JP2013062121A - Active material for sodium ion battery and sodium ion battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an active material for a sodium ion battery, in which deposition of metal Na is suppressed.SOLUTION: According to the present invention, an active material for a sodium ion battery containing an M element, a Ti element, an O element and an S element which are group III elements, and having an MTiOScrystalline phase is provided to solve the problem.

Description

  The present invention relates to a sodium ion battery active material useful as, for example, a negative electrode active material, and a sodium ion battery using the same.

  A sodium ion battery is a battery in which Na ions move between a positive electrode and a negative electrode. Since Na is abundant compared to Li, the sodium ion battery has an advantage that it is easy to reduce the cost compared to the lithium ion battery. In general, a sodium ion battery includes a positive electrode active material layer containing a positive electrode active material, a negative electrode active material layer containing a negative electrode active material, and an electrolyte layer formed between the positive electrode active material layer and the negative electrode active material layer. And have.

  Conventionally, it is known to use a carbon material as a negative electrode active material used in a sodium ion battery. For example, Non-Patent Document 1 discloses using hard carbon as a negative electrode active material of a sodium ion battery. Further, Patent Document 1 discloses a sodium ion secondary battery using a negative electrode active material containing a carbon material obtained by carbonizing and activating a specific cyclic compound as a single body or as a main component. Patent Document 2 discloses a nonaqueous electrolyte secondary battery including a negative electrode containing a carbon material as a storage material for sodium ions and lithium ions.

On the other hand, Non-Patent Document 2 discloses physical property evaluation of Na _x Y ₂ Ti ₂ O ₅ S ₂ . However, this document merely evaluates the physical properties of Na _x Y ₂ Ti ₂ O ₅ S ₂ and does not evaluate the battery characteristics at all. In Non-Patent Document 2, Na is forcibly introduced into Y ₂ Ti ₂ O ₅ S ₂ as a method for synthesizing Na _x Y ₂ Ti ₂ O ₅ S _2. There is no description that it can be done, and of course there is no description that suggests that it can function as an active material. Non-Patent Document 3 discloses evaluation of physical properties of Li _x Y ₂ Ti ₂ O ₅ S ₂ . However, this document merely evaluates the physical properties of Li _x Y ₂ Ti ₂ O ₅ S ₂ and does not evaluate the battery characteristics at all. Non-Patent Document 4 discloses physical property evaluation of Nd ₂ Ti ₂ O ₅ S ₂ . However, this document merely evaluates the physical properties of Nd ₂ Ti ₂ O ₅ S ₂ and does not evaluate the battery characteristics at all.

JP 2009-129742 A JP-A-11-040156

S. Komada et al., “Advanced Carbon Anode for Na-Ion Batteries”, 216th ECS Meeting, Abstract # 684 Sophie G. Denis et al., “Two alternative products from the intercalation of alkali metals into cation-defective Ruddlesden‐Popper oxysulfides”, Chemical Communications 2356-2357, (2001) Geoffrey Hyett et al., “Electronically Driven Structural Distortions in Lithium Intercalates of the n = 2 Ruddlesden-Popper-Type Host Y2Ti2O5S2: Synthesis, Structure, and Properties of LixY2Ti2O5S2 (0 <x <2)”, Journal of the American Chemical Society , 126, 1980-1991 (2004) M. Goga et al., “Ln2Ti2S2O5 (Ln = Nd, Pr, Sm): a novel series of defective Ruddlesden-Popper phases”, Chemical communications, 1999, 979-980

  As described above, it is known to use a carbon material as a negative electrode active material used in a sodium ion battery. However, since carbon materials usually react electrochemically with Na ions at a very low potential (Na reference), there is a problem that metal Na is likely to precipitate. For example, hard carbon electrochemically reacts with Na ions at about 0.1 V with respect to Na.

  This invention is made | formed in view of the said problem, and it aims at providing the active material for sodium ion batteries which suppressed precipitation of metal Na.

In order to achieve the above object, the present invention contains a Group III element, M element, Ti element, O element and S element, and contains an M ₂ Ti ₂ O ₅ S ₂ crystal phase. An active material for a sodium ion battery is provided.

According to the present invention, since it has a M ₂ Ti ₂ O ₅ S ₂ crystal phase, it can be an active material for a sodium ion battery that suppresses the precipitation of metal Na. The present inventors have found that the M ₂ Ti ₂ O ₅ S ₂ crystal phase can occlude and release Na ions and is useful as an active material of a sodium ion battery. Moreover, since the active material for sodium ion batteries of this invention has O element and shows the behavior as an oxide, it has the advantage that thermal stability is superior to the conventional carbon material.

In the above invention, preferably contains mainly the _{M 2 Ti} 2 _O 5 _S 2 crystal phase. It is because precipitation of metal Na can be suppressed more.

  In the said invention, it is preferable that the said M element is at least one of Y and Nd.

In the above invention, comprises the M element at least Y, in X-ray diffraction measurement using a CuKα ray, the peak intensity of the _{Y 2 Ti} 2 _O 5 _S 2 crystal phase in 2 [Theta] = 34.5 ° and _{I A} the peak intensity of _Y 2 _Ti 2 _{O 7} crystalline phase and _{I B} in the 2 [Theta] = 35.6 °, a peak intensity of TiS ₂ in 2 [Theta] = 34.1 ° in the case of the _{I C,} of I B / _{I a} value is 0.3 or less, _and it is preferable the value of I C / _{I a} is 0.15 or less. It is because it can be set as the active material for sodium ion batteries with fewer impurities.

  In the said invention, it is preferable that Na insertion-release electric potential with respect to metal Na is 0.5V or more. This is because precipitation of metal Na can be suppressed.

  Further, in the present invention, it contains a Group III element M element, Ti element, O element and S element, is crystalline, and has a Na insertion / extraction potential of 0.5 V or more with respect to metal Na. An active material for a sodium ion battery is provided.

  According to the present invention, since the Na insertion / release potential with respect to metal Na is equal to or higher than a predetermined value, an active material for a sodium ion battery in which precipitation of metal Na is suppressed can be obtained. Moreover, since the active material for sodium ion batteries of this invention has O element and shows the behavior as an oxide, it has the advantage that thermal stability is superior to the conventional carbon material.

In the above invention, it is preferred to have a crystal phase having a structure part of the M element positioned at the A site of the Ruddlesden-Popper structure A ₃ B ₂ C ₇ is deficient. It is because it can be set as the active material for batteries whose electric potential is higher than a carbon material.

  In the said invention, it is preferable that the said M element is at least one of Y and Nd.

  In the said invention, it is preferable that the said sodium ion battery active material is a negative electrode active material. It is because precipitation of metal Na can be suppressed and a highly safe battery can be obtained. Furthermore, since there are abundant active materials with higher potentials, a high voltage sodium ion battery can be obtained.

  In the present invention, a positive electrode active material layer containing a positive electrode active material, a negative electrode active material layer containing a negative electrode active material, and an electrolyte layer formed between the positive electrode active material layer and the negative electrode active material layer And the positive electrode active material or the negative electrode active material is the above-described sodium ion battery active material.

  ADVANTAGE OF THE INVENTION According to this invention, precipitation of metal Na can be suppressed by using the active material for sodium ion batteries mentioned above, and it can be set as a highly safe sodium ion battery.

  In the said invention, it is preferable that the said negative electrode active material is the said active material for sodium ion batteries. It is because precipitation of metal Na can be suppressed and it can be set as a highly safe battery. Furthermore, since there are abundant active materials with higher potentials, a high-voltage sodium ion battery can be obtained.

  In this invention, there exists an effect that the active material for sodium ion batteries which suppressed precipitation of metal Na can be provided.

It is a schematic sectional drawing which shows an example of the sodium ion battery of this invention. 3 is a result of X-ray diffraction measurement for the active material obtained in Example 1. FIG. 3 is a result of X-ray diffraction measurement for an active material obtained in Example 2. FIG. It is an evaluation result of the charging / discharging characteristic of the battery for evaluation using the active material obtained in Example 1. It is a result of the X-ray-diffraction measurement with respect to the active material obtained in Example 1 and Examples 3-1 to 3-4. FIG. 6 is an enlarged view of FIG. 5.

  Hereinafter, the active material for sodium ion batteries and the sodium ion battery of the present invention will be described in detail.

A. First, the sodium ion battery active material of the present invention will be described. The active material for sodium ion batteries of the present invention can be broadly divided into two embodiments. Hereinafter, the active material for a sodium ion battery of the present invention will be described separately for the first embodiment and the second embodiment.

1. 1st embodiment The 1st embodiment of the active material for sodium ion batteries of this invention is described. The active material for a sodium ion battery according to the first embodiment contains an M element, a Ti element, an O element and an S element, which are Group III elements, and an M ₂ Ti ₂ O ₅ S ₂ crystal phase. It is what.

According to this embodiment, since it has a M ₂ Ti ₂ O ₅ S ₂ crystal phase, it can be an active material for a sodium ion battery that suppresses the precipitation of metal Na. The present inventors have found that the M ₂ Ti ₂ O ₅ S ₂ crystal phase can occlude and release Na ions and is useful as an active material of a sodium ion battery. Moreover, since the active material for sodium ion batteries of this embodiment has an O element and shows a behavior as an oxide, it has an advantage that it has better thermal stability than a conventional carbon material.

The active material for sodium ion batteries of this embodiment contains an M ₂ Ti ₂ O ₅ S ₂ crystal phase. The presence of the M ₂ Ti ₂ O ₅ S ₂ crystal phase can be confirmed by X-ray diffraction (XRD) or the like. Further, the M ₂ Ti ₂ O ₅ S ₂ crystal phase is considered to correspond to a crystal phase having a defective Ruddlesden-Popper structure. In general, the Ruddlesden-Popper structure has a composition represented by the general formula A _{n + 1} B _n C _{3n + 1} (n is an integer), and has a layered structure in which perovskite structures and rock salt structures are alternately stacked. Here, when n = 2, the above general formula can be expressed as A ₃ B ₂ C ₇ . When this A ₃ B ₂ C ₇ is compared with M ₂ Ti ₂ O ₅ S ₂ in this embodiment, M is located at the A site, Ti is located at the B site, and O and C are located at the C site. S will be located. Further, if M is located at 3 atoms in the A site, it corresponds to a complete Ruddlesden-Popper structure, but in this embodiment, M is located at only 2 atoms. Therefore, it is considered that a defect occurs in the A site, and Na ions are inserted and desorbed in the defective part, so that the function as an active material is remarkably exhibited. The reaction between the M ₂ Ti ₂ O ₅ S ₂ crystal phase and Na ions is considered as follows, and the M ₂ Ti ₂ O ₅ S ₂ crystal phase is a so-called insertion / desorption type active material. It seems to function as.
M ₂ Ti ₂ O ₅ S ₂ + xNa ⁺ + xe ⁻ ⇔Na _x M ₂ Ti ₂ O ₅ S ₂

  The M element in this embodiment is usually a trivalent group III element, and corresponds to Sc, Y, lanthanoids and actinoids. Among them, the M element is preferably at least one of Y, Nd, Sc, Pr, Sm, Gd, Tb, Dy and Er, more preferably at least one of Y, Nd and Sc, and Y and Nd. More preferably, it is at least one of the following.

Moreover, it is preferable that the active material for sodium ion batteries of this embodiment has a large ratio of the M ₂ Ti ₂ O ₅ S ₂ crystal phase, and specifically contains mainly the M ₂ Ti ₂ O ₅ S ₂ crystal phase. It is preferable to do. It is because precipitation of metal Na can be suppressed more. Here, “mainly composed of M ₂ Ti ₂ O ₅ S ₂ crystal phase” means that the proportion of the M ₂ Ti ₂ O ₅ S ₂ crystal phase in the crystal phase contained in the active material for sodium ion battery is The biggest thing. The ratio of the M ₂ Ti ₂ O ₅ S ₂ crystal phase contained in the active material for sodium ion batteries is preferably 50 mol% or more, more preferably 60 mol% or more, and further preferably 70 mol% or more. preferable. Further, the sodium ion battery active material of this embodiment may be composed of only the M ₂ Ti ₂ O ₅ S ₂ crystal phase (single-phase active material). The ratio of the M ₂ Ti ₂ O ₅ S ₂ crystal phase contained in the active material for sodium ion batteries can be determined, for example, by preparing a battery using metal Na as a counter electrode and measuring its capacity. .

  The sodium ion battery active material of this embodiment preferably has a Na insertion / release potential of 0.5 V or more with respect to metal Na, more preferably within a range of 0.5 V to 1.1 V. More preferably, it is in the range of 6V to 1.0V. If the Na insertion / release potential is too low, the precipitation of metal Na may not be sufficiently suppressed. If the Na insertion / release potential is too high, the battery voltage may be reduced when used as a negative electrode active material. Because there is. In this embodiment, the Na insertion / extraction potential of the active material for a sodium ion battery can be defined as the average value of the Na insertion potential and the Na elimination potential. Further, the Na insertion potential and the Na elimination potential can be determined by a cyclic voltammetry (CV) method. In this embodiment, the Na insertion potential and the Na elimination potential are each preferably 0.5 V or more.

In this embodiment, the M element contains at least Y, and in the X-ray diffraction measurement using CuKα ray, the peak intensity of the Y ₂ Ti ₂ O ₅ S ₂ crystal phase at 2θ = 34.5 ° is expressed as I is _a, the peak intensity of _Y 2 _Ti 2 _{O 7} crystal phase at 2 [Theta] = 35.6 ° and _{I B,} the peak intensity of TiS ₂ in 2 [Theta] = 34.1 ° in the case of the _{I C, I} B / _I when the value of _a is 0.3 or less, _and it is preferable the value of I C / _{I a} is 0.15 or less. It is because it can be set as the active material for sodium ion batteries with fewer impurities. Note that the positions of the peaks of I _{A to} I _C may slightly vary depending on the state of the crystal lattice. For this reason, the position of the peak includes a range of ± 0.2 °.

The value of I _B / I _A is usually 0.3 or less, preferably 0.1 or less, and more preferably 0.05 or less. This is because if I _B / I _A is too large, the battery capacity may be reduced by the Y ₂ Ti ₂ O ₇ crystal phase that is an impurity. On the other hand, the value of I _C / I _A is usually 0.15 or less and preferably 0.12 or less. When I C _/ I _A is too large, TiS ₂ as an impurity reacts with water, there is a possibility that hydrogen sulfide is generated.

  The sodium ion battery active material of this embodiment may be used as a positive electrode active material or a negative electrode active material, but the latter is preferred. It is because precipitation of metal Na can be suppressed and a highly safe battery can be obtained. Furthermore, since there are abundant active materials with higher potentials, a high voltage sodium ion battery can be obtained.

Moreover, the sodium ion battery active material of the present embodiment tends to improve the electronic conductivity as the proportion of the M ₂ Ti ₂ O ₅ S ₂ crystal phase increases. If the electronic conductivity of the active material itself is high, the amount of conductive material used can be reduced, and the amount of active material used can be increased accordingly. As a result, there is an advantage that the capacity of the battery can be increased. The electronic conductivity (room temperature) of the active material for sodium ion batteries of this embodiment is, for example, preferably 10 ⁻⁷ S / cm or more, and more preferably 10 ⁻⁵ S / cm or more.

  The shape of the active material for sodium ion batteries of this embodiment is preferably particulate. Moreover, the average particle diameter (D50) of the active material for sodium ion batteries is, for example, preferably in the range of 1 nm to 100 μm, and more preferably in the range of 10 nm to 30 μm.

Moreover, the manufacturing method of the active material for sodium ion batteries of this embodiment will not be specifically limited if it is a method which can obtain the active material for sodium ion batteries mentioned above. As a manufacturing method of the active material for sodium ion batteries of this embodiment, a solid-phase method can be mentioned, for example. As a specific example of the solid phase method, a raw material composition in which M ₂ O ₃ (M is a Group III element), TiO ₂ and TiS ₂ are mixed in such a ratio that an M ₂ Ti ₂ O ₅ S ₂ crystal phase is obtained. The method of preparing a thing and baking the raw material composition can be mentioned. At this time, in order to suppress unnecessary side reactions, it is preferable to perform heating in a vacuum state. Further, for example, if M ₂ O ₃ , TiO ₂ and TiS ₂ are mixed in equimolar amounts, the composition of M ₂ Ti ₂ O ₅ S ₂ can be obtained stoichiometrically.

In this embodiment, a raw material composition containing M ₂ O ₃ (M is a Group III element), TiO ₂ and TiS ₂ is used, and the ratio of TiS ₂ to M ₂ O _{3 is} expressed in molar ratio. Thus, it is preferable to perform at least one of making it larger than 1 and making the ratio of TiO ₂ to M ₂ O ₃ smaller than 1 in terms of molar ratio. This is because an active material for a sodium ion battery with fewer impurities can be obtained. _The ratio of TiS ₂ and TiO ₂ with respect to M 2 _{O 3} is preferably adjusted so that the value of the value and _I C / _{I A} of the above-mentioned _I B / _{I A} is obtained.

Here, as described above, in order to obtain M ₂ Ti ₂ O ₅ S ₂ , TiS ₂ , TiO ₂ and M ₂ O ₃ may be used in equimolar amounts in terms of composition. When the composition is used, a slight impurity (M ₂ Ti ₂ O ₇ crystal phase) is generated. The mechanism by which the M ₂ Ti ₂ O ₇ crystal phase is generated is assumed as follows. That is, since TiS ₂ contained in the raw material composition becomes hydrogen sulfide (H ₂ S) and titanium oxide (TiO ₂ ) by reacting with moisture, it is considered that sulfur deficiency and oxygen excess occur due to the composition. Moreover, it is thought that not M ₂ Ti ₂ O ₅ S ₂ crystal phase but M ₂ Ti ₂ O ₇ crystal phase occurs due to excess oxygen. On the other hand, even if sulfur deficiency occurs by increasing the ratio of TiS ₂ and making sulfur exist excessively with respect to the equimolar composition of TiS ₂ , TiO ₂ and M ₂ O ₃ , M ₂ Ti ₂ O ₇ crystalline phase can be inhibited from generating. Further, for example, by reducing the proportion of TiO ₂ and reducing the proportion of oxygen in advance, it is possible to suppress the generation of the M ₂ Ti ₂ O ₇ crystal phase. Especially, in this embodiment, it is preferable to increase the ratio of TiS ₂ and decrease the ratio of TiO ₂ . This is because excessive or deficient Ti is less likely to occur.

For example, when the ratio of TiS ₂ is increased, the ratio of TiS ₂ with respect to M ₂ O ₃ is usually larger than 1 and preferably 1.02 or more, more preferably 1.05 or more in terms of molar ratio. . Similarly, the molar ratio of TiS ₂ to M ₂ O ₃ is preferably less than 1.15, more preferably 1.13 or less, and even more preferably 1.1 or less. On the other hand, for example, the case of reducing the proportion of TiO _2, the percentage of TiO ₂ relative to M 2 _{O 3} in molar ratio, usually less than 1, it preferably 0.98 or less, 0.95 or less More preferred. Similarly, the molar ratio of TiO ₂ to M ₂ O ₃ is preferably greater than 0.85, more preferably 0.87 or more, and even more preferably 0.9 or more.

In the raw material composition, when the ratio of M ₂ O ₃ is 1 mol part, the total ratio of TiS ₂ and TiO ₂ is preferably in the range of 1.9 mol part to 2.1 mol part, for example, More preferably, it is in the range of 1.95 mol parts to 2.05 mol parts. This is because, when the ratio of the total of TiS ₂ and TiO ₂ is within the above range, Ti excess or deficiency is less likely to occur.

  The firing temperature is not particularly limited as long as the desired sodium ion battery active material can be obtained. For example, the firing temperature is in the range of 800 ° C to 1400 ° C, and in particular, in the range of 1000 ° C to 1200 ° C. It is preferable to be within. This is because if the firing temperature is too low, solid phase reaction may not occur, and if the firing temperature is too high, an unnecessary crystal phase may be generated. Moreover, although baking time is not specifically limited, For example, it is preferable to exist in the range of 24 hours-384 hours, and it is more preferable that it is in the range of 48 hours-192 hours. Moreover, it is preferable to perform baking in a vacuum from a viewpoint of a side reaction prevention.

2. Second Embodiment Next, a second embodiment of the active material for sodium ion batteries of the present invention will be described. The active material for a sodium ion battery according to the second embodiment contains a Group III element, an M element, a Ti element, an O element, and an S element, is crystalline, and has an Na insertion / extraction potential with respect to metal Na It is characterized by being 0.5 V or more.

  According to this embodiment, since the Na insertion / extraction potential with respect to metal Na is a predetermined value or more, it can be set as the active material for sodium ion batteries which suppressed metal Na precipitation. Moreover, since the active material for sodium ion batteries of this embodiment has an O element and shows a behavior as an oxide, it has an advantage that it has better thermal stability than a conventional carbon material.

  The active material for a sodium ion battery of this embodiment is generally characterized in that the Na insertion / extraction potential with respect to metal Na is 0.5 V or more. Is the same as described in “1. First embodiment” above.

Moreover, it is preferable that the active material for sodium ion batteries of this embodiment has a crystal phase having a structure in which part of the M element located at the A site of the Ruddlesden-Popper structure A ₃ B ₂ C ₇ is missing. This is because it is considered that Na ions are inserted / desorbed into / from the defect site and the function as an active material is remarkably exhibited. In particular, it is preferable that the active material for a sodium ion battery of the present embodiment contains the crystal phase as a main component.

  Further, the physical properties, manufacturing method and other matters of the active material for sodium ion battery of the present embodiment are the same as the contents described in the above “1. First embodiment”, so the description here is omitted. .

B. Next, the sodium ion battery of the present invention will be described. The sodium ion battery of the present invention includes a positive electrode active material layer containing a positive electrode active material, a negative electrode active material layer containing a negative electrode active material, and an electrolyte formed between the positive electrode active material layer and the negative electrode active material layer. The positive electrode active material or the negative electrode active material is the above-mentioned active material for a sodium ion battery.

  FIG. 1 is a schematic cross-sectional view showing an example of the sodium ion battery of the present invention. A sodium ion battery 10 shown in FIG. 1 includes a positive electrode active material layer 1, a negative electrode active material layer 2, an electrolyte layer 3 formed between the positive electrode active material layer 1 and the negative electrode active material layer 2, and a positive electrode active material. It has a positive electrode current collector 4 that collects current from the layer 1, a negative electrode current collector 5 that collects current from the negative electrode active material layer 2, and a battery case 6 that houses these members. The sodium ion battery of the present invention is characterized in that the positive electrode active material layer 1 or the negative electrode active material layer 2 contains the active material for sodium ion battery described in the above-mentioned “A. Active material for sodium ion battery”. .

ADVANTAGE OF THE INVENTION According to this invention, precipitation of metal Na can be suppressed by using the active material for sodium ion batteries mentioned above, and it can be set as a highly safe sodium ion battery.
Hereinafter, the sodium ion battery of the present invention will be described for each configuration.

1. Negative electrode active material layer First, the negative electrode active material layer in the present invention will be described. The negative electrode active material layer in the present invention is a layer containing at least a negative electrode active material. The negative electrode active material layer may contain at least one of a conductive material, a binder, and a solid electrolyte material in addition to the negative electrode active material.

  In the present invention, the negative electrode active material is preferably the sodium ion battery active material described in "A. Sodium ion battery active material" above. It is because precipitation of metal Na can be suppressed and it can be set as a highly safe battery. Furthermore, since there are abundant active materials with higher potentials, a high-voltage sodium ion battery can be obtained. On the other hand, in the present invention, the above-described active material for sodium ion battery may be used for the positive electrode active material, and a conventional active material may be used for the negative electrode active material. In this case, it is necessary to use an active material having a lower potential than the above-described active material for a sodium ion battery as the negative electrode active material. Furthermore, since the sodium ion battery active material described above does not contain Na, the negative electrode active material preferably contains Na. That is, it is preferable to use Na-containing active materials such as metal Na and Na alloy as the negative electrode active material.

  The material for the conductive material is not particularly limited as long as it has desired electronic conductivity, and examples thereof include a carbon material. Furthermore, specific examples of the carbon material include acetylene black, ketjen black, carbon black, coke, carbon fiber, and graphite. The material of the binder is not particularly limited as long as it is chemically and electrically stable. For example, fluorine-based materials such as polyvinylidene fluoride (PVDF) and polytetrafluoroethylene (PTFE) are used. Examples thereof include a binder and a rubber-based binder such as styrene butadiene rubber. The solid electrolyte material is not particularly limited as long as it has desired ionic conductivity, and examples thereof include an oxide solid electrolyte material and a sulfide solid electrolyte material. The solid electrolyte material will be described in detail in “3. Electrolyte layer” described later.

  The content of the negative electrode active material in the negative electrode active material layer is preferably larger from the viewpoint of capacity, for example, in the range of 60 wt% to 99 wt%, particularly in the range of 70 wt% to 95 wt%. Is preferred. Further, the content of the conductive material is preferably less as long as desired electronic conductivity can be ensured, and is preferably in the range of 1% by weight to 30% by weight, for example. Further, the content of the binder is preferably less as long as the negative electrode active material and the like can be stably fixed, and is preferably in the range of, for example, 1% by weight to 30% by weight. Further, the content of the solid electrolyte material is preferably smaller as long as desired ion conductivity can be ensured, and is preferably in the range of 1 wt% to 40 wt%, for example.

  The thickness of the negative electrode active material layer varies greatly depending on the configuration of the battery, but is preferably in the range of 0.1 μm to 1000 μm, for example.

2. Next, the positive electrode active material layer in the present invention will be described. The positive electrode active material layer in the present invention is a layer containing at least a positive electrode active material. The positive electrode active material layer may contain at least one of a conductive material, a binder, and a solid electrolyte material in addition to the positive electrode active material.

  In the present invention, the positive electrode active material is preferably an active material having a higher potential than the above-described active material for a sodium ion battery. It is because precipitation of metal Na can be suppressed and it can be set as a highly safe battery. Furthermore, since there are abundant active materials with higher potentials, a high-voltage sodium ion battery can be obtained.

When using the sodium ion battery active material described above as the negative electrode active material, a general active material can be used as the positive electrode active material. Examples of such a positive electrode active material include a layered active material, a spinel active material, and an olivine active material. Specific examples of the positive electrode active material include NaFeO ₂ , NaNiO ₂ , NaCoO ₂ , NaMnO ₂ , NaVO ₂ , Na (Ni _X Mn _1-X ) O ₂ (0 <X <1), Na (Fe _X Mn _{1− X 2} ) O ₂ (0 <X <1), NaVPO ₄ F, Na ₂ FePO ₄ F, Na ₃ V ₂ (PO ₄ ) _{3 and the} like.

  The shape of the positive electrode active material is preferably particulate. The average particle diameter (D50) of the positive electrode active material is preferably in the range of 1 nm to 100 μm, for example, and in particular in the range of 10 nm to 30 μm. The content of the positive electrode active material in the positive electrode active material layer is preferably higher from the viewpoint of capacity, for example, in the range of 60 wt% to 99 wt%, particularly in the range of 70 wt% to 95 wt%. Is preferred. The type and content of the conductive material, binder, and solid electrolyte material used for the positive electrode active material layer are the same as those described for the negative electrode active material layer described above. Omitted. The thickness of the positive electrode active material layer varies greatly depending on the configuration of the battery, but is preferably in the range of 0.1 μm to 1000 μm, for example.

3. Electrolyte Layer Next, the electrolyte layer in the present invention will be described. The electrolyte layer in the present invention is a layer formed between the positive electrode active material layer and the negative electrode active material layer. Ion conduction between the positive electrode active material and the negative electrode active material is performed via the electrolyte contained in the electrolyte layer. The form of the electrolyte layer is not particularly limited, and examples thereof include a liquid electrolyte layer, a gel electrolyte layer, and a solid electrolyte layer.

The liquid electrolyte layer is usually a layer using a non-aqueous electrolyte. The nonaqueous electrolytic solution usually contains a sodium salt and a nonaqueous solvent. Examples of sodium salts include inorganic sodium salts such as NaPF ₆ , NaBF ₄ , NaClO ₄ and NaAsF ₆ ; and NaCF ₃ SO ₃ , NaN (CF ₃ SO ₂ ) ₂ , NaN (C ₂ F ₅ SO ₂ ) ₂ , NaC An organic sodium salt such as (CF ₃ SO ₂ ) ₃ can be used. Examples of the non-aqueous solvent include ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), butylene carbonate (BC), γ-butyrolactone, sulfolane, Examples include acetonitrile, 1,2-dimethoxymethane, 1,3-dimethoxypropane, diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, and any mixture thereof. The concentration of the sodium salt in the nonaqueous electrolytic solution is, for example, in the range of 0.3 mol / L to 5 mol / L, and preferably in the range of 0.8 mol / L to 1.5 mol / L. This is because if the sodium salt concentration is too low, there is a possibility that the capacity will decrease at the high rate, and if the sodium salt concentration is too high, the viscosity will increase and the capacity may decrease at low temperatures. In the present invention, a low volatile liquid such as an ionic liquid may be used as the nonaqueous electrolytic solution.

  The gel electrolyte layer can be obtained, for example, by adding a polymer to the non-aqueous electrolyte and gelling. Specifically, gelation can be performed by adding a polymer such as polyethylene oxide (PEO), polyacrylonitrile (PAN), or polymethyl methacrylate (PMMA) to the nonaqueous electrolytic solution.

The solid electrolyte layer is a layer made of a solid electrolyte material. The solid electrolyte material is not particularly limited as long as it has Na ion conductivity, and examples thereof include oxide solid electrolyte materials and sulfide solid electrolyte materials. Examples of the oxide solid electrolyte material include Na ₃ Zr ₂ Si ₂ PO ₁₂ , β-alumina solid electrolyte (Na ₂ O-11Al ₂ O ₃ etc.) and the like. Examples of the sulfide solid electrolyte material include Na ₂ S—P ₂ S ₅ .

  The solid electrolyte material in the present invention may be amorphous or crystalline. The shape of the solid electrolyte material is preferably particulate. The average particle diameter (D50) of the solid electrolyte material is preferably in the range of 1 nm to 100 μm, for example, and in particular in the range of 10 nm to 30 μm.

  The thickness of the electrolyte layer varies greatly depending on the type of electrolyte and the configuration of the battery. For example, the thickness of the electrolyte layer is preferably in the range of 0.1 μm to 1000 μm, and more preferably in the range of 0.1 μm to 300 μm.

4). Other Configurations The sodium ion battery of the present invention has at least the negative electrode active material layer, the positive electrode active material layer, and the electrolyte layer described above. Furthermore, it usually has a positive electrode current collector for collecting current of the positive electrode active material layer and a negative electrode current collector for collecting current of the negative electrode active material layer. Examples of the material for the positive electrode current collector include SUS, aluminum, nickel, iron, titanium, and carbon. On the other hand, examples of the material for the negative electrode current collector include SUS, copper, nickel, and carbon. In addition, the thickness and shape of the positive electrode current collector and the negative electrode current collector are preferably appropriately selected according to the use of the battery.

  The sodium ion battery of the present invention may have a separator between the positive electrode active material layer and the negative electrode active material layer. This is because a battery with higher safety can be obtained. Examples of the material for the separator include porous films such as polyethylene, polypropylene, cellulose, and polyvinylidene fluoride; and nonwoven fabrics such as a resin nonwoven fabric and a glass fiber nonwoven fabric. Moreover, the battery case of a general battery can be used for the battery case used for this invention. Examples of the battery case include a SUS battery case.

5. Sodium ion battery The sodium ion battery of this invention will not be specifically limited if it has the positive electrode active material layer, negative electrode active material layer, and electrolyte layer which were mentioned above. The sodium ion battery of the present invention may be a battery in which the electrolyte layer is a solid electrolyte layer, a battery in which the electrolyte layer is a liquid electrolyte layer, or a battery in which the electrolyte layer is a gel electrolyte layer. May be. Further, the sodium ion battery of the present invention may be a primary battery or a secondary battery, but among them, a secondary battery is preferable. This is because it can be repeatedly charged and discharged and is useful, for example, as an in-vehicle battery. In addition, examples of the shape of the sodium ion battery of the present invention include a coin type, a laminate type, a cylindrical type, and a square type. Moreover, the manufacturing method of a sodium ion battery is not specifically limited, It is the same as the manufacturing method in a general sodium ion battery.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.

  Hereinafter, the present invention will be described in more detail with reference to examples.

[Example 1]
First, Y ₂ O ₃ , TiO ₂ and TiS ₂ (all manufactured by Aldrich) were prepared as raw materials. Next, Y ₂ O ₃ , TiO ₂ and TiS ₂ were weighed in equimolar amounts and mixed in a mortar to obtain a raw material composition. Next, the raw material composition was put in a quartz tube and vacuum-sealed (degree of vacuum: 10 ⁻⁵ Pa). Then, it heated up from room temperature to 1100 degreeC over 24 hours, and baked on the conditions of 1100 degreeC and 5 days (120 hours). After cooling, the resulting material was pulverized in a mortar to adjust the particle size. This obtained the sodium ion battery active material (YTOS) of the present invention.

[Example 2]
First, Nd ₂ O ₃ , TiO ₂ and TiS ₂ (all made by Aldrich) were prepared as raw materials. Next, Nd ₂ O ₃ , TiO ₂ and TiS ₂ were weighed in equimolar amounts and mixed in a mortar to obtain a raw material composition. Next, the raw material composition was put in a quartz tube and vacuum-sealed (degree of vacuum: 10 ⁻⁵ Pa). Then, it heated up from room temperature to 1100 degreeC over 24 hours, and baked on the conditions of 1100 degreeC and 4 days (96 hours). After cooling, the resulting material was pulverized in a mortar to adjust the particle size. This obtained the active material for sodium ion batteries of this invention.

[Evaluation 1]
(1) X-ray diffraction measurement Using the active material obtained in Example 1, X-ray diffraction (XRD) measurement using CuKα rays was performed. The result is shown in FIG. From the chart shown in FIG. 2, it was confirmed that the obtained active material contained a Y ₂ Ti ₂ O ₅ S ₂ crystal phase. The peaks indicating the Y ₂ Ti ₂ O ₅ S ₂ crystal phase are 2θ = 15.6 °, 23.4 °, 23.9 °, 26.2 °, 30.8 °, 31.3 °, 33.6. It appeared at 34.5 °, 36.4 °, 41.3 °, 43.0 °, 46.6 °, 47.8 ° and 48.2 °.

Using the active material obtained in Example 2, X-ray diffraction (XRD) measurement using CuKα rays was performed. The result is shown in FIG. From the chart shown in FIG. 3, it was confirmed that the obtained active material contained a Nd ₂ Ti ₂ O ₅ S ₂ crystal phase. The peaks indicating the Nd ₂ Ti ₂ O ₅ S ₂ crystal phase are 2θ = 15.4 °, 25.8 °, 30.3 °, 32.8 °, 35.9 °, 40.6 °, 42.4. Appeared at 47.0 °.

(2) Charge / Discharge Characteristics An evaluation battery was prepared using the active material (YTOS) obtained in Example 1, and the charge / discharge characteristics of the active material were evaluated. First, an active material (YTOS), a conductive material (acetylene black 60 wt% + VGCF 40 wt%), and a binder (polyvinylidene fluoride, PVDF), an active material: a conductive material: a binder = 65: 20: A paste was obtained by mixing at a weight ratio of 15 and kneading. Next, the obtained paste was coated on a copper foil with a doctor blade, dried, and pressed to obtain a test electrode having a thickness of 10 μm.

Thereafter, a CR2032-type coin cell was used, the test electrode was used as a working electrode, metal Na was used as a counter electrode, and a polyethylene / polypropylene / polyethylene porous separator (thickness: 25 μm) was used as a separator to obtain a battery for evaluation. As the electrolytic solution, a solution obtained by dissolving NaPF ₆ at a concentration of 1 mol / L in a solvent in which EC (ethylene carbonate) and DMC (dimethyl carbonate) were mixed in the same volume was used.

  The obtained battery for evaluation was charged and discharged at a battery evaluation environmental temperature of 25 ° C. and a current rate of C / 10. The voltage range was 0.01V to 2.5V. The result is shown in FIG. As shown in FIG. 4, a plateau portion was generated at 0.7 V when Na was inserted, and a plateau portion was generated at 0.9 V when Na was desorbed. From this, it was confirmed that this active material had a Na insertion / release potential of 0.5 V or more with respect to metal Na.

(3) Cyclic voltammetry measurement By performing cyclic voltammetry (CV) measurement on the evaluation battery using the active material obtained in Example 1, Na insertion of the active material with respect to metallic Na The desorption potential was calculated. The measurement conditions were an electrochemical measurement system (made by Solartron, 147055BEC type), a potential range of 0.01 V to 2.5 V (vs Na / Na ⁺ ), and a sweep rate of 0.1 mV / sec. As a result, the Na insertion potential is 0.68 V (vs Na / Na ⁺ ), the Na elimination potential is 0.88 V (vs Na / Na ⁺ ), and the Na insertion elimination potential is 0.78 V (vs Na / Na ⁺ ). ⁺ ).

[Example 3-1]
First, Y ₂ O ₃ , TiO ₂ and TiS ₂ (all manufactured by Aldrich) were prepared as raw materials. Next, TiS ₂ , TiO ₂ and Y ₂ O ₃ were weighed so that the molar ratio was 1.05: 0.95: 1.00 and mixed in a mortar to obtain a raw material composition. Next, the raw material composition was put in a quartz tube and vacuum-sealed (degree of vacuum: 10 ⁻⁵ Pa). Then, it heated up from room temperature to 1100 degreeC over 24 hours, and baked on the conditions of 1100 degreeC and 4 days (96 hours). After cooling, the resulting material was pulverized in a mortar to adjust the particle size. This obtained the active material for sodium ion batteries of this invention.

[Example 3-2]
An active material was obtained in the same manner as in Example 3-1, except that TiS ₂ , TiO _2, and Y ₂ O ₃ were weighed so that the molar ratio was 1.10: 0.90: 1.00. .

[Example 3-3]
An active material was obtained in the same manner as in Example 3-1, except that TiS ₂ , TiO _2, and Y ₂ O ₃ were weighed so that the molar ratio was 1.15: 0.85: 1.00. .

[Example 3-4]
An active material was obtained in the same manner as in Example 3-1, except that TiS ₂ , TiO _2, and Y ₂ O ₃ were weighed so that the molar ratio was 1.20: 0.80: 1.00. .

[Evaluation 2]
Using the active materials obtained in Example 1 and Examples 3-1 to 3-4, X-ray diffraction (XRD) measurement using CuKα rays was performed. The result is shown in FIG. As shown in FIG. 5, it was confirmed that Example 1 and Examples 3-1 to 3-4 all have a Y ₂ Ti ₂ O ₅ S ₂ crystal phase. FIG. 6 is an enlarged view of FIG. In Example 1, the peak of the Y ₂ Ti ₂ O ₇ crystal phase appears at 2θ = 35.6 °, and in Examples 3-3 and 3-4, the peak of TiS ₂ is 2θ = 34.1 ° due to excessive sulfur. Appeared in. On the other hand, in Examples 3-1 and 3-2, the Y ₂ Ti ₂ O ₇ crystal phase and the peak of TiS ₂ were not confirmed. Further, as shown in FIG. 6, the peak intensity of _{Y 2 Ti} 2 _O 5 _S 2 in 2 [Theta] = 34.5 ° and _{I A,} the peak intensity of _Y 2 _Ti 2 _{O 7} in 2θ = 35.6 ° I and _B, and the peak intensity of TiS ₂ in 2 [Theta] = 34.1 ° and _{I C,} the value of I B / _{I a} and _I C / _{I a} was as shown in table 1 below.

As shown in Table 1, the active materials obtained in Examples 3-1 and 3-2 do not have Y ₂ Ti ₂ O ₇ crystal phase and TiS ₂ peaks, which are impurities, and are simple. It was confirmed that the active material was composed of the phase Y ₂ Ti ₂ O ₅ S ₂ crystal phase. Incidentally, the value of I _{C /} I _A is increased in Example 1, is probably to be due located in the shoulder of the peak of the next.

DESCRIPTION OF SYMBOLS 1 ... Positive electrode active material layer 2 ... Negative electrode active material layer 3 ... Electrolyte layer 4 ... Positive electrode collector 5 ... Negative electrode collector 6 ... Battery case 10 ... Sodium ion battery

Claims (11)

A sodium ion battery active material comprising a group III element, an M element, a Ti element, an O element, and an S element, and an M ₂ Ti ₂ O ₅ S ₂ crystal phase. The active material for a sodium ion battery according to claim 1, comprising the M ₂ Ti ₂ O ₅ S ₂ crystal phase as a main component.   The sodium ion battery active material according to claim 1, wherein the M element is at least one of Y and Nd. The M element includes at least Y;
In X-ray diffraction measurement using a CuKα line, 2 [Theta] = the peak intensity of the _{Y 2 Ti} 2 _O 5 _S 2 crystal phase in 34.5 ° and _{I A, Y} in _{2θ = 35.6 ° 2 Ti 2 O} 7 the peak intensity of the crystalline phase and _{I B,} the peak intensity of TiS ₂ in 2 [Theta] = 34.1 ° in the case of the _{I C,} not more than the value 0.3 of _I B / I _{a, and, I} C / active material for a sodium ion battery according to any one of claims of claims 1 to 3, characterized in that the value of I _a is 0.15 or less.   The sodium ion battery active material according to any one of claims 1 to 4, wherein a Na insertion / extraction potential with respect to metal Na is 0.5 V or more.   Sodium ion characterized in that it contains a Group III element M element, Ti element, O element and S element, is crystalline, and has a Na insertion / release potential of 0.5 V or more with respect to metal Na Battery active material. 7. The active material for a sodium ion battery according to claim 6, wherein the active material for a sodium ion battery according to claim 6 has a crystal phase having a structure in which a part of the M element located at the A site of the Ruddlesden-Popper structure A ₃ B ₂ C ₇ is missing.   The sodium ion battery active material according to claim 6 or 7, wherein the M element is at least one of Y and Nd.   The active material for a sodium ion battery according to any one of claims 1 to 8, wherein the active material is a negative electrode active material. A sodium ion battery having a positive electrode active material layer containing a positive electrode active material, a negative electrode active material layer containing a negative electrode active material, and an electrolyte layer formed between the positive electrode active material layer and the negative electrode active material layer There,
The sodium ion battery, wherein the positive electrode active material or the negative electrode active material is an active material for a sodium ion battery according to any one of claims 1 to 9.   The sodium ion battery according to claim 10, wherein the negative electrode active material is the active material for a sodium ion battery.

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