JP6395052B2 - Titanium oxide and manufacturing method thereof, active material for secondary battery and manufacturing method thereof, and secondary battery using titanium oxide as active material - Google Patents

Description

  The present invention relates to a titanium oxide and a manufacturing method thereof, an active material for a secondary battery and a manufacturing method thereof, and a secondary battery using the titanium oxide as an active material.

  In recent years, secondary batteries are mounted on many portable electronic devices such as mobile phones and notebook computers, most of which are lithium secondary batteries. Secondary batteries such as lithium secondary batteries are expected to be put into practical use as large batteries such as hybrid vehicles and power load leveling systems, and their importance is increasing.

  For example, a lithium secondary battery is mainly composed of an electrode composed of a positive electrode and a negative electrode containing a material capable of reversibly occluding and releasing lithium, and a separator or solid electrolyte containing a non-aqueous electrolyte. And

  In the future, when applications such as automobile power supplies, high-capacity backup power supplies, and emergency power supplies are assumed, it is predicted that secondary batteries with higher capacity and longer life will be required. Therefore, development of a secondary battery having a higher capacity and a longer life is required by combining various active materials.

For example, a lithium secondary battery comprising a titanium oxide represented by the formula Li ₂ Ti ₆ O ₁₃ as a main component and a monoclinic Na ₂ Ti ₆ O ₁₃ type tunnel structure. Active materials have been proposed (see Patent Document 1 and Non-Patent Document 1).

On the other hand, as a titanium oxide having a similar chemical composition, a titanium oxide represented by the formula Li ₂ Ti ₃ O ₇ and having an orthorhombic NaLiTi ₃ O ₇ type crystal structure is used as an active material for a lithium secondary battery. It has been proposed to be used as a substance (see Non-Patent Document 2). Furthermore, a titanium oxide represented by the formula HLiTi ₃ O ₇ obtained by exchanging Li of the titanium oxide represented by the formula Li ₂ Ti ₃ O ₇ with H is used as an active material for a lithium secondary battery. It has also been proposed to use it (see Non-Patent Document 3).

JP 2010-123424 A

K. Kataoka et al. , Chem. Mater. , 23, 2344 (2011) Kazuaki Chiba et al., 81st Electrochemical Society, Abstracts, 1R12, P370 (2014) Kazuaki Chiba et al., The 7th International Conference on Advanced Storage Batteries for Electric Vehicles, P-18 (2014)

However, even when the titanium oxide described in Patent Document 1 and Non-Patent Document 1 (hereinafter also referred to as “conventional Li ₂ Ti ₆ O ₁₃ ”) is used as an active material for a secondary battery, At present, the capacity and charge / discharge cycle characteristics of secondary batteries are not sufficient.

In addition, the inventors have evaluated the electrochemical characteristics of the titanium oxides (Li ₂ Ti ₃ O ₇ , HLiTi ₃ O ₇ ) described in Non-Patent Document 2 and Non-Patent Document 3, respectively. As a result, although any titanium oxide can improve the capacity and charge / discharge cycle characteristics of the secondary battery as compared with the conventional Li ₂ Ti ₆ O ₁₃ , there is room for further improvement. It has been found. In particular, it is considered that there is room for improvement in that the capacity at the time of lithium desorption is low and the irreversible capacity (the difference between the capacity at the time of lithium insertion and the capacity at the time of lithium desorption) is high.

  The present invention has been made in view of the above, and has a higher capacity and longer life than before, a titanium oxide that can be used as an active material for a secondary battery with a high capacity at the time of lithium desorption and a low irreversible capacity. The purpose is to provide. The present invention also provides a method for producing the titanium oxide, an active material for a secondary battery mainly containing the titanium oxide, a method for producing the active material, and a secondary battery using the titanium oxide as an active material. Objective.

The present invention relates to a titanium oxide represented by the formula Li _{(2-x + 2α)} Na _x Ti ₆ O _{(13 + α)} . In the formula, x satisfies 0 ≦ x <1, and α satisfies 0 ≦ α <0.3. In the powder X-ray diffraction pattern using CuKα rays, the titanium oxide of the present invention exhibits a maximum peak in the range of diffraction angle 2θ of 18 ° ± 0.5 °, and further 10.5 ° ± 0.5. Peaks are shown in the ranges of °, 16 ° ± 0.5 ° and 19 ° ± 0.5 °, respectively.

The titanium oxide is preferably synthesized by performing a heat treatment on a precursor represented by the formula H _(1-y1) Li _{(1 + y1-y2)} Na _y2 Ti ₃ O ₇ . In the precursor formula, y1 and y2 satisfy 0 ≦ y1 + y2 <1. The crystal structure of the precursor is an orthorhombic NaLiTi ₃ O ₇ type tunnel structure.

  The heat treatment of the precursor is preferably performed in a temperature range of 300 ° C. or higher and lower than 550 ° C. in air or vacuum.

The precursor is preferably synthesized by proton exchange in which at least one of the starting materials Na and Li represented by the formula Li _(2-z) Na _z Ti ₃ O ₇ is exchanged for H. In the formula of the starting material, z satisfies 0 ≦ z <1. The crystal structure of the starting material is an orthorhombic NaLiTi ₃ O ₇ type tunnel structure.

The starting material is preferably synthesized by lithium ion exchange in which Na of NaLiTi ₃ O ₇ produced from a sodium raw material, a lithium raw material and a titanium raw material is exchanged for Li.

  This invention relates to the manufacturing method of the active material for secondary batteries by which the titanium oxide of this invention is synthesize | combined by the said manufacturing method.

  The present invention relates to an active material for a secondary battery containing the titanium oxide as a main component.

  The present invention relates to a secondary battery including a positive electrode, a negative electrode, and an electrolyte. At least one of the positive electrode and the negative electrode contains an active material for a secondary battery containing the titanium oxide as a main component.

According to the present invention, it is possible to produce a novel titanium oxide represented by the formula Li _{(2-x + 2α)} Na _x Ti ₆ O _{(13 + α)} , and this novel titanium oxide can be used as an active material of an electrode material. By using it, it is possible to provide a secondary battery active material and a secondary battery that have a higher capacity and a longer life than the conventional Li ₂ Ti ₆ O ₁₃ . Furthermore, by using this novel titanium oxide as an active material for an electrode material, a secondary battery active material and a secondary battery having a higher capacity at the time of lithium desorption and a lower irreversible capacity than HLiTi ₃ O ₇ Can be provided.

It is an example of the synthesis | combination flowchart of the titanium oxide of this invention. It is a schematic view showing the crystal structure of NaLiTi ₃ O ₇ having a tunnel structure orthorhombic. It is a fragmentary sectional view which shows typically an example of the secondary battery of this invention. 2 is a powder X-ray diffraction pattern of titanium oxide according to Example 1 and Reference Example 1. FIG. 2 is a powder X-ray diffraction pattern of a titanium oxide according to Comparative Example 1. It is a FTIR spectrum of the titanium oxide which concerns on Example 1 and Reference Example 1. It is a figure which shows the voltage change accompanying the lithium insertion / elimination reaction in Example 1 and Reference Example 1. It is a figure which shows the voltage change accompanying the lithium insertion / detachment | desorption reaction in the comparative example 1. FIG. It is a figure which shows the relationship between the cycle number of the lithium secondary battery which concerns on Example 1 and Reference Example 1, and lithium insertion capacity. It is a figure which shows the relationship between the cycle number of the lithium secondary battery which concerns on Example 1 and Reference Example 1, and lithium desorption capacity.

[Production method of titanium oxide]
FIG. 1 is an example of a synthesis flowchart of the titanium oxide of the present invention. The titanium oxide of the present invention is preferably synthesized by performing a heat treatment of the following precursor.
Precursor: Formula H _(1-y1) Li _{(1 + y1-y2)} Na _y2 Ti ₃ O ₇ (wherein y1 and y2 satisfy 0 ≦ y1 + y2 <1), and the crystal structure is orthorhombic This is a type of NaLiTi ₃ O ₇ type tunnel structure.

(Precursor H _(1-y1) Li _{(1 + y1-y2)} Na _y2 Ti ₃ O ₇ )
FIG. 2 is a schematic diagram showing a crystal structure of NaLiTi ₃ O ₇ having an orthorhombic tunnel structure. In FIG. 2, each of a plurality of triangular faces constitutes a TiO ₆ octahedron. O is arranged at each vertex of the octahedron, and its center is occupied by Ti. In FIG. 2, the larger sphere located in the vicinity of the octahedron represents Na, and the smaller sphere represents Li. In this way, a structure in which alkali metal ions such as Na and Li are one-dimensionally arranged in a gap between a three-dimensional skeleton structure such as an octahedron is called a tunnel structure.

The chemical composition of the precursor is not particularly limited as long as the precursor is represented by the formula H _(1-y1) Li _{(1 + y1-y2)} Na _y2 Ti ₃ O ₇ . Typically, as shown in FIG. 1, HLiTi ₃ O ₇ where y1 = y2 = 0. However, 0 <y1 + y2 <1 may be sufficient. In this case, 0 <y1 + y2 ≦ 0.3 is preferable, 0 <y1 + y2 ≦ 0.2 is more preferable, and 0 <y1 + y2 ≦ 0.1 is more preferable. Moreover, 0 <y1 ≦ 0.2 is preferable, 0 <y1 ≦ 0.1 is more preferable, 0 <y2 ≦ 0.2 is preferable, and 0 <y2 ≦ 0.1 is more preferable.

In the precursor represented by the formula H _(1-y1) Li _{(1 + y1-y2)} Na _y2 Ti ₃ O ₇ , the orthorhombic lattice constant is determined by the type and amount ratio of Na, Li and H Is done. Specifically, the a-axis length is preferably in the range of 16.7 to 16.8 mm, the b-axis length is 5.7 to 5.8 mm, and the c-axis length is preferably in the range of 11.0 to 11.2 mm.

The precursor is preferably synthesized by proton exchange in which at least one of the following starting materials Na and Li is exchanged for H.
Starting material: represented by the formula Li _(2-z) Na _z Ti ₃ O ₇ (wherein z satisfies 0 ≦ z <1), the crystal structure of the orthorhombic NaLiTi ₃ O ₇ type It is a tunnel structure.

(Starting material _{Li (2-z) Na z} Ti 3 O 7)
The starting material represented by the formula Li _(2-z) Na _z Ti ₃ O ₇ is typically Li ₂ Ti ₃ O ₇ where z = 0, as shown in FIG. However, 0 <z <1 may be sufficient. In this case, 0 <z ≦ 0.2 is preferable, and 0 <z ≦ 0.1 is more preferable.

The starting material is obtained by lithium ion exchange in which Na of a composite titanium oxide NaLiTi ₃ O ₇ (hereinafter also referred to as NaLiTi ₃ O ₇ polycrystal) generated from a sodium raw material, a lithium raw material, and a titanium raw material is exchanged for Li. It is preferable to be synthesized.

(Synthesis of NaLiTi ₃ O ₇ )
NaLiTi ₃ O ₇ polycrystal is prepared by weighing and mixing at least one sodium raw material, at least one lithium raw material, and at least one titanium raw material so as to have a chemical composition of NaLiTi ₃ O _7. It can be produced by heating in an atmosphere containing oxygen gas such as air.

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 lithium raw material, at least one of lithium (metallic lithium) and a lithium compound is used. The lithium compound is not particularly limited as long as it contains lithium. For example, oxides such as Li ₂ O and Li ₂ O ₂ , salts such as Li ₂ CO ₃ and LiNO ₃ , hydroxides such as LiOH, and the like Is mentioned. Among these, Li ₂ CO _{3 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 a sodium raw material, a lithium raw material, and a titanium raw material is prepared. The mixing ratio of the sodium raw material, the lithium raw material, and the titanium raw material is preferably mixed so that the chemical composition of NaLiTi ₃ O ₇ is obtained. Further, since sodium and lithium are easily volatilized during heating, the amount of sodium and the amount of lithium may be slightly more excessive than 1 in the above chemical formula, and 1.0 to 1 for 1/3 of the amount of titanium, respectively. Is preferably in the range of .1. The mixing method is not particularly limited as long as they can be mixed uniformly, and may be mixed by a wet or dry method using a known mixer such as a mixer.

  The mixture is then fired. The firing temperature can be appropriately set depending on the raw material, and is usually about 600 ° C. to 1200 ° C., preferably 700 ° C. to 1050 ° C. Also, the firing atmosphere is not particularly limited, and it is usually performed 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, and 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, the mixture may be repeatedly fired, cooled and pulverized twice or more. Note that the degree of pulverization may be adjusted as appropriate according to the firing temperature and the like.

The thus obtained NaLiTi ₃ O ₇ has an orthorhombic NaLiTi ₃ O ₇ type tunnel structure as shown in FIG.

(Lithium ion exchange of NaLiTi ₃ O ₇ )
Li _(2-z) Na _z Ti ₃ O ₇ in which almost all of the sodium in NaLiTi ₃ O ₇ was exchanged for lithium by applying a lithium ion exchange reaction to NaLiTi ₃ O ₇ obtained as described above. Is obtained.

In this case, it is preferable that the pulverized NaLiTi ₃ O ₇ is mixed with a lithium compound and heated to advance the lithium ion exchange reaction with the lithium molten salt. The lithium compound is preferably a salt that melts at a relatively low temperature, such as lithium nitrate, lithium chloride, lithium bromide, or lithium iodide, and these can be used alone or in combination of two or more. The mixing ratio is usually as a percentage of the weight of the total lithium compound to the weight of _{NaLiTi 3 O 7, NaLiTi 3 O} 7: total lithium compound = 1: 2 to 1: 50, and preferably 1: 2 to 1: is 15 .

  The temperature of the lithium ion exchange treatment is usually in the range of 30 ° C to 500 ° C, preferably 200 ° C to 450 ° C. The treatment time is usually 2 hours to 72 hours, preferably 2 hours to 50 hours, more preferably 2 hours to 10 hours.

After the lithium ion exchange treatment, the obtained product is washed with ethanol or the like and then dried to obtain the target starting material represented by the formula Li _(2-z) Na _z Ti ₃ O ₇ . No particular limitation is imposed on the washing method, in the case of Li ₂ Ti ₃ O ₇ is preferably used an organic solvent having a high solubility in the lithium salt. For example, methanol, ethanol, hexanol, etc. are mentioned. The drying method is not particularly limited, and a normal method may be used, or natural drying in a desiccator or the like may be used.

The amount of sodium remaining in the starting material Li _(2-z) Na _z Ti ₃ O ₇ thus obtained can be controlled by changing the conditions for the exchange treatment. The amount of sodium can be, for example, below the detection limit of chemical analysis, or a significant amount can be left.

The crystal structure of the starting material Li _(2-z) Na _z Ti ₃ O ₇ thus obtained is the same as that of NaLiTi ₃ O ₇ before the lithium ion exchange reaction, and is orthorhombic NaLiTi _3. This is an O ₇ type tunnel structure. That is, in FIG. 2, it has a crystal structure in which Na represented by the larger sphere is replaced with Li.

(Starting material _Li (proton exchange _{2-z) Na z Ti 3} O 7)
By applying a proton exchange reaction to the starting material Li _(2-z) Na _z Ti ₃ O ₇ obtained as described above, a precursor in which part or all of Na and Li in the starting material is exchanged with H is obtained. The body H _(1-y1) Li _{(1 + y1-y2)} Na _y2 Ti ₃ O ₇ is obtained.

When performing proton exchange against Li ₂ Ti ₃ O ₇ and the like of _{Li (2-z) Na z} Ti 3 O 7, Although the detailed mechanism of proton exchange, Na Site (in Figure 2, larger It is presumed that Na or Li located in the sphere) is preferentially exchanged for H, and then Li located in the Li site (the smaller sphere in FIG. 2) is exchanged for H.

Thus precursor _{H (1-y1)} obtained by _{Li (1 + y1-y2)} Na y2 Ti 3 O 7 , depending on the conditions of the exchange process, appropriately changing the exchange rate of H (proton) Is possible. Therefore, H _(1-y1) Li _{(1 + y1-y2)} Na _y2 Ti ₃ O ₇ such as HLiTi ₃ O ₇ can be obtained by reducing the exchange amount of H.

HLiTi _{3 H (1-y1)} of O _7, etc. _{Li (1} + _y1-y2) when obtaining Na y2 _Ti 3 _{O 7,} water such as ion-exchange water, or the proton exchange with an aqueous solution containing a weak acid such as acetic acid It is preferable to perform proton exchange using ion-exchanged water. Even when proton exchange is performed using an aqueous solution containing a strong acid such as hydrochloric acid, H _(1-y1) Li _{(1 + y1−)} can be performed by a method such as reducing the acid concentration, shortening the treatment time, or lowering the treatment temperature. _y2) Na _y2 Ti ₃ O ₇ can be obtained.

In the proton exchange treatment, the pulverized starting material Li _(2-z) Na _z Ti ₃ O ₇ is dispersed in the above-described aqueous solution containing acid, ion-exchanged water, etc., held for a certain period of time, and then dried. It is preferable to do. A known drying method can be applied to the drying, but vacuum drying or the like is more preferable.

HLiTi _{3 H (1-y1)} of O _7, etc. _{Li (1} + _y1-y2) when obtaining Na y2 _Ti 3 _{O 7,} as the processing time is usually 10 hours to 10 days, preferably 1 day to 7 days is there. In order to shorten the treatment time, it is preferable to exchange ion-exchanged water or the like with a new one as appropriate. Furthermore, in order to facilitate the exchange reaction, the treatment temperature is preferably higher than room temperature and 30 ° C to 100 ° C.

(Precursor H _(1-y1) Li _{(1 + y1-y2)} Na _y2 Ti ₃ O ₇ heat treatment)
By subjecting the precursor H _(1-y1) Li _{(1 + y1-y2)} Na _y2 Ti ₃ O ₇ obtained above to a heat treatment, the target titanium oxide Li _{(2-x + 2α)} Na _x Ti _{6 is obtained.} O _{(13 + α)} is obtained.

  The heat treatment atmosphere is not particularly limited, and examples thereof include air (in the air), vacuum, oxidizing atmosphere, reducing atmosphere, and inert atmosphere. In these, it is preferable to heat-process in air or a vacuum.

  The heat treatment temperature is preferably 300 ° C. or higher and lower than 550 ° C., more preferably 350 ° C. or higher and lower than 500 ° C., and further preferably 400 ° C. or higher and lower than 480 ° C.

  The heat treatment time can be appropriately set according to the heat treatment temperature, and is usually about 20 minutes to 10 hours, preferably 0.5 hours to 5 hours, more preferably 0.5 hours to 3 hours. is there. The heat treatment time means a time for maintaining the heat treatment temperature.

  Examples of the cooling method after the heat treatment include natural cooling (cooling in the furnace) and slow cooling.

  If necessary, the heat treatment may be repeated twice or more. At that time, the heat treatment conditions (temperature, atmosphere, time, etc.) may all be the same or different.

[Titanium oxide]
The titanium oxide of the present invention has the formula Li _{(2-x + 2α)} Na _x Ti ₆ O _{(13 + α)} (wherein x satisfies 0 ≦ x <1 and α satisfies 0 ≦ α <0.3). It is represented by

The titanium oxide of the present invention is typically Li ₂ Ti ₆ O ₁₃ where x = α = 0, as shown in FIG. However, 0 <x <1 may be sufficient. In this case, 0 <x ≦ 0.2 is preferable, and 0 <x ≦ 0.1 is more preferable. Further, depending on the proportion of protons contained in the precursor before the heat treatment, 0 <α <0.3 (preferably 0 <α ≦ 0.2, more preferably 0 <α ≦ 0.1). is there.

  The titanium oxide of the present invention shows a maximum peak in a diffraction angle 2θ of 18 ° ± 0.5 ° (preferably 18 ° ± 0.3 °) in a powder X-ray diffraction pattern using CuKα rays. . Further, the diffraction angle 2θ is 10.5 ° ± 0.5 ° (preferably 10.5 ° ± 0.3 °), 16 ° ± 0.5 ° (preferably 16 ° ± 0.3 °) and 19 Each peak is shown in the range of ± 0.5 ° (preferably 19 ° ± 0.3 °).

Titanium oxide of the present invention, in the Fourier transform infrared absorption ^spectrum, it is preferable that peak in the range of 3500cm ^-1 ~3600cm -1 is not confirmed. The peak in the vicinity of 3500 cm ⁻¹ is derived from OH stretching vibration, and since this peak is not confirmed, it is considered that H does not exist in the titanium oxide.

Among the titanium oxides represented by the formula Li _{(2-x + 2α)} Na _x Ti ₆ O _{(13 + α)} represented by Li ₂ Ti ₆ O ₁₃ , those showing the above powder X-ray diffraction pattern have been known so far. It wasn't. In addition, there has been no disclosure of applying such a titanium oxide as an electrode active material. Furthermore, it has not been clear whether the titanium oxide can be obtained by heat-treating HLiTi ₃ O ₇ , which is an orthorhombic NaLiTi ₃ O ₇ type tunnel structure.

According to the present invention, it is possible to produce a novel titanium oxide represented by the formula Li _{(2-x + 2α)} Na _x Ti ₆ O _{(13 + α)} , and this novel titanium oxide can be used as an active material of an electrode material. By using it, it is possible to provide a secondary battery active material and a secondary battery that have a higher capacity and a longer life than the conventional Li ₂ Ti ₆ O ₁₃ . Furthermore, by using this novel titanium oxide as an active material for an electrode material, a secondary battery active material and a secondary battery having a higher capacity at the time of lithium desorption and a lower irreversible capacity than HLiTi ₃ O ₇ Can be provided.

[Active materials for secondary batteries]
The active material for a secondary battery of the present invention is used for an electrode (a positive electrode and a negative electrode) of a secondary battery, and contains the titanium oxide as a main component. That is, the active material for a secondary battery of the present invention has the formula Li _{(2-x + 2α)} Na _x Ti ₆ O _{(13 + α)} (wherein x is 0 ≦ x <1, α is 0 ≦ α <0. 3)), and the titanium oxide has a diffraction angle 2θ of 18 ° ± 0 in a powder X-ray diffraction pattern using CuKα rays. A maximum peak is shown in the range of 0.5 °, and peaks are further shown in the ranges of 10.5 ° ± 0.5 °, 16 ° ± 0.5 °, and 19 ° ± 0.5 °.

  In the active material for a secondary battery of the present invention, the “main component” of titanium oxide means that the content of the titanium oxide is 51% by weight or more, preferably 70% by weight or more, more preferably 90% by weight. More preferably, it means 100% by weight. As long as the function of the present invention is not impaired, the active material for a secondary battery may contain a component other than the main component.

Since the titanium oxide of the present invention is as described in [Titanium oxide], its detailed description is omitted.
In addition, as long as the active material for secondary batteries of this invention has the titanium oxide of this invention as a main component, only 1 type of titanium oxide of this invention may be contained, and the titanium oxide of this invention contains Two or more kinds may be included.

  The active material for a secondary battery of the present invention can be produced using the titanium oxide of the present invention. Since the manufacturing method of the titanium oxide of this invention is as having demonstrated in [the manufacturing method of a titanium oxide], the detailed description is abbreviate | omitted.

[Secondary battery]
The secondary battery of the present invention is a secondary battery configured to include a positive electrode, a negative electrode, an electrolyte, and, if necessary, other battery elements, and at least one of the positive electrode and the negative electrode is the titanium oxide described above. The active material for secondary batteries which has a thing as a main component is contained.

  The secondary battery of the present invention employs a battery element of a conventionally known secondary battery as it is, except that at least one of the positive electrode and the negative electrode contains the active material for a secondary battery mainly composed of the above titanium oxide. can do. The secondary battery of the present invention may have any configuration of a coin type, a button type, a cylindrical type, and an all solid type.

  The secondary battery of the present invention is preferably a lithium secondary battery, but may be a metal secondary battery other than a lithium secondary battery, such as a sodium secondary battery, a potassium secondary battery, a magnesium secondary battery, A calcium secondary battery etc. can be mentioned.

  Hereinafter, a lithium secondary battery, particularly a coin-type lithium secondary battery will be described as an example of the secondary battery of the present invention. Each battery element described below can be similarly applied to lithium batteries other than coin-type lithium secondary batteries and secondary batteries other than lithium secondary batteries.

  FIG. 3 is a partial cross-sectional view schematically showing an example of the secondary battery of the present invention. FIG. 3 shows an example in which the secondary battery of the present invention is a coin-type lithium secondary battery. The lithium secondary battery 1 includes a negative electrode terminal 2, a negative electrode 3, a separator 4 impregnated with an electrolytic solution, an insulating packing 5, a positive electrode 6, and a positive electrode can 7.

  As shown in FIG. 3, the positive electrode can 7 is disposed on the lower side, and the negative electrode terminal 2 is disposed on the upper side. The outer shape of the lithium secondary battery 1 is formed by the positive electrode can 7 and the negative electrode terminal 2. Between the positive electrode can 7 and the negative electrode terminal 2, the positive electrode 6 and the negative electrode 3 are provided in layers in order from the lower side. Between the positive electrode 6 and the negative electrode 3, a separator 4 impregnated with an electrolytic solution that separates them from each other is interposed. The positive electrode can 7 and the negative electrode terminal 2 are electrically insulated by an insulating packing 5.

  In the secondary battery of the present invention, the electrode active material is prepared by blending the above-mentioned active material for the secondary battery with a conductive agent, a binder or the like as necessary, and this is crimped to the current collector. By doing so, an electrode can be produced. 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 blending of the active material for the secondary battery, the conductive agent, the binder and the like in the electrode mixture is not particularly limited. Usually, the conductive agent is about 1 to 30% by weight (preferably 5 to 25% by weight), the binder is 0 to 30% by weight (preferably 3 to 10% by weight), and the balance is the active material for the secondary battery. It is preferable to blend so as to be.

  A well-known battery element can also be employ | adopted for a separator, a battery container, etc.

  Known electrolytes and solid electrolytes can also be used 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.

When the secondary battery of the present invention is a lithium secondary battery, as the counter electrode with respect to the electrode, for example, a metal lithium, a lithium alloy, or the like that functions as a negative electrode and stores lithium can be employed. . Alternatively, a known electrode that functions as a positive electrode and occludes lithium, such as lithium cobalt oxide (LiCoO ₂ ) and spinel type lithium manganese oxide (LiMn ₂ O ₄ ), can also be used as the counter electrode. . 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. Especially, it is preferable to use the active material of this invention as a negative electrode active material.

  Even when the secondary battery of the present invention is other than a lithium secondary battery, the electrode containing the active material of the present invention can function as a positive electrode or a negative electrode, and the active material of the present invention is used as a negative electrode active material. Is preferred.

  The present invention is not limited to the above-described embodiment, and modifications, improvements, and the like within the scope that can achieve the object of the present invention are included in the present invention.

  Examples of the present invention will be described below. The present invention is not limited to these examples.

[Production of Na _0.1 Li _1.9 Ti ₃ O ₇ (Starting Material)]
A sodium carbonate (Na ₂ CO ₃ ) powder having a purity of 99% or more, a lithium carbonate (Li ₂ CO ₃ ) having a purity of 99.99% or more and a titanium dioxide (TiO ₂ ) powder having a purity of 99.99% or more in a molar ratio Na: Weighed so that Li: Ti = 1.01: 1.03: 3.00. These were mixed in a mortar, then filled in a JIS standard gold crucible, and heated in an air in a high temperature condition using an electric furnace. The firing temperature was 950 ° C. and the firing time was 24 hours. Thereby, a NaLiTi ₃ O ₇ polycrystal having a tunnel structure (FIG. 2) was obtained.

When the chemical composition of the obtained sample was analyzed by an ICP emission spectroscopic analyzer (trade name ICPS-8000, manufactured by Shimadzu Corporation), Na: Li: Ti = 1.0: 1.0: 3.0 was obtained. The chemical formula of ₃ O ₇ was confirmed to be valid.

  Furthermore, powder X-ray diffraction measurement of the sample was performed using a powder X-ray diffractometer (trade name D8 ADVANCE, manufactured by Bruker), and it was confirmed that the sample had a single phase of an orthorhombic tunnel structure.

When the lattice constant was obtained by the least square method using each index and its surface spacing, the following values were obtained, which were in good agreement with the values of the known NaLiTi ₃ O ₇ (for example, VB Nalbandyan, Solid) State Sci. 9, 329 (2007)).
a = 16.4781mm (error: within 0.0004mm)
b = 5.7356 mm (error: within 0.0002 mm)
c = 11.2226mm (error: within 0.0003mm)

The NaLiTi ₃ O ₇ polycrystal obtained above was dried and pulverized. The pulverized product was mixed with a lithium nitrate (LiNO ₃ ) powder having a purity of 99% or more and a mixture of lithium chloride (LiCl) having a purity of 99% or more (molar ratio 88:12) by weight ratio of NaLiTi ₃ O ₇ : (LiNO ₃ + LiCl) = 1: 7.5. Subsequently, these were mixed in a mortar, then filled in an alumina crucible, and held in an air atmosphere at 400 ° C. for 5 hours using an electric furnace to carry out a lithium ion exchange treatment. Then, after thoroughly washing with ethanol, it was naturally dried and then subjected to lithium ion exchange treatment again to obtain a starting material Na _0.1 Li _1.9 Ti ₃ O ₇ polycrystal.

When the chemical composition of the obtained sample was analyzed by ICP emission spectrometry, Na: Li: Ti = 0.10: 1.9: 3.0 was obtained, and Na _0.1 Li _1.9 Ti ₃ O ₇ The chemical formula was confirmed.

Furthermore, it was confirmed by powder X-ray diffraction measurement that it is a single phase of an orthorhombic tunnel structure. The powder X-ray diffraction pattern of the starting material Na _0.1 Li _1.9 Ti ₃ O ₇ was in good agreement with the known powder diffraction pattern of Li ₂ Ti ₃ O ₇ (see, for example, Kazuaki Chiba et al., No. 7 (Refer to the abstract of the Advanced Conference on Advanced Storage Battery for Rotating Electric Vehicles, P-18 (2014)).

When the lattice constant was obtained by the least square method using each index and its surface spacing, the following values were obtained.
a = 16.7306 mm (error: within 0.0002 mm)
b = 5.7186 mm (error: within 0.0001 mm)
c = 11.0919 mm (error: within 0.0002 mm)

When the particle shape of the starting material Na _0.1 Li _1.9 Ti ₃ O ₇ polycrystal thus obtained was examined with a scanning electron microscope (SEM) (manufactured by Keyence, trade name VE-8800), The Na _0.1 Li _1.9 Ti ₃ O ₇ polycrystal is confirmed to be composed of primary particles having an isotropic shape of about 1 μm square while maintaining the shape of NaLiTi ₃ O _7. It was done.

[Reference Example 1: Production of HLiTi ₃ O ₇ (Precursor)]
The starting material (Na _0.1 Li _1.9 Ti ₃ O ₇ polycrystal) obtained above was pulverized, and 1.0 g of the pulverized product was put into 50 ml of ion-exchanged water and heated to 90 ° C. while bathing. For 3 days, proton exchange treatment was performed. Then, by vacuum drying at 90 ° C., to obtain a HLiTi ₃ O ₇ polycrystal body as a precursor.

As a result of ICP emission spectroscopic analysis of the obtained sample, the amount of Li was lower than that of Na _0.1 Li _1.9 Ti ₃ O _{7 as} a starting material.

Further, as a result of thermal analysis (TGA) (manufactured by Shimadzu Corporation, trade name DTG-60), a weight reduction of 3.0 wt% was confirmed by heating up to 450 ° C. This is explained by the following decomposition reaction (calculated value 3.4 wt% reduction).
2HLiTi ₃ O ₇ → H ₂ O ↑ + Li ₂ Ti ₆ O ₁₃

From the above results, it is considered that the obtained sample is reasonable in the chemical formula of HLiTi ₃ O ₇ although Na remains slightly.

Further, powder X-ray diffraction measurement confirmed that the phase was orthorhombic single phase. The powder X-ray diffraction pattern of HLiTi ₃ O _{7 according} to Reference Example 1 is shown in FIG.

When the lattice constant was obtained by the least square method using each index and its surface spacing, the following values were obtained.
a = 16.7510 mm (error: within 0.0005 mm)
b = 5.7621 mm (error: within 0.0002 mm)
c = 11.1136 mm (error: within 0.0004 mm)

Moreover, FTIR measurement was performed with a Fourier transform infrared spectrophotometer (manufactured by Agilent Technologies, trade name Cary 660 FTIR). The FTIR spectrum of HLiTi ₃ O _{7 according} to Reference Example 1 is shown in FIG. In HLiTi ₃ O _{7 according} to Reference Example 1, a peak around 3500 cm ⁻¹ was confirmed.

[Example 1: Production of novel Li ₂ Ti ₆ O ₁₃ ]
The object obtained by filling the crushed and dried product of the precursor (HLiTi ₃ O ₇ polycrystal) obtained above into an alumina crucible and holding it in air at 450 ° C. for 1 hour using an electric furnace. Li ₂ Ti ₆ O ₁₃ was obtained.

As described in Reference Example 1, a weight reduction of 3.0 wt% was confirmed by heating HLiTi ₃ O ₇ to 450 ° C., which was explained by the following decomposition reaction (calculated value 3.4 wt% reduction). The
2HLiTi ₃ O ₇ → H ₂ O ↑ + Li ₂ Ti ₆ O ₁₃

From the above results, it is considered that the obtained sample is reasonable in terms of the chemical formula of Li ₂ Ti ₆ O ₁₃ although Na remains slightly.

FIG. 4 shows a powder X-ray diffraction pattern of Li ₂ Ti ₆ O _{13 according} to Example 1. Similar to HLiTi ₃ O _{7 according} to Reference Example 1, in Li ₂ Ti ₆ O _{13 according} to Example 1, a maximum peak was confirmed at about 18.2 °, and about 10.6 ° and about 15.9. Peaks were confirmed at about 19.2 ° and at about 19.2 °, respectively. Furthermore, a peak different from that of HLiTi ₃ O _{7 according} to Reference Example 1 was confirmed.

The FTIR spectrum of Li ₂ Ti ₆ O _{13 according} to Example 1 is shown in FIG. Unlike HLiTi ₃ O _{7 according} to Reference Example 1, in Li ₂ Ti ₆ O _{13 according} to Example 1, a peak near 3500 cm ⁻¹ was not confirmed. From this result, it is considered that H does not exist in Li ₂ Ti ₆ O _{13 according} to Example 1.

[Comparative Example 1: Conventional Li ₂ Ti ₆ O ₁₃ ]
FIG. 5 is a powder X-ray diffraction pattern of Li ₂ Ti ₆ O _{13 according} to Comparative Example 1. Specifically, it is a conventional powder X-ray diffraction pattern of Li ₂ Ti ₆ O ₁₃ described in Patent Document 1 (Japanese Patent Laid-Open No. 2010-123424). 4 and 5, the crystal structure of Li ₂ Ti ₆ O _{13 according} to Example 1 is clearly different from the crystal structure of the conventional Li ₂ Ti ₆ O ₁₃ described in Patent Document 1. Can be confirmed.

[Electrical characteristics evaluation]
(Production of lithium secondary battery)
The titanium oxide obtained in Example 1 and Reference Example 1 was used as an active material, acetylene black as a conductive agent, and tetrafluoroethylene as a binder were mixed at a weight ratio of 5: 5: 1. An electrode was produced by pressure bonding to a mesh. For each electrode, a 1M solution prepared by dissolving lithium metal in a counter electrode and lithium hexafluorophosphate in a mixed solvent (volume ratio 1: 2) of ethylene carbonate (EC) and dimethyl carbonate (DMC) is used as an electrolytic solution. A lithium secondary battery (coin-type cell) having the structure shown in FIG. The battery was produced according to a known cell configuration / assembly method.

(Lithium insertion / extraction test)
Each lithium secondary battery produced was subjected to an electrochemical lithium insertion / extraction test at a current density of 10 mA / g and a cutoff potential of 3.0 V to 1.0 V under a temperature condition of 25 ° C.

(Charge / discharge cycle test)
A charge / discharge cycle test was performed on each of the produced lithium secondary batteries. The measurement conditions were a current density of 10 mA / g under a temperature condition of 25 ° C., and a cut-off potential of 3.0 V to 1.0 V.

  FIG. 7 is a diagram showing voltage changes associated with lithium insertion / extraction reactions in Example 1 and Reference Example 1. FIG. In FIG. 7, a curve in which the cell voltage decreases as the capacity increases indicates a voltage change when lithium is inserted, and a curve in which the cell voltage increases as the capacity increases indicates a voltage change when lithium is desorbed.

FIG. 8 is a diagram showing voltage changes associated with lithium insertion / extraction reactions in Comparative Example 1. Specifically, a voltage variation diagram Patent Document 1 of the prior are described in (JP 2010-123424 JP) _Li 2 _Ti 6 _{O 13.}

According to Patent Document 1, conventional Li ₂ Ti ₆ O ₁₃ is used as an active material, acetylene black as a conductive agent, and tetrafluoroethylene as a binder are mixed in a weight ratio of 10: 5: 1. An electrode is prepared, and a 1M solution in which lithium metal is counter electrode and lithium hexafluorophosphate is dissolved in a mixed solvent of ethylene carbonate (EC) and dimethyl carbonate (DMC) (volume ratio 1: 1) is used as an electrolyte. A lithium secondary battery (coin-type cell) having the structure shown in FIG. 3 is produced. The fabricated lithium secondary battery is subjected to an electrochemical lithium insertion / extraction test at a current density of 10 mA / g and a cut-off potential of 1.0 V under a temperature condition of 25 ° C. Thereafter, a charge / discharge cycle test is performed at a cut-off potential of 3.0V to 1.0V.

As shown in FIG. 8, the lithium secondary battery using Li ₂ Ti ₆ O _{13 according} to Comparative Example 1 has a potential flat portion in the vicinity of 1.5 V, and the lithium insertion capacity at the first cycle is the weight of the active material. Per 217 mAh / g, lithium desorption capacity is 120 mAh / g per active material weight. Therefore, the irreversible capacity _{C 3} is 97 mAh / g. From the second cycle onward, reversible lithium insertion / extraction is performed at a capacity of about 85 to 95 mAh / g.

On the other hand, the lithium secondary battery using HLiTi ₃ O _{7 according} to Reference Example 1 has potential flat portions in the vicinity of 1.3 V and 1.5 V, as shown in FIG. 252 mAh / g per unit, lithium desorption capacity is 158 mAh / g per active material weight. Thus, irreversible capacity _{C 2} is 94mAh / g.

Furthermore, the lithium secondary battery using Li ₂ Ti ₆ O _{13 according} to Example 1 has a potential flat portion in the vicinity of 1.3 V, 1.6 V, and 2.0 V, and the lithium insertion capacity is based on the weight of the active material. 222 mAh / g, lithium desorption capacity is 185 mAh / g per active material weight. Thus, irreversible capacity _{C 1} is 37 mAh / g.

From the results of FIG. 7 and FIG. 8, HLiTi ₃ O ₇ (Reference Example 1) having an orthorhombic NaLiTi ₃ O ₇ type tunnel structure and Li ₂ Ti ₆ O ₁₃ (Example 1) which is a heat treatment body thereof. ) As an active material, it was found that the capacity of the secondary battery can be made higher than that of the conventional Li ₂ Ti ₆ O ₁₃ (Comparative Example 1). Furthermore, it was found that by performing heat treatment on HLiTi ₃ O ₇ (Reference Example 1) to obtain Li ₂ Ti ₆ O ₁₃ (Example 1), lithium desorption capacity can be increased and irreversible capacity can be decreased. did.

Note that Li ₂ Ti ₆ O _{13 according} to Example 1 has a lower lithium insertion capacity than HLiTi ₃ O _{7 according} to Reference Example 1. However, when these titanium oxides are used as negative electrode active materials such as lithium secondary batteries, the lithium desorption capacity is more important than the lithium insertion capacity, and a high lithium desorption capacity is desired. . Therefore, it is considered that Li ₂ Ti ₆ O _{13 according} to Example 1 having a higher lithium desorption capacity than HLiTi ₃ O ₇ according to Reference Example 1 is particularly preferably used as the negative electrode active material.

  FIG. 9 is a diagram showing the relationship between the number of cycles and the lithium insertion capacity of the lithium secondary batteries according to Example 1 and Reference Example 1 obtained by performing the above-described charge / discharge cycle test. The lithium insertion capacity after 10 cycles was found to be 150 mAh / g or more in both Reference Example 1 and Example 1, which was higher than Comparative Example 1 (see FIG. 8, approximately 90 mAh / g). Furthermore, it was found that the lithium insertion capacity (186 mAh / g) of Example 1 was higher than the lithium insertion capacity (157 mAh / g) of Reference Example 1.

  FIG. 10 is a diagram illustrating the relationship between the number of cycles and the lithium desorption capacity of the lithium secondary batteries according to Example 1 and Reference Example 1. The same tendency as the lithium insertion capacity is observed for the lithium desorption capacity. That is, it was found that both Reference Example 1 and Example 1 were 150 mAh / g or higher, which was higher than Comparative Example 1 (see FIG. 8, approximately 85 mAh / g). Furthermore, it was found that the lithium desorption capacity (185 mAh / g) of Example 1 was higher than that of Reference Example 1 (156 mAh / g).

From the results of FIG. 9 and FIG. 10, the cycle characteristics of the lithium secondary battery are improved by performing heat treatment on HLiTi ₃ O ₇ (Reference Example 1) to obtain Li ₂ Ti ₆ O ₁₃ (Example 1). It was also confirmed that it was possible.

1 Secondary battery (lithium secondary battery)
2 Negative electrode terminal 3 Negative electrode 4 Separator 5 impregnated with electrolyte 5 Insulation packing 6 Positive electrode 7 Positive electrode can

Claims (8)

A titanium oxide represented by the formula Li _{(2-x + 2α)} Na _x Ti ₆ O _{(13 + α)} ,
In the formula, x satisfies 0 ≦ x <1, α satisfies 0 ≦ α <0.3,
In the powder X-ray diffraction pattern using CuKα rays, the diffraction angle 2θ shows a maximum peak in the range of 18 ° ± 0.5 °, and further, 10.5 ° ± 0.5 °, 16 ° ± 0.5 Titanium oxide showing peaks in the range of ° and 19 ° ± 0.5 °, respectively. A method for producing a titanium oxide according to claim 1,
The precursor represented by the formula H _(1-y1) Li _{(1 + y1-y2)} Na _y2 Ti ₃ O ₇ is heat-treated,
In the precursor formula, y1 and y2 satisfy 0 ≦ y1 + y2 <1,
The method for producing a titanium oxide, wherein the crystal structure of the precursor is an orthorhombic NaLiTi ₃ O ₇ type tunnel structure.   The method for producing a titanium oxide according to claim 2, wherein the heat treatment of the precursor is performed in a temperature range of 300 ° C. or higher and lower than 550 ° C. in air or in vacuum. The precursor is synthesized by proton exchange in which at least one of the starting materials Na and Li represented by the formula Li _(2-z) Na _z Ti ₃ O ₇ is exchanged for H,
In the formula of the starting material, z satisfies 0 ≦ z <1,
4. The method for producing a titanium oxide according to claim 2, wherein the crystal structure of the starting material is an orthorhombic NaLiTi ₃ O ₇ type tunnel structure. 5. Production method of the starting material, the Na Sodium material and NaLiTi ₃ O ₇ generated from the lithium material and the titanium raw material is synthesized by lithium ion exchange to replace the Li, titanium oxide according to claim 4. A method for producing an active material for a secondary battery, comprising:
The manufacturing method of the active material for secondary batteries with which the titanium oxide of Claim 1 is synthesize | combined by the manufacturing method of any one of Claims 2-5.   The active material for secondary batteries which has the titanium oxide of Claim 1 as a main component. A secondary battery comprising a positive electrode, a negative electrode, and an electrolyte,
A secondary battery in which at least one of the positive electrode and the negative electrode contains the active material for a secondary battery mainly comprising the titanium oxide according to claim 1.