in Example 2 consisting only of the cubic rock salt type crystal phase is higher than that of the sample obtained in Comparative Example 2 in which the monoclinic layered rock salt type crystal phase coexists. From this point of view, it was confirmed to be excellent.

Example 3
60.60 g of iron (III) nitrate nonahydrate and 15.80 g of potassium permanganate (total amount 0.25 mol, Fe: Mn molar ratio = 6: 4) were added to 700 ml of distilled water and completely dissolved. A lithium hydroxide solution (a solution in which 60 g of anhydrous lithium hydroxide and 200 ml of ethanol were dissolved in 1000 ml of distilled water) was prepared in another beaker. This lithium hydroxide solution was placed in a titanium beaker and stirred. While stirring this lithium hydroxide solution, the aqueous metal salt solution was gradually added dropwise at room temperature over 2 to 3 hours to form an Fe-Mn precipitate. After confirming that the reaction solution was completely alkaline (pH 11 or more), the reaction solution containing a coprecipitate was blown with air at room temperature for 1 day with stirring to ripen the precipitate.

  The resulting precipitate was washed with distilled water and filtered, and this precipitated product was placed in a polytetrafluoroethylene beaker together with 50 g of lithium hydroxide monohydrate, 50 g of potassium chlorate and 600 ml of distilled water. Stir. The pH of this aqueous solution was 11 or more. Thereafter, it was placed in a hydrothermal reactor (autoclave) and hydrothermally treated at 220 ° C. for 5 hours.

  After the hydrothermal treatment is completed, the reaction furnace is cooled to near room temperature, the beaker containing the hydrothermal treatment reaction solution is taken out of the autoclave, and the generated precipitate is washed with distilled water to remove excess lithium hydroxide and the like. Salts were removed. The powder (lithium manganese composite oxide) obtained by filtration was added to a lithium hydroxide-sucrose aqueous solution in which 5.25 g of lithium hydroxide monohydrate and 0.71 g of sucrose were dissolved in 100 ml of distilled water. Then, the mixture was dispersed and mixed with stirring, and after stirring, dried at 100 ° C. overnight and pulverized to prepare a powder. Next, the temperature of the obtained powder is raised to 500 ° C. in a nitrogen stream over 3 hours, then calcined at that temperature in nitrogen for 1 hour, and then cooled to near room temperature in the furnace to remove excess lithium salt and the like. For this purpose, the fired product was washed with distilled water, filtered and dried to obtain a powdery product (lithium manganese composite oxide).

Comparative Example 3
60.60 g of iron (III) nitrate nonahydrate and 19.79 g of manganese chloride tetrahydrate (total amount 0.25 mol, Fe: Mn molar ratio = 6: 4) were added to 500 ml of distilled water and completely dissolved. . A lithium hydroxide solution (a solution in which 50 g of lithium hydroxide monohydrate and 150 ml of ethanol were dissolved in 500 ml of distilled water) was prepared in another beaker. This lithium hydroxide solution was placed in a titanium beaker, stirred, and allowed to stand in a thermostatic chamber cooled to −10 ° C. After confirming that the solution was cooled to −10 ° C., the aqueous metal salt solution was gradually added dropwise to the stirred lithium hydroxide solution over 2 to 3 hours to form an Fe—Mn precipitate. After confirming that the reaction solution was completely alkaline (pH 11 or higher), air was blown into the reaction solution containing the coprecipitate under stirring at room temperature for 2 days to ripen the precipitate.

  The obtained precipitate was washed with distilled water and filtered, and this precipitated product was mixed with 50 g of lithium hydroxide monohydrate, 309 g of potassium hydroxide, 50 g of potassium chlorate and 400 ml of distilled water, and a polytetrafluoroethylene beaker. Placed in and stirred well. The pH of this aqueous solution was 11 or more. Thereafter, it was placed in a hydrothermal reactor (autoclave) and hydrothermally treated at 220 ° C. for 48 hours.

  After the hydrothermal treatment is completed, the reaction furnace is cooled to near room temperature, the beaker containing the hydrothermal treatment reaction solution is taken out of the autoclave, and the generated precipitate is washed with distilled water to remove excess lithium hydroxide and the like. Salts were removed. The powder (lithium manganese composite oxide) obtained by filtration was added to a lithium hydroxide aqueous solution in which 5.25 g of lithium hydroxide monohydrate was dissolved in 100 ml of distilled water, and dispersed and mixed while stirring. After stirring, the powder was dried overnight at 100 ° C. and pulverized to produce a powder.

  Next, the temperature of the obtained powder is raised to 700 ° C. in the air over 1 hour, then calcined in the air at that temperature for 20 hours, and then cooled to near room temperature in the furnace to remove excess lithium salt and the like. For this purpose, the fired product was washed with distilled water, filtered and dried to obtain a powdery product (lithium manganese composite oxide).

X-Ray Diffraction Results FIG. 8 shows X-ray diffraction (XRD) diagrams of the powder products obtained in Example 3 and Comparative Example 3. Rietveld analysis was performed on these XRD patterns using the analysis program RIETAN-2000 (F. Izumi and T. Ikeda, Mater. Sci. Forum, vol.321-324 p.198-203 (2000).) The crystallographic parameters shown in Table 9 were calculated.

From FIG. 8, in the sample obtained in Example 3, only the peak derived from the crystal phase of the cubic rock salt type (α-LiFeO ₂ type) structure is observed, whereas the sample obtained in Comparative Example 3 A peak (▼) derived from the crystal phase of the monoclinic layered rock salt type (Li ₂ MnO ₃ type) structure was also observed. The broad peak observed around 2θ = 20 ° of the sample obtained in Example 3 is a short-range ordered arrangement (twice the lattice constant) in the cubic rock salt type crystal phase as in the sample of Example 1. This is a component derived from a superlattice line equivalent to 111).

  From the above, the sample obtained in Example 3 consists only of the crystal phase of the cubic rock salt structure, whereas the sample obtained in Comparative Example 3 is monoclinic in addition to the crystal phase of the cubic rock salt type. It was confirmed that the crystal phase of the crystal rock salt type layered structure was 35% by weight.

Chemical composition and powder properties
The chemical composition of each sample obtained in Example 3 and Comparative Example 3 was determined using ICP emission analysis, and the specific surface areas of both samples were determined using a BET specific surface area meter. The results are shown in Table 10 below.

  As is apparent from Table 10, the powder products obtained in Example 3 and Comparative Example 3 were within the composition range of the composite oxide of the present invention with respect to the x value and m value in the composition formula. In addition, since the sample obtained in Example 3 has a larger specific surface area than the sample obtained in Comparative Example 3, it is considered that the primary particles are small.

Evaluation of charge / discharge characteristics (Charge / discharge cycle characteristics at room temperature (active material amount 5mg))
Except for using the sample obtained in Example 3 or Comparative Example 3 as the positive electrode active material, a lithium ion secondary battery was prepared in the same manner as in Example 1 with the amount of the positive electrode active material set to 5 mg. A charge / discharge test was performed according to the discharge test conditions. The results are shown in Table 11 below and FIG. The discharge capacity retention rate (%) after 10 cycles is expressed by (discharge capacity after 10 cycles) × 100 / (initial discharge capacity).
Charging / discharging test conditions:
Test temperature: 30 ° C, current density (per active material): 40mA / g
Potential range: 2.0-4.8V (Charging only Constant current up to 4.8V-Constant voltage charging (until it drops to 10mA / g))

As is clear from FIG. 9 and Table 11, the sample obtained in Example 3 has almost the same discharge capacity after 10 cycles and the initial discharge energy density as compared with the sample obtained in Comparative Example 3. It can be seen that the initial charge / discharge efficiency and the initial discharge capacity are improved.
From this result, the sample obtained in Example 3 consisting only of the cubic rock salt type crystal phase has a higher initial charge / discharge efficiency than the sample obtained in Comparative Example 3 containing the monoclinic layered rock salt type crystal phase. It was confirmed that it was excellent from the viewpoint.

Example 4
Add 120.00 g of 30% aqueous solution of titanium (IV) sulfate and 19.79 g of manganese (II) chloride tetrahydrate (total amount 0.25 mol, Ti: Mn molar ratio = 6: 4) to 500 ml of distilled water and dissolve completely. I let you. A lithium hydroxide solution (an aqueous solution in which 60 g of anhydrous lithium hydroxide was dissolved in 1000 ml of distilled water) was prepared in another beaker. This lithium hydroxide solution was placed in a titanium beaker and stirred. While stirring the lithium hydroxide solution, the metal salt aqueous solution was gradually added dropwise at room temperature over 2 to 3 hours to form a Ti-Mn precipitate. After confirming that the reaction solution was completely alkaline (pH 11 or more), the reaction solution containing a coprecipitate was blown with air at room temperature for 1 day with stirring to ripen the precipitate.

  The resulting precipitate was washed with distilled water and filtered, and the precipitated product was placed in a polytetrafluoroethylene beaker with 50 g of lithium hydroxide monohydrate, 50 g of potassium chlorate and 600 ml of distilled water, and stirred well. did. The pH of this aqueous solution was 11 or more. Thereafter, it was placed in a hydrothermal reactor (autoclave) and hydrothermally treated at 220 ° C. for 5 hours.

  After the hydrothermal treatment is completed, the reaction furnace is cooled to near room temperature, the beaker containing the hydrothermal treatment reaction solution is taken out of the autoclave, and the generated precipitate is washed with distilled water to remove excess lithium hydroxide and the like. Salts were removed. The powder (lithium manganese composite oxide) obtained by filtration was added to a lithium hydroxide-sucrose aqueous solution in which 5.25 g of lithium hydroxide monohydrate and 0.71 g of sucrose were dissolved in 100 ml of distilled water. Then, the mixture was dispersed and mixed with stirring, and after stirring, dried at 100 ° C. overnight and pulverized to prepare a powder. Next, the temperature of the obtained powder is raised to 600 ° C. in a nitrogen stream over 3 hours, then calcined in nitrogen at that temperature for 1 hour, and then cooled to near room temperature in the furnace to remove excess lithium salt and the like. For this purpose, the fired product was washed with distilled water, filtered and dried to obtain a powdery product (lithium manganese composite oxide).

Comparative Example 4
Except for changing the amount of metal salt used to 30% titanium (IV) sulfate aqueous solution 100.00 g and manganese chloride (II) tetrahydrate 24.74 g (total amount 0.25 mol, Ti: Mn molar ratio = 5: 5) In the same manner as in Example 4, Ti-Mn precipitate preparation, aging, hydrothermal treatment, water washing treatment and filtration were performed. The powder (lithium manganese composite oxide) obtained by filtration was added to a lithium hydroxide aqueous solution in which 5.25 g of lithium hydroxide monohydrate was dissolved in 100 ml of distilled water, and dispersed and mixed while stirring. After stirring, the powder was dried overnight at 100 ° C. and pulverized to produce a powder. Next, the temperature of the obtained powder is raised to 650 ° C. in the air for 1 hour, then fired at that temperature in the air for 20 hours, and then cooled to near room temperature in the furnace to remove excess lithium salt and the like. The fired product was washed with distilled water, filtered and dried to obtain a powdery product (lithium manganese composite oxide).

X-ray diffraction results Fig. 10 shows X-ray diffraction (XRD) diagrams of the powder products obtained in Example 4 and Comparative Example 4. Rietveld analysis was performed on these XRD patterns using the analysis program RIETAN-2000 (F. Izumi and T. Ikeda, Mater. Sci. Forum, vol.321-324 p.198-203 (2000).) The crystallographic parameters shown in Table 12 were calculated.

From FIG. 10, in the sample obtained in Example 4, only the peak derived from the crystal phase of the cubic rock salt type (Li ₂ TiO ₃ type) structure is observed, whereas the sample obtained in Comparative Example 4 is A peak (▼) derived from the crystal phase of the monoclinic layered rock salt type (Li ₂ MnO ₃ type) structure was observed. The broad peak (●) observed in the vicinity of 2θ = 20 ° of the sample obtained in Example 4 is a short-range order component derived from the cubic rock salt type crystal phase, as in the sample of Example 1. is there.

From Table 12 above, the sample obtained in Example 4 consists only of a cubic rock salt type crystal phase, whereas the sample obtained in Comparative Example 4 has a cubic phase of the cubic rock salt type structure. It was not included, and it was confirmed that it consisted only of the monoclinic layered rock salt type (Li ₂ MnO ₃ ) crystal phase.

Chemical composition and powder properties
The chemical composition of each sample obtained in Example 4 and Comparative Example 4 was determined using ICP emission analysis, and the specific surface areas of both samples were determined using a BET specific surface area meter. The results are shown in Table 13 below.

  As is apparent from Table 13, the sample obtained in Example 4 was within the composition range of the composite oxide of the present invention with respect to the x value and n value in the composition formula, but was obtained in Comparative Example 4. In the sample, the total value of n value and m value, which is the total amount of Ti and Fe, was outside the composition range of the composite oxide of the present invention. From the measurement results of the specific surface area, it is considered that the sample obtained in Example 4 and the sample obtained in Comparative Example 4 have substantially the same primary particle size.

Evaluation of charge / discharge characteristics (Charge / discharge cycle characteristics at room temperature (active material amount 5mg))
Except for using the sample obtained in Example 4 or Comparative Example 4 as the positive electrode active material, a lithium ion secondary battery was prepared in the same manner as in Example 1 with a positive electrode active material amount of 5 mg. A charge / discharge test was performed according to the discharge test conditions. The results are shown in Table 11 below and FIG. The discharge capacity retention rate (%) after 10 cycles is expressed by (discharge capacity after 10 cycles) × 100 / (initial discharge capacity).
Charging / discharging test conditions:
Test temperature: 30 ° C, current density (per active material): 40mA / g
Potential range: 2.0-4.8V (Charging only Constant current up to 4.8V-Constant voltage charging (until it drops to 10mA / g))

  As is clear from FIG. 11 and Table 14, the sample obtained in Example 4 was compared with the sample obtained in Comparative Example 4, the discharge capacity after 10 cycles, the discharge capacity retention rate after 10 cycles, and the initial discharge capacity. It can be seen that the initial discharge average voltage and the initial discharge energy density are substantially the same, but the initial charge / discharge efficiency is excellent.

  From this result, the sample obtained in Example 4 consisting only of the cubic rock salt type crystal phase is more in terms of initial charge / discharge efficiency than the sample obtained in Comparative Example 4 consisting only of the layered rock salt type crystal phase. It was confirmed that it was excellent.

Example 5
Distillation of iron (III) nitrate nonahydrate 30.30 g, 30% titanium sulfate aqueous solution 60.00 g and potassium permanganate 15.80 g (total amount 0.25 mol, Fe: Ti: Mn molar ratio = 3: 3: 4) in 700 ml Added to water and completely dissolved. A lithium hydroxide solution (a solution in which 60 g of anhydrous lithium hydroxide and 200 ml of ethanol were dissolved in 1000 ml of distilled water) was prepared in another beaker. This lithium hydroxide solution was placed in a titanium beaker and stirred. While stirring this lithium hydroxide solution, the above metal salt aqueous solution was gradually added dropwise over 2 to 3 hours at room temperature to form a Fe—Ti—Mn precipitate. After confirming that the reaction solution was completely alkaline (pH 11 or more), the reaction solution containing a coprecipitate was blown with air at room temperature for 1 day with stirring to ripen the precipitate.

  The obtained precipitate was washed with distilled water and filtered, and this precipitated product was placed in a polytetrafluoroethylene beaker together with 50 g of lithium hydroxide monohydrate, 50 g of potassium chlorate and 600 ml of distilled water, Stir well. The pH of this aqueous solution was 11 or more. Thereafter, it was placed in a hydrothermal reactor (autoclave) and hydrothermally treated at 220 ° C. for 5 hours.

  After the hydrothermal treatment is completed, the reaction furnace is cooled to near room temperature, the beaker containing the hydrothermal treatment reaction solution is taken out of the autoclave, and the generated precipitate is washed with distilled water to remove excess lithium hydroxide and the like. Salts were removed. The powder (lithium manganese composite oxide) obtained by filtration was added to a lithium hydroxide-sucrose aqueous solution in which 5.25 g of lithium hydroxide monohydrate and 0.71 g of sucrose were dissolved in 100 ml of distilled water. Then, the mixture was dispersed and mixed with stirring, and after stirring, dried at 100 ° C. overnight and pulverized to prepare a powder. Next, the temperature of the obtained powder is raised to 600 ° C. in a nitrogen stream over 3 hours, then calcined in nitrogen at that temperature for 1 hour, and then cooled to near room temperature in the furnace to remove excess lithium salt and the like. For this purpose, the fired product was washed with distilled water, filtered and dried to obtain a powdery product (lithium manganese composite oxide).

Comparative Example 5
500 ml of iron (III) nitrate nonahydrate 20.20 g, 30% titanium sulfate aqueous solution 40.00 g and manganese chloride tetrahydrate 29.69 g (total amount 0.25 mol, Fe: Ti: Mn molar ratio = 2: 2: 6) In distilled water and completely dissolved. A lithium hydroxide solution (a solution in which 60 g of anhydrous lithium hydroxide was dissolved in 1000 ml of distilled water) was prepared in another beaker. This lithium hydroxide solution was placed in a titanium beaker and stirred. While stirring this lithium hydroxide solution, the above metal salt aqueous solution was gradually added dropwise over 2 to 3 hours at room temperature to form a Fe—Ti—Mn precipitate. After confirming that the reaction solution was completely alkaline (pH 11 or more), the reaction solution containing a coprecipitate was blown with air at room temperature for 1 day with stirring to ripen the precipitate.

  The resulting precipitate was washed with distilled water and filtered, and this precipitated product was placed in a polytetrafluoroethylene beaker together with 50 g of lithium hydroxide monohydrate, 50 g of potassium chlorate and 600 ml of distilled water. Stir. The pH of this aqueous solution was 11 or more. Thereafter, it was placed in a hydrothermal reactor (autoclave) and hydrothermally treated at 220 ° C. for 5 hours.

  After the hydrothermal treatment is completed, the reaction furnace is cooled to near room temperature, the beaker containing the hydrothermal treatment reaction solution is taken out of the autoclave, and the generated precipitate is washed with distilled water to remove excess lithium hydroxide and the like. Salts were removed. The powder (lithium manganese composite oxide) obtained by filtration was added to a lithium hydroxide aqueous solution in which 5.25 g of lithium hydroxide monohydrate was dissolved in 100 ml of distilled water, and dispersed and mixed while stirring. After stirring, the powder was dried overnight at 100 ° C. and pulverized to produce a powder. Next, the temperature of the obtained powder is raised to 650 ° C. in the air for 1 hour, then fired at that temperature in the air for 20 hours, and then cooled to near room temperature in the furnace to remove excess lithium salt, etc. The fired product was washed with distilled water, filtered and dried to obtain a powdery product (lithium manganese composite oxide).

X-ray diffraction results Fig. 12 shows X-ray diffraction (XRD) diagrams of the powder products obtained in Example 5 and Comparative Example 5. Rietveld analysis was performed on these XRD patterns using the analysis program RIETAN-2000 (F. Izumi and T. Ikeda, Mater. Sci. Forum, vol.321-324 p.198-203 (2000).) The crystallographic parameters shown in Table 15 were calculated.

From FIG. 12, in the sample obtained in Example 5, only the peak derived from the crystal phase of the cubic rock salt type (Li ₂ TiO ₃ ) structure is recognized, whereas in the sample obtained in Comparative Example 5, A peak (▼) derived from the crystal phase of the monoclinic layered rock salt type (Li ₂ MnO ₃ ) structure was observed. The broad peak (●) observed in the vicinity of 2θ = 20 ° of the sample obtained in Example 5 is the short-range ordered arrangement (lattice constant) in the cubic rock salt type crystal phase as in the sample of Example 1. This is a component derived from a superlattice line equivalent to twice the number of .

From Table 14 above, the sample obtained in Example 5 consists only of a cubic rock salt type crystal phase, whereas the sample obtained in Comparative Example 5 contains a crystal phase of a cubic rock salt type structure. It was confirmed that it consisted only of the monoclinic layered rock salt type (Li ₂ MnO ₃ type) crystal phase.

Chemical composition and powder properties
The chemical composition of each sample obtained in Example 5 and Comparative Example 5 was determined by ICP emission analysis, and the specific surface areas of both samples were determined using a BET specific surface area meter. The results are shown in Table 16 below.

  As is clear from Table 16, the sample obtained in Example 5 had the x value, m value, and n value in the composition formula all within the composition range of the composite oxide of the present invention. For the sample obtained in 5, the total value of m value and n value in the composition formula was outside the composition range of the composite oxide of the present invention. In addition, about the primary particle size, from the measured value of a specific surface area, it is thought that the sample obtained in Example 5 has a smaller value.

Evaluation of charge / discharge characteristics (Charge / discharge cycle characteristics at room temperature (active material amount 5mg))
Except that the sample obtained in Example 5 or Comparative Example 5 was used as the positive electrode active material, a lithium ion secondary battery was produced in the same manner as in Example 1 except that the amount of the positive electrode active material was 5 mg. A charge / discharge test was performed according to the test conditions. The results are shown in FIG.
Charging / discharging test conditions:
Test temperature: 30 ° C, current density (per active material): 40mA / g,
Potential range: 1.5-4.8V (constant current up to 4.8V only for initial charge-constant voltage charge (until it drops to 10mA / g))

  As is apparent from FIG. 13 and Table 17, the sample obtained in Example 5 was inferior in discharge capacity after 10 cycles compared to the sample obtained in Comparative Example 5, and the initial average discharge voltage, initial discharge capacity, The initial discharge energy density is the same, but the initial charge / discharge efficiency is close to 100%, and the initial charge / discharge efficiency of the sample obtained in Comparative Example 5 is 60%. It is clear that

Claims (7)

Composition formula: Li _{1 + x} (Mn _1-mn Fe _m Ti _n ) _1-x O ₂ (0 <x <1/3, 0 ≦ m ≦ 0.70, 0 ≦ n ≦ 0.70, 0.55 ≦ m + n <1 ) is represented by, it a lithium-manganese-based composite oxide, wherein the main crystal phase is a crystal phase of cubic rock-salt type structure,
Lithium manganese in which the ratio of the crystal phase of the cubic rock salt type structure to the crystal phase of the layered rock salt type structure is cubic rock salt type structural crystal phase: layered rock salt type structural crystal phase (weight ratio) = 100: 0 to 93: 7 Complex oxides. At least one compound selected from the group consisting of a titanium compound and an iron compound and a mixed aqueous solution containing a manganese compound are made alkaline to form a precipitate, and the resulting precipitate is combined with a water-soluble lithium compound and the absence of an oxidizing agent. 2. The method for producing a lithium manganese composite oxide according to claim 1, wherein hydrothermal treatment is performed under alkaline conditions. The method for producing a lithium manganese composite oxide according to claim 2 , wherein the aqueous solution used for the hydrothermal treatment further contains a reducing agent. 4. The method for producing a lithium manganese composite oxide according to claim 1, wherein after the hydrothermal treatment is performed by the method of claim 2 or 3 , a firing treatment is performed in the presence of a lithium compound. At least one compound selected from the group consisting of a titanium compound and an iron compound, and a mixed aqueous solution containing a manganese compound is made alkaline to form a precipitate, and the obtained precipitate together with a water-soluble lithium compound and an oxidizing agent is subjected to alkaline conditions. hydrothermal treatment under, the product lithium compound after the hydrothermal treatment, the production method of lithium manganese oxide of claim 1, wherein the firing in a reducing atmosphere. A lithium ion secondary battery positive electrode material comprising the lithium manganese composite oxide according to claim 1 . The lithium ion secondary battery which uses the positive electrode material for lithium ion secondary batteries of Claim 6 as a component.

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