JPWO2007007581A1 - Positive electrode material for lithium secondary battery, method for producing the same, and lithium secondary battery using the same - Google Patents

Abstract

The present invention has a Li0.44MnO2 type tunnel structure using an inexpensive manganese oxide raw material with few resource constraints, and has an operating voltage range (about 4 V) equivalent to that of an existing practical positive electrode material. Provides a novel positive electrode material that can be stably charged and discharged at a high capacity, a method for producing the same, and a lithium secondary battery that includes this material as a positive electrode active material and uses various negative electrode materials. In the present invention, LixMn1-yTiyO2 (0.5 ≦ x ≦ 1, 0 ≦ y <0.56) is expressed as a chemical composition formula, and the crystal structure belongs to an orthorhombic system and has a tunnel structure occupied by lithium. A lithium secondary battery positive electrode material composed of lithium, manganese, titanium, and oxygen is used to constitute a lithium secondary battery.

Description

  The present invention relates to a positive electrode material for a lithium secondary battery, a manufacturing method thereof, and a lithium secondary battery containing the material as a positive electrode active material.

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

  This lithium secondary battery uses a positive electrode having a lithium-containing transition metal composite oxide as an active material and a material capable of inserting and extracting lithium, such as lithium metal, lithium alloy, metal oxide, or carbon. A main component is a negative electrode as a substance and a separator or solid electrolyte containing a non-aqueous electrolyte.

Among these components, those studied as positive electrode active materials include layered rock salt type lithium cobalt oxide (LiCoO ₂ ), layered rock salt type lithium nickel oxide (LiNiO ₂ ), spinel type lithium manganese oxide ( LiMn ₂ O ₄ ) and the like.

In particular, the layered rock salt type lithium cobalt oxide LiCoO ₂ has a secondary battery operating voltage (difference between the redox potential of the transition metal in the positive electrode and the redox potential of the negative electrode element), charge / discharge capacity. Excellent battery performance such as (amount of lithium that can be desorbed and inserted from the positive electrode) is expected to increase further in the future as a positive electrode constituent material for lithium secondary batteries.
However, since this compound contains cobalt, which is a rare metal, as a main component, it is one of the high-cost factors for lithium secondary batteries. Furthermore, considering that about 20% of the world's cobalt production is already used in the battery industry, it is unclear whether only the cathode material made of LiCoO ₂ can meet future demand growth. is there.

Further, the layered rock salt type lithium nickel oxide LiNiO ₂ using nickel cheaper than cobalt is advantageous in terms of cost and capacity, and is being developed as a promising alternative material for lithium cobalt oxide. . However, the lithium secondary battery using this lithium nickel oxide as the positive electrode active material has the risk of decomposition, heat generation, ignition, etc. if kept at a high temperature due to the instability of the positive electrode active material in the charged state. There are still many issues that need to be resolved regarding safety.

In addition, from the viewpoint of the cobalt-based oxide substitute material, low-cost and low-cost manganese oxide is used as a raw material, and further, manganese and oxygen accompanying oxidation-reduction reaction of Mn ³⁺ and Mn ⁴⁺ are used. Manganese positive electrode materials that can withstand changes in chemical bonding are promising materials.

Among them, the spinel-type lithium manganese oxide LiMn ₂ O ₄ is used less expensive manganese than cobalt and nickel, and since it is excellent in safety in the charged state, partly in LiCoO ₂ It has been put to practical use instead. However, there is a problem that the capacity is small compared to LiCoO ₂ and LiNiO ₂ . Further, since there is a problem of remarkable characteristic deterioration due to dissolution of manganese in an electrolytic solution at 50 ° C. or higher, substitution of LiCoO ₂ by this material has not progressed as expected.

On the other hand, as a feature of the crystal structure, research has been conducted to synthesize Li _0.44 MnO ₂ by an ion exchange method using Na _0.44 MnO ₂ having a one-dimensional tunnel structure as a starting material. Since this compound has two types of tunnels having different sizes, it is considered that ion diffusion is easy. For example, the compound has attracted attention as a positive electrode material having high output (capable of rapid charge / discharge). (See Non-Patent Documents 1 and 2)
However, since the battery voltage reported so far is about 3 V and the battery capacity is about 100 mAh / g, it has not reached a practical level.
A. R. Armstrong, H .; Huang, R.A. A. Jennings, P.M. G. Bruce, J. et al. Mater. Chem. 8, 255-259 (1998) M.M. M.M. Doeff, A.M. Anapolsky, L.A. Edman, T .; J. et al. Richardson, L.M. C. De Jonghe, J.A. Electrochem. Soc. , 148, A230-A236 (2001)

Therefore, in the current lithium secondary battery, whether or not it is a positive electrode material that can be substituted for LiCoO ₂ has a voltage flat part accompanying manganese trivalent to tetravalent oxidation-reduction reaction in the vicinity of 4 V, and is stable. Whether or not it is a chargeable / dischargeable manganese oxide-based positive electrode material is the criterion.
The inventors of the present invention have raised the temperature of the above-described ion exchange treatment so that a novel lithium manganese oxide that can be charged and discharged even in a 4 V region and has a high capacity, and a titanium substitution product thereof (Li _x Mn _{1− y} Ti _y O ₂ found (0.4 <x <0.5,0 ≦ y <0.56), previously proposed. (see Patent documents 1 to 3)
However, the discharge capacity that can be realized with this material is about 4 mA charge / discharge capacity in the battery using the carbon negative electrode, about 60 mAh / g in the initial discharge capacity, and about 150 mAh / g in the battery using the lithium negative electrode. In order to realize the theoretical capacity (193 mAh / g), it was necessary to further improve the capacity.
Japanese Patent Application No. 2004-065452 Japanese Patent Application No. 2004-080970 Japanese Patent Application No. 2004-080971

On the other hand, from the viewpoint of further improving the energy density of the battery, a battery using lithium metal or a lithium alloy as a negative electrode material has been studied. For example, in order to ensure the safety of the battery, many studies have been made on a “lithium polymer secondary battery” using a solid polymer as an electrolyte. For this purpose, there has been a demand for a positive electrode material that exhibits the maximum performance in the use of a lithium negative electrode, and development of a new material having a high voltage and a high capacity is being promoted.
In addition, for the purpose of reducing the weight of the battery itself for use as a power source for portable electronic devices, etc., development that replaces the constituent elements of the positive electrode material oxide that can be used with various negative electrode materials with light elements with as small an atomic weight as possible is also included. It is being advanced.

In the above-described spinel type lithium manganese oxide LiMn ₂ O ₄ , in a battery using a lithium negative electrode, lithium insertion is possible up to the chemical composition of Li ₂ Mn ₂ O ₄ , but the insertion reaction involves a structural change. It is known to cause capacity deterioration rapidly and does not meet the above-mentioned purpose.

Therefore, the present invention solves the above-mentioned current problems by using an inexpensive manganese oxide raw material with less resource restrictions, and provides a Li _0.44 MnO ₂ type tunnel structure as described above. And a new positive electrode material that can be stably charged and discharged with a high capacity in an operating voltage region (about 4 V) equivalent to that of an existing practical positive electrode material, a manufacturing method thereof, and this material as a positive electrode active material And providing a lithium secondary battery using various negative electrode materials.

The present inventor has intensively studied in view of the problems of the prior art including the prior inventions described in Patent Documents 1 to 3 (hereinafter collectively referred to as “prior application invention”). As a result, lithium insertion treatment using the lithium manganese titanium oxide Li _x Mn _1-y Ti _y O ₂ (0.4 <x <0.5, 0 ≦ y <0.56) according to the invention of the prior application as a raw material. And found that the amount of lithium in the oxide is increased while maintaining the original crystal structure, and the capacity in the 4V region is greatly increased to a value close to the theoretical capacity, and the present invention is completed. It came to do.

That is, this invention provides the lithium manganese titanium oxide positive electrode material shown in the following 1-6, its manufacturing method, and a lithium secondary battery using the same.
1. A tunnel represented by Li _x Mn _1-y Ti _y O ₂ (0.5 ≦ x ≦ 1, 0 ≦ y <0.56) as a chemical composition formula, belonging to an orthorhombic system as a crystal structure, and occupied by lithium A lithium secondary battery positive electrode material comprising lithium, manganese, titanium, and oxygen having a structure.
2. ₁ manufactured by lithium insertion treatment using Li _x Mn _1-y Ti _y O ₂ (0.40 <x <0.50, 0 ≦ y <0.56) prepared in advance as a starting material 1 The manufacturing method of the lithium secondary battery positive electrode material of description.
3. 3. The method for producing a positive electrode material according to 2, wherein the lithium insertion treatment is performed in a molten salt containing a lithium compound, or in an organic solvent or an aqueous solution in which the lithium compound is dissolved.
4). A lithium secondary battery, wherein the positive electrode of the lithium secondary battery having a positive electrode, a negative electrode, and an electrolyte material is composed of the positive electrode material described in 1.
5. 5. The lithium secondary battery according to 4, wherein a lithium or lithium alloy negative electrode is used as the negative electrode of the battery, and charging and discharging can be performed stably in a voltage range of 4V.
6). 5. The lithium secondary battery according to 4, wherein a carbon negative electrode is used as the negative electrode of the battery and can be stably charged and discharged in a voltage range of 4V.

According to the present invention, an inexpensive raw material can be used to stably charge and discharge a lithium secondary battery in a high operating voltage range (about 4 V) equivalent to an existing lithium cobalt oxide positive electrode material. Thus, a novel lithium manganese titanium oxide cathode material having a capacity larger than that of the existing cathode lithium manganese oxide spinel can be obtained.
In addition, the lithium secondary battery of the present invention using the above lithium manganese titanium oxide positive electrode material has high voltage and high capacity, can exhibit excellent charge / discharge cycle characteristics, and is highly practical. .

It is a schematic diagram which shows one example of the lithium secondary battery of this invention. 2 is an X-ray powder diffraction pattern of the positive electrode material of the present invention obtained in Examples 1 and 2. FIG. It is a figure which shows the initial stage discharge characteristic of the battery obtained in Example 1 and Comparative Example 1. It is a figure which shows the initial stage discharge characteristic of the battery obtained in Example 1 and Comparative Example 2. It is a figure which shows the initial stage discharge characteristic of the battery obtained in Example 3 and Comparative Examples 3 and 4. FIG. It is a figure which shows the discharge output characteristic of the battery obtained in Example 4. FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Button type lithium secondary battery 2 Negative electrode terminal 3 Negative electrode 4 Separator + Electrolyte 5 Insulation packing 6 Positive electrode 7 Positive electrode can

(Positive electrode material for lithium secondary battery and manufacturing method thereof)
Lithium manganese titanium oxide Li _x Mn _1-y Ti _y O ₂ (0.40 <x <0.50, 0 ≦ y <0.56) positive electrode material and The Li _x Mn _1-y Ti _y O ₂ (0.5 ≦ x ≦ 1, 0 ≦ y <0.56) positive electrode material according to the present invention is Na _x Mn _1-y Ti _y O ₂ (0 .40 <x <0.50, 0 ≦ y <0.56) It has a tunnel structure similar to that of the compound, and the ratio of manganese to titanium can be freely selected within the above composition range.

  In the case of a sodium compound, sodium can be occluded only by about 0.40 <x <0.50 due to repulsion due to electrostatic energy of sodium ions in the structure, and thus sodium was ion-exchanged to lithium. In the positive electrode material of the prior invention, the amount of lithium was inevitably the same value as the amount of sodium. However, in the case of lithium having a small ionic radius as compared with sodium, it becomes possible to occlude lithium more densely. Therefore, the maximum lithium occlusion amount (theoretical capacity) predicted crystallographically is x = 0. 66.

  In addition, it is well known in intercalation chemistry that when lithium insertion treatment is performed, more lithium is occluded compared to the crystallographically predicted lithium site. If lithium can also contribute to the battery reaction, the battery capacity can be increased.

The Li _x Mn _1-y Ti _y O ₂ (0.5 ≦ x ≦ 1, 0 ≦ y <0.56) positive electrode material of the present invention is the lithium manganese titanium oxide Li _x Mn _{1 —} by subjecting the lithium insertion process _{y Ti y O 2 (0.40 <} x <0.50,0 ≦ y <0.56) positive electrode material, it can be made. By this lithium insertion treatment, the total amount of lithium in the positive electrode material can be set to 0.4 <x ≦ 1 (where x is larger than x in the starting material), but 0.5 ≦ x It is preferable that ≦ 1, especially 0.6 <x ≦ 1.

  The positive electrode material of the present invention is characterized in that sodium contained in the starting material can be almost completely replaced with lithium by ion exchange treatment and lithium insertion treatment due to the characteristics of the crystal structure and the production process. . However, it is generally known that such a method leaves significant or impurity-grade sodium.

That is, the Li _x Mn _1-y Ti _y O ₂ (0.5 ≦ x ≦ 1, 0 ≦ y <0.56) positive electrode material of the present invention contains lithium, manganese, titanium, and oxygen as main constituent elements. However, it may contain an impurity element such as sodium as long as the effect of the present invention is not hindered.

The Li _x Mn _1-y Ti _y O ₂ (0.5 ≦ x ≦ 1, 0 ≦ y <0.56) positive electrode material of the present invention has an amount of manganese and titanium within the range of 0 ≦ y <0.56. It is characterized by being able to select freely. Substituting titanium has been confirmed in the prior application invention to increase the stability of the crystal structure and to increase trivalent manganese that contributes to the charge / discharge reaction. The preferable amount of titanium is correlated with the amount of lithium in the structure, but is in the range of 0 ≦ y <0.56, more preferably 0 ≦ y <0.4.

Moreover, the Li _x Mn _1-y Ti _y O ₂ (0.5 ≦ x ≦ 1, 0 ≦ y <0.56) positive electrode material of the present invention has a Li _0.44 MnO ₂ type tunnel structure as a whole. Although it is desirable to have it, other crystal structures may be partially included within a range that does not hinder the effects of the present invention.

Next, the production method of the present invention will be described in more detail.
The Li _x Mn _1-y Ti _y O ₂ (0.5 ≦ x ≦ 1, 0 ≦ y <0.56) positive electrode material of the present invention is the lithium manganese titanium oxide Li _x Mn _{1 —} the _{y Ti y O 2 (0.40 <} x <0.50,0 ≦ y <0.56) positive electrode material is prepared as a starting material.
Further, the lithium manganese-titanium oxide as a starting material _{Li x Mn 1-y Ti y} O 2 (0.40 <x <0.50,0 ≦ y <0.56) positive electrode material, sodium manganese titanium oxide Na _x Mn _1-y Ti _y O ₂ (0.40 <x <0.50, 0 ≦ y <0.56) is used as a raw material.

The Na _x Mn _1-y Ti _y O ₂ (0.40 <x <0.50, 0 ≦ y <0.56) compound is, for example, (1) at least one of sodium and sodium compounds, (2) manganese and It can be produced by firing a mixture containing at least one manganese compound, (3) titanium and at least one titanium compound.

As the sodium raw material, at least one of sodium (metallic sodium) and a sodium compound is used. The sodium compound is not particularly limited as long as it contains sodium. For example, oxides such as Na ₂ O and Na ₂ O ₂ , salts such as Na ₂ CO ₃ and NaNO ₃ , hydroxides such as NaOH, etc. Is mentioned. Among these, Na ₂ CO ₃ is particularly preferable.

As the manganese raw material, at least one of manganese (metallic manganese) and a manganese compound is used. The manganese compound is not particularly limited as long as it contains manganese. For example, Mn ₃ O ₄ , Mn ₂ O ₃ , MnO _{2 and} other oxides, MnCO ₃ , MnCl _{2 and} other salts, Mn (OH) ₂ And hydroxides such as MnOOH and the like. Among these, Mn ₂ O ₃ , MnO _{2 and the} like are particularly preferable.

As the titanium raw material, at least one of titanium (metallic titanium) and a titanium compound is used. The titanium compound is not particularly limited as long as it contains titanium, and examples thereof include oxides such as TiO, Ti ₂ O ₃ and TiO ₂ , salts such as TiCl _{4 and the} like. Among these, TiO ₂ is particularly preferable.

First, a mixture containing these is prepared. The mixing ratio of the sodium raw material, the manganese raw material, and the titanium raw material is preferably mixed so that the tunnel structure is generated. Specifically, the chemical composition formula may be Na _x Mn _1-y Ti _y O ₂ (0.40 <x <0.50, 0 ≦ y <0.56). For example, mixing may be performed so that Na / (Mn + Ti) is about 0.4 to 0.7, preferably 0.43 to 0.55 in terms of molar ratio. Usually, when baking is performed at a high temperature, the contained sodium tends to volatilize, and the amount of sodium in the product is often less than the charged composition. It is preferable to increase the amount charged. Further, the ratio between manganese and titanium may be arbitrarily selected within the range of (0 ≦ y <0.56).

  Moreover, a mixing method is not specifically limited as long as these can be mixed uniformly, For example, what is necessary is just to mix by a wet type or a dry type using well-known mixers, such as a mixer.

  The mixture is then fired. The firing temperature can be appropriately set according to the composition of the mixture, etc., but is usually about 600 to 1200 ° C., preferably 800 to 1050 ° C. Also, the firing atmosphere is not particularly limited, but usually it may be carried out in an oxidizing atmosphere or air. The firing time can be appropriately changed according to the firing temperature and the like. The cooling method is not particularly limited, but it may be naturally cooled (cooled in the furnace) or gradually cooled.

  After firing, the fired product may be pulverized by a known method as necessary, and the above firing step may be further performed. That is, in the method of the present invention, it is preferable that the mixture is repeatedly fired, gradually cooled and pulverized twice or more. Note that the degree of pulverization may be appropriately adjusted according to the firing temperature and the like.

Next, the calcined Na _x Mn _1-y Ti _y O ₂ (0.40 <x <0.50, 0 ≦ y <0.56) in a molten salt containing a lithium compound, or in an organic solvent or aqueous solution By carrying out the ion exchange treatment, the crystal structure of Li _0.44 MnO ₂ type is obtained, and the chemical composition formula Li _x Mn _1-y Ti _y O ₂ (0.40 <x <0.50, 0 ≦ y <0.56) is obtained.

In this case, while pulverized Na _x Mn _1-y Ti _y O ₂ (0.40 <x <0.50, 0 ≦ y <0.56) is dispersed in the molten salt containing the lithium-containing compound. It is preferable to perform an ion exchange treatment. As the molten salt, a molten salt containing any one or more of salts that melt at a low temperature such as lithium nitrate, lithium chloride, lithium bromide, and lithium iodide can be used. As a preferred method, a lithium compound and a powder of Na _x Mn _1-y Ti _y O ₂ fired product are mixed well. The mixing ratio is usually ₂ to 40, preferably 10 to 30, in terms of the molar ratio of Na in Li / Na _x Mn _1-y Ti _y O ₂ in the molten salt.

The ion exchange temperature is 260 ° C to 330 ° C. When the ion exchange temperature is lower than 260 ° C., sodium in Na _x Mn _1-y Ti _y O ₂ (0.40 <x <0.50, 0 ≦ y <0.56) is completely transferred to lithium. A substantial amount of sodium remains in the product without being exchanged. On the other hand, when the ion exchange temperature is higher than 330 ° C., a part of the ion exchange temperature changes to a spinel structure, so that a uniform crystal structure cannot be obtained. The treatment time is usually 2 to 20 hours, preferably 5 to 15 hours.

Furthermore, as a method of ion exchange treatment, a method of treating in an organic solvent or an aqueous solution in which a lithium compound is dissolved is also suitable. In this case, pulverized Na _x Mn _1-y Ti _y O ₂ (0.40 <x <0.50, 0 ≦ y <0.56) is put into the organic solvent in which the lithium-containing compound is dissolved. The treatment is performed at a temperature below the boiling point of the organic solvent. In order to increase the ion exchange rate, it is preferable to perform ion exchange while refluxing the solvent near the boiling point of water or an organic solvent. The treatment temperature is usually 30 ° C to 200 ° C, preferably 60 ° C to 180 ° C. Further, the treatment time is not particularly limited, but it is usually 5 to 50 hours, preferably 10 to 20 hours, because a reaction time is required at a low temperature.

  The lithium-containing compound used in the present invention is preferably a hydroxide, carbonate, acetate, nitrate, oxalate, halide, butyllithium, etc., and these may be used alone or in combination of two or more as required. Used. Further, as the organic solvent used in the present invention, higher alcohols such as hexanol and ethoxyethanol, ethers such as diethylene glycol monoethyl ether, or organic solvents having a boiling point of 140 ° C. or higher are good in workability. preferable. These may be used alone or in combination of two or more as required.

The density | concentration of the lithium containing compound in an organic solvent or aqueous solution is 3-10 mol% normally, Preferably it is 5-8 mol%. The dispersion concentration of Na _x Mn _1-y Ti _y O _{2 in} the organic solvent or aqueous solution is not particularly limited, but is preferably 1 to 20% by weight from the viewpoints of operability and economy.

After the ion exchange treatment, the obtained product is thoroughly washed with distilled water, then washed with methanol and ethanol, and dried to obtain the target Li _x Mn _1-y Ti _y O ₂ (0.40). <X <0.50, 0 ≦ y <0.56). The washing method and the drying method are not particularly limited, and a normal method may be used, or natural drying in a desiccator may be used.

Next, in Li _x Mn _1-y Ti _y O ₂ (0.40 <x <0.50, 0 ≦ y <0.56) prepared by ion exchange treatment, in a molten salt containing a lithium compound, Alternatively, by performing an ion insertion treatment in an organic solvent or an aqueous solution, it has a crystal structure of Li _0.44 MnO ₂ type and has a chemical composition formula Li _x Mn _1-y Ti _y O ₂ (0.5 ≦ x ≦ 1 , 0 ≦ y <0.56).

In this case, Li _x Mn _1-y Ti _y O ₂ (0.40 <x <0.50, 0 ≦ y <0.56) prepared in advance is dispersed in the molten salt containing the lithium-containing compound. However, it is preferable to perform a lithium insertion process. As the molten salt, lithium nitrate is used, and as an additive, any one of salts such as lithium hydroxide, lithium iodide, lithium bromide, lithium oxide, lithium peroxide, lithium carbonate, and lithium chloride is used. Add more. As a preferred method, the additive and Li _x Mn _1-y Ti _y O ₂ powder are mixed well. The mixing ratio is usually 0.01 to 10, preferably 0.1 to 3 in terms of a molar ratio of additive / Li _x Mn _1-y Ti _y O _{2 in} the molten salt.

  The temperature of the lithium insertion process is 260 ° C to 330 ° C. When the processing temperature is higher than 330 ° C., a part of the processing temperature changes to a spinel structure, so that a uniform crystal structure cannot be obtained. The treatment time is usually 2 to 20 hours, preferably 5 to 15 hours. The insertion process is more effective if it is repeated several times, preferably 2-3 times.

Furthermore, as a method for the lithium insertion treatment, a treatment method in an organic solvent or an aqueous solution in which a lithium compound is dissolved is also suitable. In this case, Li _x Mn _1-y Ti _y O ₂ (0.40 <x <0.50, 0 ≦ y <0.56) ion-exchanged in advance in an organic solvent in which the lithium-containing compound is dissolved. It is charged and treated at a temperature below the boiling point of the organic solvent. In order to increase the lithium insertion rate, it is preferable to perform the insertion treatment while refluxing the solvent near the boiling point of the organic solvent. The treatment temperature is usually 30 ° C to 200 ° C, preferably 60 ° C to 180 ° C. Further, the treatment time is not particularly limited, but it is usually 5 to 50 hours, preferably 10 to 20 hours, because a reaction time is required at a low temperature.

  As the lithium-containing compound used in the present invention, hydroxide, oxide, peroxide, carbonate, acetate, nitrate, oxalate, halide, butyllithium and the like are preferable. Are used in combination of two or more. Further, as the organic solvent used in the present invention, higher alcohols such as hexanol and ethoxyethanol, ethers such as diethylene glycol monoethyl ether, or organic solvents having a boiling point of 140 ° C. or higher are good in workability. preferable. These may be used alone or in combination of two or more as required.

The density | concentration of the lithium containing compound in an organic solvent or aqueous solution is 3-10 mol% normally, Preferably it is 5-8 mol%. The dispersion concentration of Li _x Mn _1-y Ti _y O _{2 in} the organic solvent or aqueous solution is not particularly limited, but is preferably 1 to 20% by weight from the viewpoints of operability and economy.

After the lithium insertion treatment, the obtained product is washed thoroughly with distilled water, then washed with methanol and ethanol, and dried to obtain the intended Li _x Mn _1-y Ti _y O ₂ (0.5 ≦ x ≦ 1, 0 ≦ y <0.56). The washing method and the drying method are not particularly limited, and a normal method may be used, or natural drying in a desiccator may be used.

(Lithium secondary battery)
The lithium secondary battery of the present invention uses the positive electrode material for a lithium secondary battery. That is, a battery element of a known lithium secondary battery (coin type, button type, cylindrical type, etc.) can be used as it is except that the lithium manganese titanium oxide of the present invention is used as the positive electrode material.
FIG. 1 is a schematic view showing an example in which the lithium secondary battery of the present invention is applied to a button type battery. The button-type battery 1 includes a negative electrode terminal 2, a negative electrode 3, a (separator + electrolyte) 4, an insulating packing 5, a positive electrode 6, and a positive electrode can 7.

  In the present invention, the above-described lithium manganese titanium oxide of the present invention is mixed with a conductive agent, a binder or the like as necessary to prepare a positive electrode mixture, and this is bonded to a current collector to bond the positive electrode. Can be made. As the current collector, a stainless mesh, aluminum foil or the like can be preferably used. As the conductive agent, acetylene black, ketjen black or the like can be preferably used. As the binder, tetrafluoroethylene, polyvinylidene fluoride, or the like can be preferably used.

  The compounding of lithium manganese titanium oxide, conductive agent, binder and the like in the positive electrode mixture is not particularly limited, but usually the conductive agent is about 1 to 30% by weight (preferably 5 to 25% by weight), and the binder. May be about 0 to 30% by weight (preferably 3 to 10% by weight), and the balance may be lithium manganese titanium oxide.

  In the lithium secondary battery of the present invention, as the counter electrode with respect to the positive electrode, for example, carbon-based materials such as graphite and MCMB (mesocarbon microbeads), alloy-based materials such as tin-based materials, lithium such as lithium metal and lithium alloy are used. A known material that can be occluded can be used. Moreover, a well-known battery element should just be employ | adopted for a separator, a battery container, etc.

  Moreover, a well-known thing is applicable also as electrolyte solution. For example, an electrolyte such as lithium perchlorate or lithium hexafluorophosphate dissolved in a solvent such as ethylene carbonate (EC), dimethyl carbonate (DMC), propylene carbonate (PC), or diethyl carbonate (DEC) It can be used as an electrolyte.

  Next, the features of the present invention will be further described with reference to examples. However, the following specific examples do not limit the present invention.

Example 1
[Manufacture of positive electrode materials]
Sodium carbonate (Na ₂ CO ₃ ), manganese oxide (Mn ₂ O ₃ ), and titanium oxide (TiO ₂ ) in a molar ratio of Na _x Mn _1-y Ti _y O ₂ (x = 0.5; y = 0, 0) 0.055, 0.11, 0.22) were uniformly mixed. The mixture was calcined in air at 900 ° C. to 1000 ° C. for 12 hours and then gradually cooled in a furnace. A series of operations (firing, gradual cooling, and pulverization) of pulverizing the obtained fired body are repeated again, and the starting material Na _0.44 having a target crystal structure of Li _0.44 MnO _{2 of} almost single phase. Mn _1-y Ti _y O ₂ was obtained.

Next, these samples were subjected to ion exchange treatment in a molten salt in which lithium nitrate and lithium chloride were mixed at a molar ratio of 88:12. The amount of Na _0.44 Mn _1-y Ti _y O _{2 in} the molten salt was a molar ratio, Li in the molten salt: Na in the sample = 20: 1, and the temperature of the molten salt was 300 ° C. An ion exchange treatment was performed for a treatment time of 10 hours, and the obtained solid was washed with distilled water, methanol, ethanol, etc. and dried to obtain a sample. As a result of analyzing the chemical composition of this sample by ICP emission spectrometry, Li _x Mn _1-y Ti _y O ₂ (0.43 ≦ x ≦ 0.44; y = 0, 0.055, 0.11, 0 .22) which is reasonable and the remaining sodium content was 0.005 in Na / Li molar ratio. Furthermore, the X-ray powder diffractometry revealed that the Li _0.44 MnO ₂ type orthorhombic tunnel structure was almost a single phase, and the lattice constants of each sample were as shown in Table 1. . Further, among the prepared samples, an X-ray powder diffraction pattern of Li _0.44 MnO ₂ (y = 0) is shown in FIG.

Next, 1 g of each sample described in Table 1 was mixed well with 22 g of lithium nitrate and 1 g of lithium hydroxide, and then heated in air at 300 ° C. for 10 hours to perform lithium insertion treatment. The obtained solid was washed with distilled water, methanol, ethanol or the like and dried to obtain a sample. As a result of analyzing the chemical composition of this sample by ICP emission analysis, the amount of lithium x was about 0.59 ≦ x ≦ 0.72, and the insertion reaction was confirmed. Further, the amount of sodium remaining and contained was below the ICP detection limit (0.01 wt%), and it was confirmed that the lithium insertion treatment was effective in further reducing the amount of sodium remaining. Furthermore, among the produced samples, an X-ray powder diffraction pattern of Li _0.63 MnO ₂ (y = 0) is shown in FIG. Table 2 shows the calculated lattice constants assuming the same structure as Li _0.44 MnO _{2 used} as a starting material. The change in the lattice constant was clarified by the lithium insertion treatment as compared with the original Li _x Mn _1-y Ti _y O ₂ (0.43 ≦ x ≦ 0.44).

[Lithium secondary battery]
20 mg of each sample of the obtained Li _x Mn _1-y Ti _y O ₂ (0.59 ≦ x ≦ 0.72; y = 0, 0.055, 0.11, 0.22) was added to the acetylene black as a conductive agent. 5 mg and 0.5 mg of tetrafluoroethylene as a binder are blended to prepare a positive electrode, lithium metal is a negative electrode material, lithium hexafluorophosphate is a mixed solvent of ethylene carbonate (EC) and diethyl carbonate (DEC) ( A lithium secondary battery (coin-type cell) having the structure shown in FIG. 1 was prepared using a 1M solution dissolved in a volume ratio of 1: 1) as an electrolytic solution, and its charge / discharge characteristics were measured. The battery was produced according to a known cell configuration / assembly method.

The obtained lithium secondary battery was subjected to a charge / discharge test under a temperature condition of 30 ° C. with a current density of 30 mA / g (corresponding to 0.2 C at C rate) and a cutoff potential of 4.8 V to 2.5 V. However, it was found that charging and discharging can be stably performed at an average discharge voltage of 3.55 to 3.64 V and an initial discharge capacity of 173 to 184 mAh / g. (Here, the C rate is the discharge rate, that is, the magnitude of the discharge current, and 1C refers to the amount of current that can be discharged in one hour. The rate is one hour. For example, 1C of a battery having a capacity of 1 Ah. Will be 1A.)
In the case of Li _0.69 Mn _0.89 Ti _0.11 O ₂ , the discharge capacity after 10 cycles was maintained at about 168 mAh / g, and the cycle characteristics were also good. Table 3 shows the initial charge capacity, initial discharge capacity, and average initial discharge voltage of each battery.

3A and 3B show initial discharge characteristics of a battery manufactured using Li _0.63 MnO ₂ and Li _0.72 Mn _0.78 Ti _0.22 O ₂ as positive electrode materials. For comparison, the battery shown in FIG. 3 (c), in which Li _0.44 MnO ₂ before insertion of Li was used as the positive electrode material in the same manner, Li _0.63 MnO ₂ has a discharge capacity in the 4V region. It can be seen that it has increased significantly. Furthermore, as seen in (b), it was confirmed that the discharge curve becomes gentle by substituting a part of Mn with titanium.

(Example 2)
[Manufacture of positive electrode materials]
1 g of each sample shown in Table 1 obtained in Example 1 was mixed well with 22 g of lithium nitrate and 1 g of lithium iodide, and then heated in air at 300 ° C. for 10 hours to perform lithium insertion treatment. It was. The obtained solid was washed with distilled water, methanol, ethanol or the like and dried to obtain a sample. As a result of analyzing the chemical composition of these samples by ICP emission analysis, the lithium amount x was about 0.67 ≦ x ≦ 0.76 as shown in Table 4, and the effectiveness of the insertion treatment was confirmed. Further, the amount of sodium remaining and contained was below the ICP detection limit (0.01 wt%), and the insertion treatment was effective in further reducing the amount of sodium remaining. Furthermore, among the produced samples, an X-ray powder diffraction pattern of Li _0.76 MnO ₂ (y = 0) is shown in FIG.
Table 4 shows the calculated lattice constants assuming the same structure as Li _0.44 MnO _{2 used} as a starting material. The change in the lattice constant was clarified by the lithium insertion treatment as compared with the original Li _x Mn _1-y Ti _y O ₂ (0.43 ≦ x ≦ 0.44). Further, it was confirmed that the ion insertion treatment by addition of lithium iodide had substantially the same effect as in Example 1 in which lithium hydroxide was added.

[Lithium secondary battery]
Using each sample of Li _x Mn _1-y Ti _y O ₂ (0.67 ≦ x ≦ 0.76) thus obtained, a positive electrode was produced in the same manner as in Example 1, and Example 1 and Similarly, when a lithium secondary battery was produced and a charge / discharge test was performed, it was confirmed that all of the lithium secondary batteries could be stably charged / discharged at an average discharge voltage of 3.54 to 3.60 V and an initial discharge capacity of 168 to 176 mAh / g. It was. Table 5 shows the initial charge capacity, initial discharge capacity, and average initial discharge voltage of each sample.

(Comparative Example 1)
For each sample of Li _x Mn _1-y Ti _y O ₂ (0.43 ≦ x ≦ 0.44) described in Table 1 obtained in Example 1 above, the positive electrode material was used without being subjected to lithium insertion treatment. In the same manner as in Example 1, a lithium secondary battery was prepared and a charge / discharge test was performed. In each case, the average discharge voltage was 3.48 to 3.54 V, and the initial discharge capacity was about 141 to 156 mAh / g. It was. For comparison, the initial discharge curve in the case of Li _0.44 MnO ₂ is shown in FIG.

(Comparative Example 2)
In order to clarify the characteristics of the lithium secondary battery using the novel lithium manganese titanium oxide according to the present invention as the positive electrode material, the existing positive electrode lithium manganese spinel Li _1.1 Mn _1.9 O ₄ is used as the positive electrode material. When a lithium secondary battery was produced in the same manner as in Example 1 and a charge / discharge test was performed under the same conditions, the average discharge voltage was 3.67 V and the initial discharge capacity was 152 mAh / g.
Further, as shown in FIG. 4B, the battery using this positive electrode material showed a large two-stage discharge curve characteristic of the spinel type. On the other hand, as shown in FIG. 4A, the battery using the Li _0.63 MnO ₂ of the present invention obtained in Example 1 of the present invention as the positive electrode material has a voltage / capacity, that is, an energy density. From this point of view, the superiority to the spinel material was confirmed.

(Example 3)
Using each sample of Li _x Mn _1-y Ti _y O ₂ (0.59 ≦ x ≦ 0.72, y = 0, 0.055, 0.11, 0.22) obtained in Example 1. A positive electrode was produced in the same manner as in Example 1, carbon (MCMB) as the negative electrode material, and lithium hexafluorophosphate as a mixed solvent (volume ratio 1: 1) of ethylene carbonate (EC) and diethyl carbonate (DEC). A lithium ion secondary battery (coin-type cell) having the structure shown in FIG. 1 was prepared using the dissolved 1M solution as an electrolytic solution, and the charge / discharge characteristics thereof were measured. The battery was produced according to a known cell configuration / assembly method.

This lithium ion secondary battery was subjected to a charge / discharge test under a temperature condition of 30 ° C. with a current density of 30 mA / g (corresponding to 0.2 C at the C rate) and a cutoff potential of 4.8 V to 2.5 V. It was found that charging and discharging can be stably performed at an average discharge voltage of 3.7 to 3.8 V and an initial discharge capacity of 114 to 120 mAh / g. In the case of Li _0.63 MnO ₂ , the discharge capacity after 10 cycles also maintained about 79 mAh / g, and the cycle characteristics were also good. Table 6 shows the initial charge capacity, initial discharge capacity, and average initial discharge voltage of each sample. Moreover, the initial discharge characteristics of Li _0.63 MnO ₂ are shown in FIG.

(Example 4)
A positive electrode was prepared in the same manner using each sample of Li _x Mn _1-y Ti _y O ₂ (0.67 ≦ x ≦ 0.76) obtained in Example 2, and in the same manner as in Example 3, When a secondary battery was produced and a charge / discharge test was performed, it was confirmed that each of the batteries could be stably charged / discharged at an average discharge voltage of 3.7 to 3.8 V and an initial discharge capacity of 100 to 119 mAh / g. Table 7 shows the initial charge capacity, initial discharge capacity, and average initial discharge voltage of each sample.

(Comparative Example 3)
For each sample of Li _x Mn _1-y Ti _y O ₂ (0.43 ≦ x ≦ 0.44) described in Table 1 obtained in Example 1 above, the positive electrode material was used without being subjected to lithium insertion treatment. In the same manner as in Example 3, a lithium secondary battery was prepared and a charge / discharge test was conducted. In each case, the average discharge voltage was 3.8 to 3.9 V, and the initial discharge capacity was about 50 to 60 mAh / g. It was. For comparison, an initial discharge curve in the case of Li _0.44 MnO ₂ is shown in FIG.

(Comparative Example 4)
In order to clarify the characteristics of the lithium secondary battery using the novel lithium manganese titanium oxide according to the present invention as the positive electrode material, the existing positive electrode lithium manganese spinel Li _1.1 Mn _1.9 O ₄ is used as the positive electrode material. When a lithium secondary battery was produced in the same manner as in Example 3 and a charge / discharge test was performed under the same conditions, the average discharge voltage was 3.84 V and the initial discharge capacity was 94 mAh / g. Further, the discharge capacity after 10 cycles in this battery is about 52 mAh / g, and the characteristics of the positive electrode material according to the present invention (average discharge voltage 3.8 V, initial discharge capacity 120 mAh / g, discharge capacity after 10 cycles 79 mAh / g). ) Was confirmed. The initial discharge curve of the battery obtained in this example is shown in FIG. 5 (c) and compared with the battery of the present invention in FIG. 5 (a).

(Example 5)
For Li _x Mn _1-y Ti _y O ₂ (x = 0.44 and 0.63, y = 0) obtained in Example 1, the same positive electrode constituent member as that in Example 1 was replaced with N-methyl-2- Diluted with pyrrolidone (NMP) to form a slurry, and a coated electrode was prepared according to a conventional method. The mixing ratio was oxide active material: conductive agent: binder = 89.5: 4.5: 6.0 (wt%). Table 8 shows the electrode physical properties of the produced positive electrode.

[Lithium secondary battery]
The positive electrode thus obtained, MCMB as the negative electrode, polyethylene microporous membrane as the separator, and lithium hexafluorophosphate electrolyte as in Example 1 were used for the lithium secondary battery (single-layer aluminum laminate cell). The output characteristics were measured. The battery was produced according to a known cell configuration / assembly method.

The obtained lithium secondary battery was charged to 4.8 V at a constant current of 30 mA / g (corresponding to 0.2 C at the C rate) under a temperature condition of 25 ° C., and discharged at 30 mA / g and 60 mA / g, respectively. , 150 mA / g, 300 mA / g, 450 mA / g, 750 mA / g, 900 mA / g, and 1050 mA / g at a constant current up to 2.5 V, the output characteristics of each sample were evaluated. The capacity retention at each rate was compared for Li _0.44 MnO ₂ and Li _0.63 MnO ₂ in FIG. In the case of Li _0.44 MnO ₂ , what was about 40% capacity retention at 1050 mA / g equivalent to 7C was found to be higher than 70% in Li _0.63 MnO _2. did. From this, it was confirmed that the lithium insertion treatment can not only increase the capacity but also increase the output.

Claims (6)

A tunnel represented by Li _x Mn _1-y Ti _y O ₂ (0.5 ≦ x ≦ 1, 0 ≦ y <0.56) as a chemical composition formula, belonging to an orthorhombic system as a crystal structure, and occupied by lithium A lithium secondary battery positive electrode material comprising lithium, manganese, titanium, and oxygen having a structure. A Li _x Mn _1-y Ti _y O ₂ (0.40 <x <0.50, 0 ≦ y <0.56) prepared in advance is used as a starting material, and is produced by a lithium insertion process. Item 2. A method for producing a positive electrode material for a lithium secondary battery according to Item 1. The method for producing a positive electrode material according to claim 2, wherein the lithium insertion treatment is performed in a molten salt containing a lithium compound, or in an organic solvent or an aqueous solution in which the lithium compound is dissolved. A lithium secondary battery comprising the positive electrode material according to claim 1, wherein a positive electrode of a lithium secondary battery having a positive electrode, a negative electrode, and an electrolyte substance. The lithium secondary battery according to claim 4, wherein lithium or a lithium alloy negative electrode is used as a negative electrode of the battery and can be stably charged and discharged in a voltage range of 4 V. The lithium secondary battery according to claim 4, wherein a carbon negative electrode is used as a negative electrode of the battery, and charging and discharging can be stably performed in a voltage range of 4V.

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