JP5644273B2 - Titanium oxide, method for producing the same, and electrochemical device using the same as member - Google Patents

Description

The present invention relates to a titanium oxide, a method for producing the same, and an electrochemical device using the titanium oxide as a member.

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 hybrid cars and power load leveling systems in the future, and their importance is increasing.

This lithium secondary battery mainly comprises a positive electrode and a negative electrode containing materials capable of reversibly occluding and releasing lithium, an electrolyte solution in which a lithium ion conductor is dissolved in a non-aqueous organic solvent, and a separator. Element.

Among these constituent elements, lithium cobalt oxide (LiCoO ₂ ), lithium manganese oxide (LiMn ₂ O ₄ ), and lithium titanium oxide (Li ₄ Ti ₅ O) are considered as active materials for electrodes. ₁₂ ) and other metal materials such as metal lithium, lithium alloy and tin alloy, and carbon materials such as graphite and MCMB (mesocarbon microbeads).

For these materials, the voltage of the battery is determined by the difference in chemical potential in the lithium content of each active material, but a lithium potential battery that is excellent in energy density is capable of forming a large potential difference depending on the combination. It is the feature.

In particular, in the combination of lithium cobalt oxide LiCoO ₂ active material and carbon material as an electrode, a voltage close to 4V is possible, the charge / discharge capacity (the amount of lithium that can be desorbed and inserted from the electrode) is large, and the safety is also high. Due to its high cost, this combination of electrode materials is widely used in current lithium secondary batteries.

On the other hand, the combination of an electrode containing a spinel-type lithium manganese oxide (LiMn ₂ O ₄ ) active material and a spinel-type lithium titanium oxide (Li ₄ Ti ₅ O ₁₂ ) active material allows lithium occlusion / desorption reactions to occur. Since it is easy to be performed smoothly and the change in the volume of the crystal lattice accompanying the reaction is smaller, it has become clear that a lithium secondary battery excellent in a long-term charge / discharge cycle can be obtained and put into practical use.

In the future, it is expected that chemical batteries such as lithium secondary batteries and capacitors will require large-sized, long-life batteries such as automobile power supplies, large-capacity backup power supplies, and emergency power supplies. There has been a need for a higher performance (high capacity) electrode active material with a combination of various oxide active materials.

Of these, the titanium oxide active material has a voltage of about 1 to 2 V when lithium metal is used for the counter electrode. Therefore, materials having various crystal structures are used as the negative electrode material. The possibility as is being studied.

Among them, titanium dioxide having a sodium bronze type crystal structure capable of a smooth lithium occlusion / desorption reaction equivalent to spinel type lithium titanium oxide and capable of higher capacity than spinel type (in this specification, “ An active material (which is abbreviated as “TiO ₂ (B)”), which has a sodium bronze type crystal structure, has attracted attention as an electrode material. (See Non-Patent Document 1)

However, when TiO ₂ (B) is used as an electrode, the irreversible capacity of the initial cycle is large, and there has been a problem in use as a negative electrode material in a high capacity lithium secondary battery.

On the other hand, as a high-capacity material, a titanium dioxide having a ramsdelite type crystal structure (in this specification, “titanium dioxide having a ramsdelite type crystal structure” is abbreviated as “TiO ₂ (R)”) is also used. , Was noticed. (See Non-Patent Document 2)

When this TiO ₂ (R) is used as an electrode, the irreversible capacity in the initial cycle is small, and a high capacity exceeding 300 mAh / g is possible. Therefore, it is expected as a high capacity oxide negative electrode material. It was. (See Non-Patent Documents 2 and 3)

However, when the charge / discharge cycle is repeated, the capacity decrease is remarkable, and it is reported that the capacity after 10 cycles is less than 200 mAh / g, and a TiO ₂ (R) active material is used as an electrode. Was a problem in terms of battery life. (See Non-Patent Document 2)

On the other hand, recently, an electrode active material having a chemical composition formula of H ₂ Ti ₁₂ O ₂₅ has been reported to have an initial capacity of 200 mAh / g or more and a small capacity decrease due to a charge / discharge cycle. (See Patent Document 1)

Furthermore, the crystal structure of this H ₂ Ti ₁₂ O ₂₅ and the above TiO ₂ (B) is very similar, and the presence of an intergrowth phase having an intermediate crystal structure between the two became clear. (See Patent Document 2)

Here, the intergrowth phase gives a pattern similar to both H ₂ Ti ₁₂ O ₂₅ and TiO ₂ (B) in the X-ray diffraction pattern, but the diffraction peak position does not match either, It refers to the case of having an intermediate crystal structure as an average structure, not a simple mixture. For example, titanium dioxide has been reported as an example of the intergrowth phase. (See Non-Patent Document 4)

In the case of using the intergrowth phase of H ₂ Ti ₁₂ O ₂₅ and TiO ₂ (B) as an electrode active material, excellent electrode characteristics have been reported. The superiority of the intergrowth structure was revealed. (See Patent Document 2)

When this is applied to TiO ₂ (R), if another basic structure capable of high capacity and an intergrowth structure can be constructed as the characteristics of the crystal structure, TiO ₂ is maintained while maintaining the characteristics of high capacity. (R) It was expected that the cycle characteristics, which were disadvantages in the case of a single crystal structure, were improved, and the capacity of the battery could be increased.

Here, the ramsdellite type crystal structure taken by TiO ₂ (R) has a double rutile chain constructed from two TiO ₆ octahedrons as a basic skeleton, and a one-dimensional space that can be occupied by lithium is formed. . (Figure 1)

That is, it was considered that improvement in characteristics can be expected by combining an oxide system having this double rutile chain as a basic structure and a large tunnel space suitable for lithium insertion capable of high capacity.

On the other hand, as the titanium oxide having the double rutile chain as a basic structure, NaTi ₂ O ₄ having a calcium ferrite type structure shown in FIG. 2 and Na _1-x Ti ₂ O _{4 in} which a part of Na is deficient are known. It was done. (See Non-Patent Documents 5 and 6)

However, there is only the above-mentioned Non-Patent Document 4 as an example of constructing an intergrowth structure with TiO ₂ (R) in known literatures and the like, and the intergrowth structure in this case is a rams delite type. Since it was constructed from a rutile structure, it was not suitable for high capacity.

JP 2008-255000 A JP 2010-150125 A

L. Brohan, R.M. Marchand, Solid State Ionics, 9-10, 419-424 (1983) R. K. B. Gover, J .; R. Tolchard, H.C. Tukamoto, T .; Murai, J. et al. T. T. et al. S. Irvine, Journal of The Electrochemical Society, 146, 4348-4353 (1999) A. Kuhn, R.A. Amandi, F.M. Garcia-Alvarado, Journal of Power Sources, 92, 221-227 (2001) Y. Takahashi, N .; Kijima, J .; Akimoto, Chemistry of Materials, 18, 748-752 (2006) J. et al. Akimoto, H. et al. Takei, Journal of Solid State Chemistry, 18, 748-752 (2006). Y. Takahashi, K .; Kataoka, K .; Ohshima, N .; Kijima, J .; Awaka, K .; Kawaguchi, J. et al. Akimoto, Journal of Solid State Chemistry, 180, 1020-1027 (2007)

Accordingly, the present invention solves the above-mentioned problems as described above, is an excellent titanium oxide as a lithium secondary battery electrode material that is excellent in long-term charge / discharge cycles and can be expected to have a high capacity, and a method for producing the same, and It is an object of the present invention to provide an electrochemical device using the above as a member.

As a result of intensive studies, the present inventor has conducted heat treatment in molten salt using Na _1-x Ti ₂ O ₄ (0 ≦ x ≦ 0.442) having a calcium ferrite type structure as a starting material, or in an acidic solution. By using the dipping process, a part of the original calcium ferrite type partial structure is changed to a ramsdellite type crystal structure, and the titanium oxide Na becomes an intergrowth structure of calcium ferrite type and ramsdellite type structure. _It can be confirmed that _1-x Li _y Ti ₂ O ₄ (0.442 <x ≦ 1, 0 ≦ y <1) can be produced, and an electrode produced using this titanium oxide as an electrode active material is used. In the lithium secondary battery, the present invention was completed by confirming a high capacity exceeding 200 mAh / g and excellent cycle characteristics.

The present invention relates to a titanium oxide Na _1-x Li _y Ti ₂ O ₄ (0.442 <x ≦ 1, 0 ≦ y <1) having a calcium ferrite type and a ramsdellite type intergrowth structure shown below, and A manufacturing method thereof is provided.
That is, the present invention has a chemical composition of Na _1-x Li _y Ti ₂ O ₄ (0.442 <x ≦ 1, 0 ≦ y <1), and the crystal structures are calcium ferrite type and ramsdellite type. It is a titanium oxide characterized by having an intergrowth structure.
Further, the present invention has a chemical composition of Na _1-x Li _y Ti ₂ O ₄ (0.442 <x ≦ 1, 0 ≦ y <1), and the crystal structure is an intercalation of calcium ferrite type and ramsdellite type. It is a titanium oxide characterized by having a growth structure and a partial ratio of the partial structure of 1: 1.
Furthermore, the present invention has a chemical composition of Na _1-x Li _y Ti ₂ O ₄ (0.442 <x ≦ 1, 0 ≦ y <1), and the crystal structure is an intercalation of calcium ferrite type and ramsdellite type. It is a titanium oxide characterized by having a growth structure and a crystal lattice of the average structure belonging to the orthorhombic system.
Further, the present invention has a chemical composition of Na _1-x Li _y Ti ₂ O ₄ (0.442 <x ≦ 1, 0 ≦ y <1), and the crystal structure is an intercalation of calcium ferrite type and ramsdellite type. It has a growth structure, its abundance ratio is 1: 1, and the crystal lattice of its average structure belongs to the orthorhombic system, and its lattice constants are 1.73 nm <a <1.76 nm, 1.04 nm <b It is a titanium oxide characterized by <1.08 nm, 0.29 nm <c <0.31 nm.
Furthermore, the present invention includes a step of heat-treating sodium titanium oxide Na _1-x Ti ₂ O ₄ (0 ≦ x ≦ 0.442) having a calcium ferrite type structure in a molten salt at 200 ° C. to 500 ° C. Na _1-x Li _y Ti ₂ O ₄ (0.442 <x ≦ 1, 0 ≦ y <1), and the crystal structure is intergrowth of calcium ferrite type and ramsdellite type A titanium oxide production method characterized by having a structure.
In the method for producing a titanium oxide of the present invention, the molten salt contains one or more salts selected from the group consisting of lithium nitrate, lithium chloride, lithium bromide, lithium iodide, and zinc chloride. Molten salt can be used.
Furthermore, in the titanium oxide production method of the present invention, in the step of molten salt treatment of sodium titanium oxide Na _1-x Ti ₂ O ₄ (0 ≦ x ≦ 0.442) having a calcium ferrite type structure, As the salt, a molten lithium salt can be used as an essential salt .
The present invention also relates to an electrochemical device selected from a lithium ion secondary battery, a lithium secondary battery, a sodium secondary battery, and an electrochemical capacitor using the titanium oxide of the present invention as an electrode material active material. .

According to the present invention, titanium oxide Na _1-x Li _y Ti ₂ O ₄ (0.442 <x ≦ 1, 0 ≦ y <1) having an intergrowth structure of calcium ferrite type and ramsdellite type structure is produced. In a battery using this titanium oxide as an electrode active material, high capacity and excellent cycle characteristics are possible.

Is a diagram showing the crystal structure of the Ramsdellite-type _TiO 2 (R). It is a diagram showing the crystal structure of the calcium ferrite type NaTi ₂ O _4. It is a schematic diagram which shows an example of a lithium secondary battery. The powder X-ray diffraction pattern of (a) Na _1-x Ti ₂ O ₄ (x = 0.1), which is the starting material of the present invention, obtained in Example 1, and (b) the intergrowth structure of the present invention. It is a powder X-ray diffraction pattern of titanium oxide. It is a figure which shows the voltage change accompanying the lithium insertion / detachment | desorption reaction of the battery using the electrode produced by using the titanium oxide of this invention obtained in Example 2 as an active material. 4 is a single crystal X-ray diffraction pattern of the titanium oxide of the present invention obtained in Example 3. FIG. It is a figure which shows the crystal structure of the titanium oxide which has the intergrowth structure of the ramsdellite type | mold of this invention obtained in Example 3, and a calcium ferrite type | mold structure, and the ratio exists. Powder X-ray diffraction pattern (a) of Na _1-x Ti ₂ O ₄ (x = 0.3), which is the starting material of the present invention obtained in Example 4, and titanium oxidation having an intergrowth structure of the present invention It is the powder X-ray diffraction pattern (b) of a thing, (c). It is a figure which shows the voltage change accompanying the lithium insertion / detachment | desorption reaction of the battery using the electrode produced using the titanium oxide of this invention obtained in Example 5 as an active material. 4 is a powder X-ray diffraction pattern of the titanium oxide of the present invention obtained in Example 6. FIG. It is a figure which shows the voltage change accompanying the lithium insertion / detachment | desorption reaction of the battery using the electrode produced by using the titanium oxide of this invention obtained in Example 7 as an active material.

As a result of intensive studies on a method for producing a titanium oxide using Na _1-x Ti ₂ O ₄ (0 ≦ x ≦ 0.442) having a calcium ferrite type structure as a starting material, the present inventors have found that the original calcium ferrite Na _1-x Li _y Ti ₂ O ₄ (0.442 <x ≦ 1, 0 ≦ y) in which a part of the type skeletal structure is changed to a ramsdellite type crystal structure and has an intergrowth structure with a calcium ferrite type structure. It was found that <1) can be produced, and it was found to be a novel compound having a new type of crystal structure.

As a result, compared with TiO ₂ (R) having a known ramsdellite structure, in a lithium secondary battery using an electrode produced using a titanium oxide having an intergrowth structure of the present invention as an active material, 200 mAh / Since it was confirmed that there was an initial capacity exceeding g and almost no capacity decrease was observed even after 10 cycles, the present invention was completed.

One of the titanium oxides of the present invention is the release of sodium contained in Na _1-x Ti ₂ O ₄ (0 ≦ x ≦ 0.442) having a known calcium ferrite type structure, and lithium Is a compound having a chemical composition of Na _1-x Li _y Ti ₂ O ₄ (0.442 <x ≦ 1, 0 ≦ y <1).
As a characteristic of the crystal structure, a part of the original calcium ferrite type skeleton structure is changed into a ramsdellite type crystal structure, and it is a compound characterized by adopting an intergrowth structure of calcium ferrite type and ramsdellite type structure.
As a more detailed characteristic of the intergrowth structure, the compound has a 1: 1 ratio of calcium ferrite type and ramsdellite type partial structures.
As a more detailed characteristic of the intergrowth structure, the crystal lattice having an average structure belongs to the orthorhombic system, and the lattice constant thereof is 1.73 nm <a <1.76 nm, 1.04 nm <b <1.08 nm. 0.29 nm <c <0.31 nm.
Moreover, this titanium oxide production method is characterized in that heat treatment is performed in a molten salt using Na _1-x Ti ₂ O ₄ (0 ≦ x ≦ 0.442) having a known calcium ferrite type structure as a starting material. It is said.
A more detailed production method using a molten salt is characterized in that a heat treatment temperature is synthesized in a temperature range of 20 ° C. or more and 500 ° C. or less using a salt containing lithium.
Further, as another method for producing this titanium oxide, a dipping treatment is carried out in an acidic solution using Na _1-x Ti ₂ O ₄ (0 ≦ x ≦ 0.442) having a known calcium ferrite type structure as a starting material. It is characterized by that.
A more detailed production method using an acidic solution is characterized in that the immersion treatment temperature is 20 ° C. or higher and 100 ° C. or lower.
Furthermore, this titanium oxide can be used as an electrode material active material in electrochemical devices such as storage batteries, lithium secondary batteries, sodium secondary batteries, and lithium primary batteries.

The production method according to the present invention will be described in more detail.
(Synthesis of Na _1-x Ti ₂ O ₄ (0 ≦ x ≦ 0.442))
Of the present invention, Na _1-x Ti ₂ O ₄ (0 ≦ x ≦ 0.442), which is a starting material, includes, as a raw material, at least one of sodium metal or a sodium compound, and titanium metal or a titanium compound. It can be produced by weighing and mixing at least one kind so as to have a chemical composition of Na _1-x Ti ₂ O ₄ (0 ≦ x ≦ 0.442), using an airtight container, and firing at a high temperature. it can. As the synthesis method, it can be produced by both atmospheric pressure synthesis and high-pressure synthesis of 10,000 atmospheres or more.

(Normal pressure synthesis of Na _1-x Ti ₂ O ₄ (0 ≦ x ≦ 0.442))
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, and examples thereof include 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, or already _{Na 2 TiO 3, Na 2 Ti} 3 O 7 , sodium titanium oxide and going on compounds such as and the like. Among these, Na ₂ Ti ₃ O _{7 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, it is particularly preferable to use both TiO ₂ and titanium metal.

First, a mixture containing these is prepared. The mixing ratio of sodium raw material and titanium material _is preferably mixed such that the chemical composition of _{Na 1-x Ti 2 O 4} (0 ≦ x ≦ 0.442). Further, since sodium easily volatilizes during heating, the amount of sodium should be slightly more excessive than 1 in the above chemical formula, and preferably in the range of 0.6 to 1.1. 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 packed into a synthesis container. The material of the synthesis container is not particularly limited as long as it does not react with the sample at a high temperature and can maintain an inert atmosphere, and examples thereof include an iron container, a nickel container, and a molybdenum container. Among these, it is particularly preferable to use a pure iron container.

The mixture is then fired. The firing temperature can be appropriately set depending on the raw material,
Usually, the temperature may be about 600 ° C to 1500 ° C, preferably 1000 ° C to 1200 ° C. Further, the firing atmosphere may be an inert atmosphere or a reducing atmosphere.

The firing time can be appropriately changed according to the firing temperature and the like. The cooling method is not particularly limited, but may be natural cooling (cooling in the furnace) or slow cooling.

(High pressure synthesis of Na _1-x Ti ₂ O ₄ (0 ≦ x ≦ 0.442))
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 O _{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. Of these, Ti ₂ O ₃ is particularly preferable.

First, a mixture containing these is prepared. The mixing ratio of sodium raw material and titanium material _is preferably mixed such that the chemical composition of _{Na 1-x Ti 2 O 4} (0 ≦ x ≦ 0.442). 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.

Next, the mixture is fired under high temperature and high pressure conditions to obtain a compound represented by a composition formula Na _1-x Ti ₂ O ₄ (0 ≦ x ≦ 0.442). Although a calcination temperature can be suitably set according to the composition etc. of a mixture, it is about 800-1700 degreeC normally, Preferably it is 1200-1600 degreeC.

The firing pressure is 10,000 to 100,000 atm, preferably 30,000 to 80,000 atm, and more preferably 40,000 to 50,000 atm. The firing time can be appropriately changed according to the firing temperature and the like. For example, when the firing temperature is 1200 to 1600 ° C., it is preferably 0.5 to 3 hours. The cooling method is not particularly limited, but is usually natural cooling (rapid cooling) or slow cooling. After firing, the fired product may be pulverized by a known method as necessary.

(Synthesis of titanium oxide Na _1-x Li _y Ti ₂ O ₄ (0.442 <x ≦ 1, 0 ≦ y <1) by molten salt treatment)
Next, the starting material Na _1-x Ti ₂ O ₄ (0 ≦ x ≦ 0.442) is used to heat-treat in the molten salt, so that the Na _1-x Li _y Ti ₂ O ₄ (0 A compound having a chemical composition of .442 <x ≦ 1, 0 ≦ y <1) is obtained.

At this time, it is preferable to perform the treatment while dispersing Na _1-x Ti ₂ O ₄ (0 ≦ x ≦ 0.442) in the molten salt. As the molten salt, one containing at least one salt that melts at a low temperature, such as lithium nitrate, lithium chloride, lithium bromide, lithium iodide, and zinc chloride, can be used. The molten salt raw material powder and Na _1-x Ti ₂ O ₄ (0 ≦ x ≦ 0.442) are preferably mixed well. The mixing ratio is usually such that the weight of the molten salt raw material is 2 to 40 times, preferably 5 to 20 times, by weight.

The temperature of the molten salt treatment is 200 ° C to 500 ° C, preferably 250 to 300 ° C. When the temperature of the molten salt treatment is lower than 200 ° C., it is difficult to sufficiently desorb sodium. On the other hand, when the temperature of the molten salt treatment is higher than 500 ° C., a part of the molten salt treatment changes to a rutile structure, so that a uniform crystal structure cannot be obtained. The treatment time is usually 1 to 30 hours, preferably 3 to 15 hours.

After the molten salt treatment, the obtained product is thoroughly washed with distilled water, then washed with methanol, ethanol, and the like, and dried to obtain the desired composition formula Na _1-x Li _y Ti ₂ O ₄ (0 .442 <x ≦ 1, 0 ≦ y <1). 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.

Depending on the conditions of the molten salt treatment, sodium is not completely eliminated, and when a lithium salt is used, lithium in the molten salt may be contained in the titanium oxide.
In addition, depending on the conditions of the molten salt treatment, it is possible to prepare a sample in which sodium is almost completely eliminated and lithium is not mixed. In this case, a new type having an intergrowth structure of calcium ferrite type and ramsdellite type structure can be prepared. It can be regarded as titanium dioxide.

(Synthesis of titanium oxide Na _1-x Li _y Ti ₂ O ₄ (0.442 <x ≦ 1, 0 ≦ y <1) by acidic solution treatment)
The titanium oxide Na _1-x Li _y Ti ₂ O ₄ (0.442 <x ≦ 1, 0 ≦ y <1) of the present invention is produced as another starting method by using a starting material Na _1-x Ti ₂ O ₄ ( 0 ≦ x ≦ 0.442) can also be obtained by immersion treatment in an acidic solution.

In this case, it is preferable that Na _1-x Ti ₂ O ₄ (0 ≦ x ≦ 0.442) is dispersed in an acidic solution, dipped for a predetermined time, and then dried. As the acid to be used, an aqueous solution containing any one or more of hydrochloric acid, sulfuric acid, nitric acid and the like having any concentration is suitable. Of these, use of dilute hydrochloric acid having a concentration of 0.1 to 1.0 N is preferable. The immersion treatment time is 10 hours to 10 days, preferably 1 day to 7 days. In order to shorten the processing time, it is preferable to replace the solution with a new one as appropriate. Further, in order to facilitate the exchange reaction, the treatment temperature is preferably higher than room temperature and 20 ° C. to 100 ° C. A known drying method can be applied to the drying, but vacuum drying or the like is more preferable.

Na _1-x Li _y Ti ₂ O ₄ (0.442 <x ≦ 1, 0 ≦ y <1) obtained in this way is free from lithium contamination due to its production method, By optimizing the conditions, it is possible to reduce the amount of sodium remaining from the starting material to below the detection limit of chemical analysis by a wet method.

(Electrochemical device)
The electrochemical device of the present invention uses an electrode containing the titanium oxide as an active material as a constituent member. That is, battery elements of known lithium secondary batteries (coin type, button type, cylindrical type, all solid type, etc.) can be used as they are except that the titanium oxide of the present invention is used as the electrode material active material.
FIG. 3 is a schematic view showing an example in which the electrochemical device of the present invention is applied to a coin-type lithium secondary battery. The coin-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.
Moreover, the electrochemical device of this invention can employ | adopt the battery element of a well-known lithium ion secondary battery or a sodium secondary battery as it is, except using the titanium oxide of this invention as an electrode material active material. Furthermore, the electrochemical device of this invention can employ | adopt a well-known electrochemical capacitor as it is, except using the titanium oxide of this invention as an electrode material active material.

In the present invention, the electrode is prepared by adjusting the electrode mixture by blending the titanium oxide active material of the present invention with a conductive agent, a binder, etc., if necessary, and crimping this to a current collector. it can. As the current collector, a stainless mesh, an aluminum mesh, an aluminum foil, a copper mesh, a copper 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 composition of the titanium oxide active material, the conductive agent, the binder, etc. in the 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. The agent may be 0 to 30% by weight (preferably 3 to 10% by weight), and the balance may be the titanium oxide active material of the present invention.

In the electrochemical device (lithium secondary battery) of the present invention, a known electrode that functions as a negative electrode and occludes lithium, such as metal lithium and lithium alloy, can be used as the counter electrode for the electrode. Alternatively, as the counter electrode, a known one that functions as a positive electrode and occludes lithium, such as lithium cobalt oxide (LiCoO ₂ ) or spinel type lithium manganese oxide (LiMn ₂ O ₄ ), can also be used. . That is, the electrode containing the active material of the present invention can function as a positive electrode or a negative electrode depending on the electrode constituent material to be combined.

In the electrochemical device of the present invention, a well-known battery element may be employed for a separator, a battery container, and the like.

Furthermore, known electrolyte solutions, solid electrolytes, and the like can be applied as the electrolyte. For example, as an electrolytic solution, an electrolyte such as lithium perchlorate or lithium hexafluorophosphate is used in a solvent such as ethylene carbonate (EC), dimethyl carbonate (DMC), propylene carbonate (PC), or diethyl carbonate (DEC). What was dissolved can be used.

Hereinafter, examples will be shown to further clarify the features of the present invention. The present invention is not limited to these examples.

(High-pressure synthesis of starting material Na _1-x Ti ₂ O ₄ (x = 0.1))
A Na ₂ O ₂ powder having a purity of 97% or more and a Ti ₂ O ₃ powder having a purity of 99.9% or more were uniformly mixed at a molar ratio of 1: 2 in a glove box substituted with argon gas. The mixture is packed in a platinum capsule and kept at 45,000 atm and 1400 ° C. for 1 hour using a cubic anvil type high pressure synthesizer, whereby the starting material Na _1-x Ti ₂ O ₄ ( x = 0.1).

When the crystal structure of the obtained compound was examined with a powder X-ray diffractometer (trade name RINT2550V, manufactured by Rigaku), it was found to be a single phase of orthorhombic system and space group Pnam having good crystallinity. It became clear. The powder X-ray diffraction pattern at this time is shown in FIG. Further, when the lattice constant was determined by the least square method using each index and its surface spacing, the following value was obtained, which was well equal to the known Na _1-x Ti ₂ O ₄ (x = 0.1) value. I did it.
a = 0.9228 nm
b = 1.0755 nm
c = 0.259nm

(Synthesis of titanium oxide Li _0.34 Na _0.001 Ti ₂ O ₄ )
Next, the obtained Na _1-x Ti ₂ O ₄ (x = 0.1) powder sample was mixed with LiNO ₃ (purity 99% or more) of about 60 times the sample by mass ratio, and made of alumina. The molten salt treatment was carried out by placing in a crucible and performing a heat treatment in air at 270 ° C. for 10 hours. After the treatment, excess LiNO ₃ was washed with pure water and dried to obtain the target Na _1-x Li _y Ti ₂ O ₄ (0.442 <x ≦ 1, 0 ≦ y <1). .

With respect to the obtained sample, X-ray diffraction data was measured by an X-ray powder diffractometer, and it was revealed that the sample was an orthorhombic almost single phase having good crystallinity. The powder X-ray diffraction pattern at this time is shown in FIG. Also, using each index and its surface spacing, the lattice constant was calculated by the least square method on the basis of the original calcium ferrite type structural model and assuming a double period in the a-axis direction. As a result, it became clear that the compound was not a known compound and was a new substance.
a = 1.476 nm
b = 1.0659 nm
c = 0.2961 nm

Further, when the chemical composition of the obtained compound was analyzed by ICP emission analysis (trade name Optima 3000, manufactured by PerkinElmer Japan), it was clear that it was a composition formula of Li _0.34 Na _0.001 Ti ₂ O _4. Thus, sodium was almost eliminated and a significant amount of lithium was confirmed to be mixed.

(Lithium secondary battery)
The titanium oxide Li _0.34 Na _0.001 Ti ₂ O ₄ thus obtained was used as an active material, acetylene black as a conductive agent, tetrafluoroethylene as a binder, and 45:45:10 by weight. An electrode is prepared by mixing so that lithium hexafluorophosphate is dissolved in a mixed solvent of ethylene carbonate (EC) and diethyl carbonate (DEC) (volume ratio 1: 1) using lithium metal as a counter electrode. A lithium secondary battery (coin-type cell) having the structure shown in FIG. 3 was prepared using the 1M solution thus prepared as an electrolytic solution, and the electrochemical lithium insertion / extraction behavior was measured. The battery was produced according to a known cell configuration / assembly method.

The fabricated lithium secondary battery was subjected to an electrochemical lithium insertion / extraction test at a current density of 10 mA / g and a cut-off potential of 3.0 V-1.0 V under a temperature condition of 25 ° C. It has been found that there are voltage flat portions near 2.3 V and 1.2 V, and reversible lithium insertion / extraction is possible. FIG. 5 shows voltage changes associated with lithium insertion / extraction reactions. The initial insertion / extraction capacities per active material weight were 226 mAh / g and 219 mAh / g, respectively. From this, it was revealed that the initial charge / discharge efficiency was 96% or more and that a discharge capacity of 220 mAh / g or more could be maintained even after 10 cycles. From the above, the titanium oxide Li _0.34 Na _0.001 Ti ₂ O ₄ active material of the present invention is capable of high capacity and highly reversible lithium insertion / extraction reaction, and as a lithium secondary battery electrode material It turned out to be promising.

(Single crystal synthesis of titanium oxide Ti ₂ O ₄ (= TiO ₂ ))
The starting material Na _1-x Ti ₂ O ₄ (x = 0.1) synthesized in Example 1 was subjected to molten salt treatment under the same conditions as in Example 1 without pulverization, and the target 0 A transparent single crystal synthesis having a size of about 1 mm square was obtained.

The selected single crystal sample was subjected to single crystal X-ray diffraction measurement using a single crystal four-axis X-ray diffractometer (trade name: AFC-7S, manufactured by Rigaku). As a result, it was confirmed that the single crystal sample was a good single crystal. Moreover, it was confirmed from the diffraction spot of strong intensity that the crystal system is orthorhombic.

Further, using the same single crystal, single crystal X-ray diffraction measurement was performed with an imaging plate type single crystal X-ray diffractometer (trade name R-AXIS RAPID-II, manufactured by Rigaku). FIG. 6 shows the obtained single crystal X-ray diffraction pattern (vibration photograph). From FIG. 6, the main reflection spot can be explained in the orthorhombic system, and it is necessary to take a double period in the a-axis direction based on the original calcium ferrite type structural model, and a further long period. The following lattice model was appropriate as the most probable lattice constant. This result was in good agreement with the powder X-ray diffraction data of Example 1.
a = 1.7513 nm
b = 1.0651 nm
c = 0.2962 nm

Further, as a result of single crystal X-ray structural analysis using the intensity data of single crystal X-ray diffraction assuming the above-mentioned lattice constant, the most appropriate analysis result in orthorhombic system and space group Pnam ( Confidence factor: R = 8.92%). As a result, it was clarified that the crystal structure of the titanium oxide has an intergrowth structure of a ramsdellite type and a calcium ferrite type structure shown in FIG. 7, and the abundance ratio thereof is 1: 1. In the figure, the layer indicated by R is a ramsdellite structure, the layer indicated by C is a partial structure of a calcium ferrite structure, and both layers are alternately laminated at a ratio of 1: 1 in the a-axis direction, and the entire crystal structure It can be seen that is built. It was confirmed that such an intergrowth structure is not a known crystal structure model but a new type of crystal structure.

In addition, the chemical composition determined from the crystal structure analysis was Ti ₂ O ₄ (= TiO ₂ ), and it was revealed that this was a new type of titanium dioxide having almost no sodium or lithium.

(Atmospheric pressure synthesis of starting material Na _1-x Ti ₂ O ₄ (x = 0.3))
Na: Ti: O molar ratio of pre-synthesized Na ₂ Ti ₃ O ₇ powder of purity 99.9% or more, metal Ti powder of purity 99.9% or more, and TiO ₂ powder of purity 99.9% or more Is weighed and mixed so that the ratio becomes 0.8: 2: 4, the mixture is sealed in a pure iron synthesis vessel, and kept in an argon gas atmosphere at a maximum temperature of 1200 ° C. for 10 hours using a tubular electric furnace. Thus, starting material Na _1-x Ti ₂ O ₄ (x = 0.3) was obtained.

When the crystal structure of the obtained compound was examined by a powder X-ray diffractometer, it was revealed that it was a single phase of orthorhombic system and space group Pnam having good crystallinity. The powder X-ray diffraction pattern at this time is shown in FIG. Further, it was confirmed that a known Na _1-x Ti ₂ O ₄ (x = 0.3) was synthesized from the value of the lattice constant determined by the least square method using each index and its surface spacing.

(Synthesis of titanium oxide Na _0.1 Ti ₂ O ₄ and Na _0.003 Ti ₂ O ₄ )
The pulverized product of Na _1-x Ti ₂ O ₄ (x = 0.3) synthesized above was immersed in a 0.5N hydrochloric acid solution as a starting material and kept at room temperature for 5 days. Then, an acidic solution treatment was performed. In order to increase the processing speed, the solution was changed every 12 hours. Thereafter, it was washed with water and dried in vacuum at 120 ° C. for 24 hours to obtain a target titanium oxide Na _1-x Ti ₂ O ₄ (0.442 <x ≦ 1) polycrystal.

When the chemical composition of the obtained sample was analyzed by ICP emission spectrometry, the chemical formula was valid with Na _0.1 Ti ₂ O ₄ . Further, when the crystal structure was examined by a powder X-ray diffractometer, it was revealed that the crystal was an orthorhombic almost single phase having good crystallinity. The powder X-ray diffraction pattern at this time is shown in FIG.

Further, for the purpose of further reducing the amount of sodium, an acidic solution treatment using a hydrochloric acid solution was again performed at 80 ° C. for 5 days. As a result, it was confirmed that the chemical composition of the obtained sample was Na _0.03 Ti ₂ O ₄ by ICP emission analysis. Further, when the crystal structure was examined by a powder X-ray diffractometer, it was found that the crystal structure was an orthorhombic almost single phase having good crystallinity. The powder X-ray diffraction pattern at this time is shown in FIG.

(Lithium secondary battery)
For the obtained Na _0.1 Ti ₂ O ₄ , an electrode was produced under the same conditions as in Example 1, and the current density was 10 mA / g and the cutoff was 3.0 V to 1.0 V under the temperature condition of 25 ° C. An electrochemical lithium insertion / extraction test was conducted at a potential. As a result, as in Example 1, it was found that there were voltage flat portions in the vicinity of about 2.3 V and 1.2 V, and reversible lithium insertion / extraction was possible. FIG. 9 shows voltage changes associated with lithium insertion / extraction reactions. The initial insertion / desorption capacities per active material weight were 184 mAh / g and 189 mAh / g, respectively. From this, the initial charge / discharge efficiency was 100% or more, and it was suggested that the remaining sodium was eliminated due to the lithium insertion / extraction reaction. It was also revealed that a discharge capacity of 205 mAh / g can be maintained even after 20 cycles. From the above, the titanium oxide Na _0.1 Ti ₂ O ₄ active material of the present invention is capable of high capacity and highly reversible lithium insertion / extraction reaction, and is promising as a lithium secondary battery electrode material. Became clear.

Further, compared with Example 2, although the capacity of the 1.2 V plateau region is slightly decreased due to the influence of the remaining sodium, no significant difference is seen in the charge / discharge curves themselves, and the different production methods However, it was suggested that a titanium oxide having the same crystal structure could be synthesized.

(Synthesis of titanium oxide Li _0.02 Na _0.003 Ti ₂ O ₄ )
Starting material Na _1-x Ti ₂ O ₄ (x = 0.3) polycrystalline material obtained in Example 4 was used as a starting material in a LiNO ₃ molten salt at 270 ° C. in the same manner as in Example 1. by treating 6 hours to obtain titanium oxide _{Na 1-x Li y Ti 2} O 4 for the purpose of (0.442 <x ≦ 1,0 ≦ y <1).

When the chemical composition of the obtained sample was analyzed by ICP emission spectrometry, the chemical formula was valid as Li _0.02 Na _0.003 Ti ₂ O ₄ . Further, when the crystal structure was examined by a powder X-ray diffractometer, it was revealed that the crystal was an orthorhombic almost single phase having good crystallinity. The powder X-ray diffraction pattern at this time is shown in FIG.

(Lithium secondary battery)
For the obtained Li _0.02 Na _0.003 Ti ₂ O ₄ , an electrode was produced under the same conditions as in Example 1 and Example 4, and the current density was 10 mA / g under the temperature condition of 25 ° C. An electrochemical lithium insertion / extraction test was performed at a cutoff potential of 0V-1.0V. As a result, as in Example 1, it was found that there were voltage flat portions in the vicinity of about 2.3 V and 1.2 V, and reversible lithium insertion / extraction was possible. FIG. 11 shows voltage changes associated with lithium insertion / extraction reactions. The initial insertion / desorption capacity per active material weight was 248 mAh / g and 227 mAh / g, respectively. From this, it was revealed that the initial charge / discharge efficiency was 91% or more and that a discharge capacity of 224 mAh / g could be maintained even after 10 cycles. From the above, the titanium oxide Li _0.02 Na _0.003 Ti ₂ O ₄ active material of the present invention is capable of high capacity and reversible lithium insertion / extraction reaction, and as a lithium secondary battery electrode material It turned out to be promising.

In addition, even when compared with the cases of Example 2 and Example 5, no significant difference was observed in the charge / discharge curves, and although the production method was different, titanium oxide having the same crystal structure could be synthesized. Was suggested.

DESCRIPTION OF SYMBOLS 1 Coin type lithium secondary battery 2 Negative electrode terminal 3 Negative electrode 4 Solid electrolyte 5 Insulation packing 6 Positive electrode 7 Positive electrode can

Claims (8)

It has a chemical composition of Na _1-x Li _y Ti ₂ O ₄ (0.442 <x ≦ 1, 0 ≦ y <1), and the crystal structure is an intergrowth structure of calcium ferrite type and ramsdellite type Titanium oxide characterized by It has a chemical composition of Na _1-x Li _y Ti ₂ O ₄ (0.442 <x ≦ 1, 0 ≦ y <1), and the crystal structure is an intergrowth structure of calcium ferrite type and ramsdellite type, And the titanium oxide characterized by the existence ratio of the partial structure being 1: 1. It has a chemical composition of Na _1-x Li _y Ti ₂ O ₄ (0.442 <x ≦ 1, 0 ≦ y <1), and the crystal structure is an intergrowth structure of calcium ferrite type and ramsdellite type, A titanium oxide characterized in that the crystal lattice of the average structure belongs to the orthorhombic system. It has a chemical composition of Na _1-x Li _y Ti ₂ O ₄ (0.442 <x ≦ 1, 0 ≦ y <1), and the crystal structure is an intergrowth structure of calcium ferrite type and ramsdellite type, The abundance ratio is 1: 1, the crystal lattice of the average structure belongs to the orthorhombic system, and the lattice constants are 1.73 nm <a <1.76 nm, 1.04 nm <b <1.08 nm, Titanium oxide characterized by 0.29 nm <c <0.31 nm. Na heat treatment at 200 ° C. to 500 ° C. in a molten salt of sodium titanium oxide Na _1-x Ti ₂ O ₄ (0 ≦ x ≦ 0.442) having a calcium ferrite type structure is included. _1-x Li _y Ti ₂ O ₄ (0.442 <x ≦ 1, 0 ≦ y <1), and the crystal structure is an intergrowth structure of calcium ferrite type and ramsdellite type A method for producing a titanium oxide, which is characterized. 6. The production of titanium oxide according to claim 5, wherein the molten salt is a molten salt containing one or more salts selected from the group consisting of lithium nitrate, lithium chloride, lithium bromide, lithium iodide, and zinc chloride. Method. In the step of subjecting sodium titanium oxide Na _1-x Ti ₂ O ₄ (0 ≦ x ≦ 0.442) having a calcium ferrite structure to a molten salt treatment, a lithium molten salt is used as an essential salt as a molten salt The method for producing a titanium oxide according to claim 5. Electrochemistry selected from lithium ion secondary batteries, lithium secondary batteries, sodium secondary batteries, and electrochemical capacitors using the titanium oxide according to any one of claims 1 to 4 as an electrode material active material. device.

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