JP6101771B1 - Positive electrode active material for sodium ion battery and method for producing the same - Google Patents

Abstract

A positive electrode active material for a sodium ion battery capable of obtaining a sodium ion battery exhibiting a large discharge capacity and a method for producing the same are provided. The following formula (A) obtained by hydrothermal reaction: NaFeaMnbMcPO4 (A) (wherein M is Mg, Ca, Sr, Y, Zr, Mo, Ba, Pb, Bi, Represents La, Ce, Nd or Gd, a, b and c satisfy 0 <a, 0 ≦ b <1, 0 <c ≦ 0.2, 2a + 2b + (valence of M) × c = 2, and The positive electrode active material for sodium ion batteries containing the olivine type sodium iron phosphate compound represented by a = 1-b- (the valence of M) × c ÷ 2. [Selection figure] None

Description

  The present invention relates to a positive electrode active material for a sodium ion battery that can effectively increase the discharge capacity of the sodium ion battery and a method for producing the same.

  While secondary batteries used for portable electronic devices, hybrid vehicles, electric vehicles, and the like are being developed, lithium ion batteries are particularly widely used because they exhibit high output characteristics and good cycle characteristics. On the other hand, lithium used as a raw material for a lithium ion battery is not necessarily abundant as a resource, and since the production area is limited, it is an expensive raw material. For this reason, sodium ion batteries (NIB) using sodium, which is an abundant resource with no uneven distribution of localities, are attracting attention, and various attempts have been made to realize such positive electrode materials for batteries.

For example, in Patent Document 1, it is represented by A _a M _b PO ₄ having _a feature in an X-ray diffraction pattern (a is 0.5 to 1.5 and b is 0.5 to 1.5). A positive electrode active material is disclosed, and such an active material is obtained by a solid phase method, and a specific example (NaFePO ₄ ) in which A is sodium and M is Fe is shown. A production method is shown in which a similar positive electrode active material is obtained through solid-liquid separation by heating a liquid material containing raw materials.
Further in Patent Document 3, Na _x M _y PO positive electrode active material for sodium secondary batteries which comprises a transition metal phosphates represented by ₄ is disclosed. Such transition metal phosphate has a specific BET specific surface area, and specific examples in which M is Fe or Mn are shown. A dry solid product obtained by evaporating water from a solid-liquid mixture is washed with water. A production method for drying is described.

JP 2009-206085 A JP 2011-134550 A JP 2010-18472 A

  However, even with the active materials described in any of the above-mentioned documents, there is a situation in which sufficient discharge capacity cannot be secured in the obtained sodium ion battery, and further improvement is required.

  Therefore, the subject of this invention is providing the positive electrode active material for sodium ion batteries which can obtain the sodium ion battery which shows a big discharge capacity, and its manufacturing method.

  Therefore, the present inventors conducted various studies on the composition and manufacturing method as a positive electrode active material for sodium ion batteries. When an olivine-type sodium iron phosphate compound containing a specific dope metal obtained by a hydrothermal reaction is used. The inventors have found that a positive electrode active material for a sodium ion battery that can exhibit a high discharge capacity can be obtained, and have completed the present invention.

That is, the present invention provides the following formula (A) obtained by a hydrothermal reaction:
NaFe _a Mn _b M _c PO ₄ (A)
(In the formula (A), M represents Mg, Ca, Sr, Y, Zr, Mo, Ba, Pb, Bi, La, Ce, Nd, or Gd. A, b, and c are 0 <a, 0 ≦ b <1, 0 <c ≦ 0.2, 2a + 2b + (M valence) × c = 2, and a = 1−b− (M valence) × c ÷ 2 is satisfied.)
It is providing the positive electrode active material for sodium ion batteries containing the olivine type sodium iron phosphate compound represented by these.
The present invention also relates to a sodium compound, an iron compound, and a metal (M) compound (M represents Mg, Ca, Sr, Y, Zr, Mo, Ba, Pb, Bi, La, Ce, Nd, or Gd). And a step of mixing the phosphoric acid compound under a nitrogen atmosphere to obtain a mixed solution (I), and a step of subjecting the obtained mixed solution to a hydrothermal reaction and then drying (II)
It is providing the manufacturing method of the said positive electrode active material for sodium ion batteries provided with this.

  According to the positive electrode active material for a sodium ion battery of the present invention, since it contains the olivine-type sodium iron phosphate compound in which a specific doped metal is present, a sodium ion battery exhibiting an excellent discharge capacity can be obtained.

Hereinafter, the present invention will be described in detail.
The positive electrode active material for a sodium ion battery of the present invention has the following formula (A) obtained by a hydrothermal reaction:
NaFe _a Mn _b M _c PO ₄ (A)
(In the formula (A), M represents Mg, Ca, Sr, Y, Zr, Mo, Ba, Pb, Bi, La, Ce, Nd, or Gd. A, b, and c are 0 <a, 0 ≦ b <1, 0 <c ≦ 0.2, 2a + 2b + (M valence) × c = 2, and a = 1−b− (M valence) × c ÷ 2 is satisfied.)
The olivine type | mold sodium iron phosphate compound represented by these is contained.

  The olivine-type sodium iron phosphate compound represented by the above formula (A) contains at least sodium and iron, and these sodium and iron contain a doped metal (M) of a heteroatom. Thus, the olivine type sodium iron phosphate compound represented by the above formula (A) containing the doped metal (M) is a compound that can be obtained by a hydrothermal reaction, and the olivine in which the doped metal (M) is interposed. By using the type sodium iron phosphate compound as the positive electrode active material, it is possible to realize a sodium ion battery exhibiting a high discharge capacity.

In the formula (A), M represents Mg, Ca, Sr, Y, Zr, Mo, Ba, Pb, Bi, La, Ce, Nd or Gd, preferably Mg, Zr or Mo, more preferably Mg or Zr. a is 0 <a, and preferably 0.1 ≦ a. b is 0 ≦ b <1, and preferably 0 ≦ b ≦ 0.9. c is 0 <c ≦ 0.2, and preferably 0 <c ≦ 0.1. These a, b, and c are numbers satisfying 2a + 2b + (M valence) × c = 2, and a = 1−b− (M valence) × c ÷ 2. Specific examples of the olivine-type sodium iron phosphate compound represented by the above formula (A) include NaFe _0.98 Mg _0.02 PO ₄ , NaFe _0.98 Zr _0.01 PO ₄ , NaFe _0.98 Mo _0.007 PO ₄ , NaFe _0.28 Mn _0.7 Mg _0.02 PO ₄ , NaFe _0.28 Mn _0.7 Zr _0.01 PO ₄ , NaFe _0.28 Mn _0.7 Mo _0.007 PO _{4 and the} like can be mentioned.

The positive electrode active material for a sodium ion battery according to the present invention contains an olivine-type sodium iron phosphate compound supported by carbon from the viewpoint of enhancing conductivity and effectively improving the discharge capacity of the obtained sodium ion battery. Is preferred. Examples of the carbon source used for supporting carbon include water-soluble carbon materials such as glucose, fructose, sucrose, polyethylene glycol, polyvinyl alcohol, carboxymethylcellulose, saccharose, starch, dextrin, and citric acid; acetylene black, ketjen black , Carbon black such as channel black, furnace black, lamp black and thermal black. Especially, about the water-soluble carbon material, glucose, fructose, sucrose, and dextrin are preferable and glucose is more preferable from a viewpoint of improving the solubility and dispersibility to a solvent and functioning effectively as a carbon material. As for carbon black, ketjen black is preferable from the viewpoint of effectively increasing the tap density of the positive electrode active material for a sodium ion battery to be produced. The water-soluble carbon material means an organic compound that is dissolved in 100 g of water at 25 ° C. in an amount of 0.4 g or more, preferably 1.0 g or more in terms of carbon atom of the water-soluble carbon material.
The amount of carbon supported is 100 to 15% by mass in terms of carbon atom in 100% by mass of the positive electrode active material for a sodium ion battery, preferably 0.1 to 15% by mass, more preferably 0.2 to 10% by mass, More preferably, it is 0.3-8 mass%.

The manufacturing method of the positive electrode active material for sodium ion batteries of the present invention includes a sodium compound, an iron compound, and a metal (M) compound (M is Mg, Ca, Sr, Y, Zr, Mo, Ba, Pb, Bi, La, Ce). , Nd or Gd.) And a step of mixing a phosphoric acid compound in a nitrogen atmosphere to obtain a mixed solution (I), and a step of subjecting the obtained mixed solution to a hydrothermal reaction followed by drying (II) )
Is provided.

Step (I) is a sodium compound, iron compound, metal (M) compound (M represents Mg, Ca, Sr, Y, Zr, Mo, Ba, Pb, Bi, La, Ce, Nd, or Gd). And a phosphoric acid compound in a nitrogen atmosphere to obtain a mixed solution.
Examples of the sodium compound include sodium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium nitrate, sodium sulfate, sodium chloride and the like. Of these, sodium hydroxide is preferable from the viewpoint of increasing reactivity.
The iron compound may be a divalent iron compound or a hydrate thereof, for example, a halide such as iron halide; a sulfate such as iron sulfate; an organic acid salt such as iron oxalate or iron acetate. As well as hydrates thereof. Especially, it is preferable to use iron sulfate or its hydrate from a viewpoint of improving a battery characteristic.
Examples of the metal (M) compound include halides including metal (M), sulfates, and acetates. Especially, it is preferable to use a sulfate from a viewpoint of improving battery characteristics.
Examples of the phosphoric acid compound include orthophosphoric acid (H ₃ PO ₄ , phosphoric acid), metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, tetraphosphoric acid, ammonium phosphate, and ammonium hydrogen phosphate. Of these, phosphoric acid is preferably used, and is preferably used as an aqueous solution having a concentration of 70 to 90% by mass.

  In addition, the liquid mixture obtained by process (I) contains water from a viewpoint of making the hydrothermal reaction in subsequent process (II) advance favorably. The amount of water used is preferably 10 to 30 mol, more preferably 12.5 to 25 mol, relative to 1 mol of sodium ions in the mixed solution.

These sodium compounds, iron compounds, metal (M) compounds, and phosphoric acid compounds increase their solubility, favorably dope metal (M), and suppress oxidation of iron compounds and metal (M) compounds. In view of the above, it is preferable to mix a sodium compound, an iron compound, a metal (M) compound, and a phosphoric acid compound in a nitrogen atmosphere. Specifically, a sodium compound and a phosphoric acid compound are mixed, After that, a mixed solution X ¹ is obtained, and an iron compound and a metal (M) compound are added to and mixed with the mixed solution X ¹ , and the obtained mixed solution X ² is subjected to step (II). .

More specifically, the sodium compound is preferably mixed with water in advance to form slurry water, and it is preferable to add a phosphoric acid compound to the slurry water. Moreover, it is good to use phosphoric acid aqueous solution as a phosphoric acid compound, and it is preferable to dripping phosphoric acid aqueous solution, stirring slurry water. By adding dropwise a small amount of phosphoric acid aqueous solution to the slurry water, the reaction in the mixed solution X ¹ proceeds well, and the precursor of the olivine-type sodium iron phosphate compound represented by the above formula (A) is added. It can produce | generate, making it disperse | distribute uniformly in a slurry, and can also suppress effectively that this precursor aggregates unnecessarily.

The dropping rate of the aqueous phosphoric acid solution into the slurry water is preferably 15 to 50 mL / min, more preferably 20 to 45 mL / min, and further preferably 28 to 40 mL / min. Moreover, the stirring time of the slurry water while dropping the phosphoric acid aqueous solution is preferably 0.5 to 24 hours, and more preferably 3 to 12 hours. Furthermore, the stirring speed of the slurry water while dropping the phosphoric acid aqueous solution is preferably 200 to 700 rpm, more preferably 250 to 600 rpm, and further preferably 300 to 500 rpm.
In addition, when stirring slurry water, it is preferable to cool to below the boiling point temperature of slurry water. Specifically, cooling to 80 ° C. or lower is preferable, and cooling to 20 to 60 ° C. is more preferable.

Then mixed sodium compound and phosphoric acid compounds, after a nitrogen atmosphere to obtain a mixture X ^1. Thus, to complete the reaction in a mixed solution X ^1, the precursor of the olivine-type sodium iron phosphate compound represented by the above formula (A) can be favorably produced. The content of Na in the mixed liquid X in ^1, compared per mole of phosphorus in the mixture X in ^1, it is preferably in the range of 1.0 to 2.95 mol, and even a 1.5 to 2.95 moles More preferably, it is 2.0-2.9 mol.
In order to obtain a nitrogen atmosphere, it is only necessary to purge nitrogen, which allows the reaction to proceed in a state where the dissolved oxygen concentration in the mixed solution X ¹ is reduced. Oxidation of a metal (M) compound etc. can be suppressed. In the mixed solution X ¹ , the precursor of the olivine-type sodium iron phosphate compound represented by the above formula (A) is trisodium phosphate (Na ₃ PO ₄ ) and exists as fine dispersed particles.

The pressure for purging nitrogen is preferably 0.1 to 0.2 MPa, more preferably 0.1 to 0.15 MPa. The temperature of the mixture X ¹ after mixing the phosphoric acid compound is preferably 20 to 80 ° C., more preferably from 20 to 60 ° C.. The reaction time is preferably 5 to 60 minutes, more preferably 15 to 45 minutes.
Further, when the purging nitrogen from the viewpoint of advancing satisfactorily reaction, the mixture is stirred for X ¹ after mixing the phosphoric acid compound are preferred. The stirring speed at this time is preferably 200 to 700 rpm, more preferably 250 to 600 rpm.

Further, from the viewpoint of more effectively suppressing oxidation of the precursor on the surface of the dispersed particles and miniaturizing the dispersed particles, the dissolved oxygen concentration in the mixture X ¹ after mixing the phosphoric acid compound in the step (I). Is preferably 0.5 mg / L or less, and more preferably 0.2 mg / L or less.

Next, at step (I), the mixed solution X ¹ iron compounds, and then adding and mixing the metal (M) compound to obtain a mixture X ^2. The content of Na in such mixture X ^2, the total from the viewpoint of satisfactorily doped with metal (M) in the olivine-type sodium iron phosphate compound, a metal atom containing Fe and M in the mixed solution X ² 1 It is preferable that it is 1.0-3.3 mol with respect to mol, It is more preferable that it is 1.5-3.3 mol, It is further more preferable that it is 2.0-3.2 mol. The content of phosphorus in the mixed solution X ² is the total 1 mol of the metal atoms including Fe and M in the mixture X ^2, is preferably from 1.0 to 1.1 mol, 1. It is more preferably 0 to 1.08 mol, and further preferably 1.0 to 1.05 mol.

In yet step (I), it includes the step of adding an antioxidant to the mixture X ¹ is preferred. Examples of such an antioxidant include sodium sulfite (Na ₂ SO ₃ ), sodium hydrosulfite (Na ₂ S ₂ O ₄ ), aqueous ammonia, and the like. By adding such an antioxidant, oxidation of iron compounds, metal (M) compounds and the like can be more effectively suppressed. The content of Na ₂ SO ₃ in the mixed solution X ¹ is preferably 0.01 to 1.0 mol, more preferably 0.03 to 0.5 mol, per 1 mol of phosphorus.
By passing through the step (I) in this way, trisodium phosphate (Na ₃ PO ₄ ) as a precursor of the olivine-type sodium iron phosphate compound represented by the above formula (A), an iron compound and a metal (M) A mixed solution X ^{2 in} which a compound or the like is present as a mixture is obtained as slurry water.

The step (I) may include a step (I-1) of further adding a water-soluble carbon material to the mixed solution X ¹ or the mixed solution X ² obtained in the step (I). Thus, a composite (secondary particle) in which carbon derived from a water-soluble carbon material is supported on the olivine-type sodium iron phosphate compound (primary particle) represented by the above formula (A) in the step (II) described later. By using this as a positive electrode active material, it is possible to effectively improve the discharge capacity of the obtained sodium ion battery.

  The amount of the water-soluble carbon material added in the step (I-1) may be an amount such that the supported amount of carbon in 100% by mass of the positive electrode active material for sodium ion battery is within the above range in terms of carbon atom. . For example, the addition amount of the water-soluble carbon material is a carbon atom equivalent with respect to 100 parts by mass of the composite (secondary particle) obtained in the step (II) described later, preferably 0.1 to 17.7 parts by mass. More preferably, the amount is 0.2 to 11.1 parts by mass, and more preferably 0.3 to 8.7 parts by mass.

Step (II) is a step in which the mixed solution X ² obtained in step (I) is subjected to a hydrothermal reaction and then dried. By subjecting the mixed solution X ² to a hydrothermal reaction, the olivine-type sodium iron phosphate compound represented by the above formula (A) can be obtained as primary particles while doping the metal (M) well, It becomes possible to make very fine particles, and a very useful positive electrode active material for a sodium ion battery can be obtained.

  The temperature in the hydrothermal reaction in the step (II) is preferably 130 to 250 ° C, more preferably 140 to 230 ° C. Such a hydrothermal reaction is preferably performed in a pressure vessel, and the pressure is preferably 0.3 to 1.5 MPa, more preferably 0.4 to 1.0 MPa, and also in a nitrogen atmosphere or a steam atmosphere. It is good to do below. The hydrothermal reaction time is preferably 0.1 to 48 hours, more preferably 0.2 to 24 hours.

  The obtained primary particles are preferably isolated by drying after filtration, washing with water. As the drying means, freeze drying or vacuum drying is used. Such primary particles can be directly used as a positive electrode active material for sodium ion batteries.

  In the step (II), a water-soluble carbon material and water are further added to the olivine-type sodium iron phosphate compound (primary particles) represented by the above formula (A) after the drying treatment and spray-dried. A step (II-2) of further adding carbon black to the step (II-1) or the obtained olivine-type sodium iron phosphate compound (primary particles) represented by the above formula (A) after the drying treatment. May be included. When this step (II-1) is included, a composite (secondary) in which carbon derived from a water-soluble carbon material is supported on the olivine-type sodium iron phosphate compound (primary particles) represented by the above formula (A). In the case where the step (II-2) is included, a composite in which carbon black is supported on the olivine-type sodium iron phosphate compound (primary particles) represented by the above formula (A). (Secondary particles) can be obtained, and by using this as a positive electrode active material, the discharge capacity of the obtained sodium ion battery can be effectively improved.

  The amount of carbon source (water-soluble carbon material or carbon black) added in the step (II-1) or the step (II-2) is such that the amount of carbon supported in 100% by mass of the positive electrode active material for sodium ion batteries is as follows: What is necessary is just the quantity which becomes in the said range by the amount of carbon atom conversion. For example, the addition amount of the carbon source is a carbon atom conversion amount with respect to 100 parts by mass of the composite (secondary particle), preferably 0.1 to 17.7 parts by mass, and more preferably 0.2 to 11.1. 1 part by mass, and more preferably 0.3 to 8.7 parts by mass.

When the step (II) includes the step (II-2), when carbon black is added to the olivine-type sodium iron phosphate compound (primary particles) represented by the above formula (A), these are mixed. Preferably, such mixing is preferably mixing by a normal ball mill, and more preferably a composite (secondary particle) is obtained by mixing by a planetary ball mill capable of revolving.
Furthermore, from the viewpoint of finely and uniformly dispersing carbon on the surface of the olivine-type sodium iron phosphate compound (primary particles) represented by the above formula (A) and effectively supporting it, compressive force and shearing force are It is more preferable to mix while adding to form a composite (secondary particle). The process of mixing while applying a compressive force and a shearing force is preferably performed in a closed container equipped with an impeller. The peripheral speed of the impeller is preferably 25 to 40 m / s, more preferably 27 to 40 m / s, from the viewpoint of effectively increasing the conductivity of the obtained positive electrode active material and improving the discharge capacity of the battery. is there. The mixing time is preferably 5 to 90 minutes, more preferably 10 to 80 minutes.
The peripheral speed of the impeller means the speed of the outermost end portion of the rotary stirring blade (impeller), which can be expressed by the following formula (X), and is mixed while applying compressive force and shearing force. The processing time may vary depending on the peripheral speed of the impeller so that it becomes longer as the peripheral speed of the impeller is slower.
Impeller peripheral speed (m / s) =
Impeller radius (m) × 2 × π × rotational speed (rpm) ÷ 60 (X)

In the step (II-2), the processing time and / or the peripheral speed of the impeller at the time of performing the mixing process while adding the compressive force and the shearing force depends on the amount of the composite (secondary particles) charged into the container. It is necessary to adjust accordingly. Then, by operating the container, it is possible to perform a process of mixing the impeller and the inner wall of the container while the compressive force and the shearing force are applied to the mixture, which is expressed by the above formula (A). The olivine-type sodium iron phosphate compound (primary particles) can be finely and uniformly dispersed on the surface.
For example, when the mixing process is performed for 6 to 90 minutes in an airtight container equipped with an impeller rotating at a peripheral speed of 25 to 40 m / s, the amount of the composite (secondary particles) charged into the container is an effective container ( Among sealed containers equipped with an impeller, a container corresponding to a part capable of accommodating a composite) per cm ³ is preferably 0.1 to 0.7 g, more preferably 0.15 to 0.4 g.

  Examples of the apparatus equipped with a closed container that can easily perform mixing while applying compressive force and shear force include a high-speed shear mill, a blade-type kneader, and the like. Fine particle composite apparatus Nobilta (manufactured by Hosokawa Micron Corporation) can be suitably used.

  The primary particles or secondary particles obtained through the step (II) are preferably fired. Such firing is preferably performed in a reducing atmosphere or an inert atmosphere. From the viewpoint of improving the crystallinity of the olivine-type sodium iron phosphate compound represented by the above formula (A), the firing temperature further includes the step (I-1) or the step (II-1). From the viewpoint of effectively supporting carbon derived from the material on the olivine-type sodium iron phosphate compound represented by the above formula (A), the temperature is preferably 500 to 800 ° C, more preferably 600 to 770 ° C, and still more preferably. Is 650-750 degreeC. The firing time is preferably 10 minutes to 3 hours, more preferably 30 minutes to 1.5 hours.

  The secondary battery to which the positive electrode for a secondary battery including the positive electrode active material for a secondary battery of the present invention can be applied is not particularly limited as long as it has a positive electrode, a negative electrode, an electrolytic solution, and a separator as essential components.

  Here, as long as sodium ions can be occluded at the time of charging and released at the time of discharging, the material configuration is not particularly limited, and a known material configuration can be used. For example, a carbon material such as sodium metal, graphite, or amorphous carbon. It is preferable to use an electrode formed of an intercalating material capable of electrochemically occluding and releasing sodium ions, particularly a carbon material.

  The electrolytic solution is obtained by dissolving a supporting salt in an organic solvent. The organic solvent is not particularly limited as long as it is an organic solvent used in an electrolyte solution of a sodium ion secondary battery. For example, carbonates, halogenated hydrocarbons, ethers, ketones, nitriles, lactones An oxolane compound or the like can be used.

The kind of the supporting salt is not particularly limited, but an inorganic salt selected from NaPF ₆ , NaBF ₄ , NaClO ₄ , NaAsF ₆ , a derivative of the inorganic salt, NaSO ₃ CF ₃ , NaC (SO ₃ CF ₃ ) ₂ , NaN (SO ₃ CF ₃ ) ₂ , NaN (SO ₂ C ₂ F ₅ ) ₂ and NaN (SO ₂ CF ₃ ) (SO ₂ C ₄ F ₉ ), and derivatives of the organic salts It is preferable that it is at least 1 type of these.

  The separator plays a role of electrically insulating the positive electrode and the negative electrode and holding the electrolytic solution. For example, a porous synthetic resin film, particularly a polyolefin polymer (polyethylene, polypropylene) porous film may be used.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples.

[Example 1]
A slurry water was obtained by mixing 5.60 g (140 mmol) of NaOH and 90 g of water. Next, the slurry water obtained was stirred at a stirring speed of 400 rpm while being kept at 40 ° C., and 5.77 g (50 mmol) of an 85% aqueous phosphoric acid solution was mixed therein to obtain a mixed solution X ¹ . Next, to a mixed solution X ¹ obtained, to obtain a mixed liquid X ¹ containing nitrogen to purge the (0.2 MPa) is adjusted to the concentration of dissolved oxygen 0.5 mg / L precursor. To this mixture _{^{X 1 FeSO 4 · 7H 2 O}} 13.62g (49mmol), was obtained _{MgSO 4 · 7H 2 O 0.25g (} 1mmol) mixture X ² added.
Here, in the mixed solution X ² , Na was 2.8 mol and phosphorus was 1 mol with respect to 1 mol in total of Fe and Mg.

Next, the mixed solution X ² was put into an autoclave, the inside of the autoclave was purged with nitrogen, and a hydrothermal reaction was performed at 200 ° C. for 3 hours. After carrying out a hydrothermal reaction, the mixture was allowed to cool, and the produced crystals were filtered, then washed with water, and lyophilized for about 12 hours to obtain primary particles (NaFe _0.98 Mg _0.02 PO ₄ ). A container provided in a planetary ball mill (P-5, manufactured by Fritsch) by mixing 10 g of the obtained primary particles and 1.25 g of glucose (5 parts by mass in terms of carbon atoms with respect to 100 parts by mass of primary particles). The solvent obtained by mixing 90 g of ethanol and 10 g of water was added thereto. Next, 100 g of a ball (ball diameter: 1 mm) was used and mixed for 1 hour at a rotation speed of 400 rpm.
The obtained mixture was filtered, the solvent was distilled off using an evaporator, and then calcined at 700 ° C. for 1 hour in a reducing atmosphere to obtain a positive electrode active material for sodium ion batteries (NaFe _0.98 Mg _0.02 PO ₄ ). .

[Example 2]
In the same manner as in Example 1, except that 0.18 g (0.5 mmol) of Zr (SO ₄ ) ₂ .4H ₂ O was added instead of MgSO ₄ .7H ₂ O, a positive electrode active material for sodium ion battery (NaFe _0.98 Zr _0.01 PO ₄ ) was obtained.

[Example 3]
Instead of MgSO ₄ .7H ₂ O, a positive electrode active material for sodium ion battery (NaFe _0.98 Mo ₀ .0) was added in the same manner as in Example 1 except that 0.054 g (0.33 mmol) of H ₂ MoO ₄ was added _{. 007} PO ₄ ).

[Example 4]
Instead of _{FeSO 4 · 7H 2 O 13.62g,} FeSO 4 · 7H 2 O 3.89g (14mmol) and _{MnSO 4 · 5H 2 O 8.44g (} 35mmol) was added which had, in the same manner as in Example 1, A positive electrode active material for sodium ion battery (NaFe _0.28 Mn _0.7 Mg _0.02 PO ₄ ) was obtained.

[Example 5]
In the same manner as in Example 4, except that 0.18 g (0.5 mmol) of Zr (SO ₄ ) ₂ .4H ₂ O was added instead of MgSO ₄ · 7H ₂ O, a positive electrode active material for sodium ion battery (NaFe _0.28 Mn _0.7 Zr _0.01 PO ₄ ) was obtained.

[Example 6]
Instead of MgSO ₄ .7H ₂ O, a positive electrode active material for sodium ion battery (NaFe _0.28 Mn _{0. 0} ) was added in the same manner as in Example 4 except that 0.054 g (0.33 mmol) of H ₂ MoO ₄ was added _{. 7} Mo _0.007 PO ₄ ) was obtained.

[Comparative Example 1]
The FeSO ₄ · 7H ₂ O and 13.90 g (50 mmol), except for not adding MgSO ₄ · 7H ₂ O, in the same manner as in Example 1 to obtain a positive electrode active material for sodium ion batteries (NaFePO ₄₎ .

[Comparative Example 2]
The FeSO ₄ · 7H ₂ O and _{4.17g (15mmol), MgSO 4 ·} 7H 2 except that O was not added, in the same manner as in Example 4, the positive electrode active material for sodium ion battery _(NaFe 0.3 Mn _{0 .7} PO ₄ ) was obtained.

<Evaluation of charge / discharge characteristics>
The positive electrode of the sodium ion secondary battery was produced using the positive electrode active material for sodium ion batteries obtained in Examples 1-6 and Comparative Examples 1-2. Specifically, the obtained positive electrode active material for sodium ion battery, ketjen black (conducting agent), and polyvinylidene fluoride (binding agent) were mixed at a weight ratio of 75: 20: 5, and N -Methyl-2-pyrrolidone was added and sufficiently kneaded to prepare a positive electrode slurry. The positive electrode slurry was applied to a current collector made of an aluminum foil having a thickness of 20 μm using a coating machine, and vacuum dried at 80 ° C. for 12 hours. Thereafter, it was punched into a disk shape of φ14 mm and pressed at 16 MPa for 2 minutes using a hand press to obtain a positive electrode.

Next, a coin-type sodium ion secondary battery was constructed using the positive electrode. As the negative electrode, a Na foil punched to φ15 mm was used. As the electrolytic solution, a solution obtained by dissolving NaPF ₆ at a concentration of 1 mol / L in a mixed solvent in which ethylene carbonate and diethyl carbonate were mixed at a volume ratio of 1: 1 was used. As the separator, a known one such as a polymer porous film such as polypropylene was used. These battery components were assembled and housed in a conventional manner in an atmosphere with a dew point of −50 ° C. or lower to produce a coin-type sodium secondary battery (CR-2032).
A charge / discharge test was performed using the manufactured sodium secondary battery to determine the discharge capacity. The charging conditions at this time are constant current and constant voltage charging with a current of 0.1 CA (17 mAh / g) and a voltage of 4.2 V, and the discharging conditions are constant current discharging with a current of 0.1 CA (17 mAh / g) and a final voltage of 2.0 V. It was. All temperatures were 30 ° C.
The results are shown in Table 1.

  From the above results, it can be seen that the positive electrode active material for sodium ion battery of the example can secure an excellent discharge capacity in the obtained sodium ion battery as compared with the positive electrode active material for sodium ion battery of the comparative example.

Claims (11)

The following formula (A) which is a hydrothermal reaction product :
NaFe _a Mn _b M _c PO ₄ (A)
(In the formula (A), M represents Mg, Ca, Sr, Y, Zr, Mo, Ba, Pb, Bi, La, Ce, Nd, or Gd. A, b, and c are 0 <a, 0 ≦ b <1, 0 <c ≦ 0.2, 2a + 2b + (M valence) × c = 2, and a = 1−b− (M valence) × c ÷ 2 is satisfied.)
The positive electrode active material for sodium ion batteries containing the olivine type sodium iron phosphate compound represented by these.   The positive electrode active material for sodium ion batteries according to claim 1, wherein carbon is supported on an olivine-type sodium iron phosphate compound.   The sodium ion battery containing the positive electrode active material for sodium ion batteries of Claim 1 or 2. Sodium compound, iron compound, metal (M) compound (M represents Mg, Ca, Sr, Y, Zr, Mo, Ba, Pb, Bi, La, Ce, Nd or Gd), and phosphate compound to nitrogen Step (I) for mixing in an atmosphere to obtain a mixture, and step (II) for drying the resulting mixture after subjecting it to a hydrothermal reaction.
The manufacturing method of the positive electrode active material for sodium ion batteries of any one of Claims 1-3 provided with these.   The manufacturing method of the positive electrode active material for sodium ion batteries of Claim 4 whose dissolved oxygen concentration in the liquid mixture obtained at process (I) is 0.5 mg / L or less.   6. The sodium ion battery according to claim 4, wherein in the mixed solution obtained in step (I), Na is 1.0 to 3.3 mol with respect to a total of 1 mol of metal atoms including Fe and M. 7. A method for producing a positive electrode active material.   The manufacturing method of the positive electrode active material for sodium ion batteries of any one of Claims 4-6 in which process (I) includes the process of adding sodium sulfite further.   The manufacturing method of the positive electrode active material for sodium ion batteries of any one of Claims 4-7 whose pressure of process (II) is 0.3-1.5 MPa.   In the liquid mixture obtained by process (I), phosphorus is 1.0-1.1 mol with respect to a total of 1 mol of the metal atom containing Fe and M, The any one of Claims 4-8. Manufacturing method of positive electrode active material for sodium ion battery. The step (I) further includes a step (I-1) of adding a water-soluble carbon material to the mixed solution X ¹ or the mixed solution X ² , for the sodium ion battery according to claim 4. A method for producing a positive electrode active material.   The step (II) includes a step (II-1) of adding a water-soluble carbon material and water and spray-drying after passing through the drying treatment, or a step (II-2) of adding carbon black. The manufacturing method of the positive electrode active material for sodium ion batteries of any one of claim | item 4 -10.