JP2017199688A - Negative electrode active material for sodium ion secondary battery, and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a negative electrode active material for an electric power storage device which has a high discharge capacity-keeping ratio, and a method for manufacturing the negative electrode active material.SOLUTION: A negative electrode active material for an electric power storage device comprises TiO, NaO and a net-forming oxide.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a negative electrode active material for an electricity storage device used for portable electronic devices, electric vehicles and the like, and a method for producing the same.

  In recent years, with the spread of portable personal computers and mobile phones, there is an increasing demand for higher capacity and smaller size of power storage devices such as lithium ion secondary batteries. If the capacity of the electricity storage device is increased, it will be easy to reduce the size of the battery. Therefore, there is an urgent need to develop the capacity of the electricity storage device.

  Carbon materials such as graphitic carbon materials and hard carbon are generally used for negative electrode active materials for power storage devices such as lithium ion secondary batteries and sodium ion secondary batteries.

Furthermore, layered sodium titanium oxide Na ₂ Ti ₃ O ₇ has been proposed as a negative electrode active material capable of inserting and extracting lithium ions and sodium ions (see Patent Document 1).

JP 2007-234233 A

However, the layered sodium titanium oxide Na ₂ Ti ₃ O ₇ negative electrode active material has a problem that the discharge capacity retention rate (cycle characteristics) is low.

  Therefore, the subject of this invention is providing the negative electrode active material for electrical storage devices with a high discharge capacity maintenance factor, and its manufacturing method.

The negative electrode active material for an electricity storage device of the present invention is characterized by containing TiO ₂ , Na ₂ O, and a network forming oxide.

The network forming oxide is preferably B ₂ O ₃ .

  The negative electrode active material for an electricity storage device of the present invention preferably contains a monoclinic crystal containing Na, Ti and O.

Further, the monoclinic crystal is preferably a crystal belonging to the space group P2 ₁ / m.

  The negative electrode active material for an electricity storage device of the present invention preferably contains an amorphous phase.

The negative electrode active material for an electricity storage device of the present invention contains TiO ₂ 10 to 75%, Na ₂ O 10 to 50%, and network-forming oxide 0.1 to 50% in terms of oxide-based mol%. preferable.

_Further, it preferably contains _{ZnO + SnO + MnO 2 + Nb} 2 O 5 + Sb 2 O 3 + Bi 2 O 3 0.1~25%.

  The negative electrode active material for an electricity storage device of the present invention is in the form of particles, and the particle surface is preferably coated with conductive carbon.

The method for producing a negative electrode active material for an electricity storage device of the present invention includes (1) a step of preparing a batch containing TiO ₂ , Na ₂ O, and a network-forming oxide, and (2) a step of melting the batch to obtain molten glass. And (3) a step of cooling the molten glass to obtain a molten solidified product.

  Furthermore, (4) pulverizing the obtained molten solidified body to obtain a molten solidified powder, and (5) firing the molten solidified powder at 500 to 1000 ° C. to obtain a crystallized glass powder. preferable.

  Furthermore, in the step (5), it is preferable to add an organic compound or conductive carbon or both to the melt-solidified powder, and perform firing in an inert or reducing atmosphere.

  ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the negative electrode active material for electrical storage devices with a high discharge capacity maintenance factor, and its manufacturing method.

2 is an X-ray diffraction pattern of the negative electrode active material of Example 1. FIG.

The negative electrode active material for an electricity storage device of the present invention is characterized by containing TiO ₂ , Na ₂ O, and a network forming oxide.

TiO ₂ is a redox component that becomes a driving force for charging and discharging. The content of TiO ₂ is preferably 10 to 75%, more preferably 20 to 70%, still more preferably 30 to 65%, and particularly preferably 40 to 60%. When the content of TiO ₂ is too small, the discharge capacity of the negative electrode active material tends to decrease. On the other hand, when the content of TiO ₂ is too large, different types of crystals other than monoclinic crystals containing Na, Ti and O are likely to be precipitated, and the electrode potential of the negative electrode active material is increased.

Na ₂ O is a component that improves lithium ion and sodium ion conductivity. The content of Na ₂ O is preferably 10 to 50%, more preferably 15 to 45%, still more preferably 20 to 42%, and particularly preferably 25 to 40%. When the Na 2 _O content is too small, the discharge capacity is lowered in the negative electrode active material, high-speed charge-discharge characteristics tend to be lowered. On the other hand, when the content of Na 2 _O is too large, chemical durability tends to decrease.

The network-forming oxide is an oxide that can form a three-dimensional irregular network structure, that is, an amorphous phase, by itself, specifically, B ₂ O ₃ , SiO ₂ , P ₂ O. ₅ , GeO _{2 and the} like. The network-forming oxide has an effect of facilitating inclusion of an amorphous phase in the negative electrode active material and improving lithium ion and sodium ion conductivity. The content of the network-forming oxide is preferably 0.1 to 50%, more preferably 1 to 40%, further preferably 3 to 30%, and 5 to 20%. Particularly preferred. When there is too little content of a network formation oxide, lithium ion and sodium ion conductivity will fall easily. On the other hand, when there is too much content of network formation oxide, there exists a tendency for the discharge capacity of a negative electrode active material to fall.

The content of B ₂ O ₃ is preferably 0.1 to 50%, more preferably 1 to 40%, and particularly preferably 3 to 30%. If the content of B ₂ O ₃ is too small, a lithium ion and sodium ion conductivity tends to decrease. On the other hand, when the content of B ₂ O ₃ is too large, the chemical durability tends to decrease.

The content of SiO ₂ is preferably 0 to 40%, more preferably 1 to 30%, and particularly preferably 3 to 20%. When the content of SiO ₂ is too large, the discharge capacity of the negative electrode active material tends to decrease.

The content of P ₂ O ₅ is preferably 0 to 25%, more preferably 1 to 20%, and particularly preferably 3 to 15%. When the content of P ₂ O ₅ is too small, it reduces the lithium ion and sodium ion conductivity, charge and discharge characteristics tends to decrease rapidly. On the other hand, when the content of P ₂ O ₅ is too large, chemical durability tends to decrease.

The content of GeO ₂ is preferably 0 to 40%, more preferably 1 to 30%, and particularly preferably 3 to 20%. When the content of GeO ₂ is too large, the discharge capacity of the negative electrode active material tends to decrease.

Moreover, the negative electrode active material for an electricity storage device of the present invention may contain ZnO, SnO, MnO ₂ , Nb ₂ O ₅ , Sb ₂ O ₃ or Bi ₂ O ₃ . By containing these components, electron conductivity becomes high and high-speed charge / discharge characteristics are easily improved. The total content of the above components is preferably 0.1 to 25%, particularly preferably 0.2 to 10%. If the total content of the above components is too large, different crystals that do not participate in charge / discharge of the electricity storage device are generated, and the discharge capacity of the negative electrode active material tends to decrease.

The negative electrode active material for an electricity storage device of the present invention preferably contains a monoclinic crystal containing Na, Ti and O. By containing a monoclinic crystal containing Na, Ti and O, the electrode potential of the negative electrode active material tends to decrease and the discharge capacity tends to increase. The monoclinic crystal containing Na, Ti and O is preferably a crystal belonging to the space group P2 ₁ / m, and has the general formula Na _x Ti _y O _{(x / 2 + 2y)} (1 ≦ x ≦ 3, 2 ≦ A crystal represented by y ≦ 4) is more preferable, and a Na ₂ Ti ₃ O ₇ crystal is particularly preferable.

  The negative electrode active material for an electricity storage device of the present invention preferably contains an amorphous phase. By including an amorphous phase, the lithium ion and sodium ion conductivity of the negative electrode active material is improved, and thus high-speed charge / discharge characteristics are easily improved.

  Furthermore, the negative electrode active material for an electricity storage device of the present invention is preferably made of crystallized glass. With crystallized glass, both the monoclinic crystal containing Na, Ti and O and the amorphous phase can be easily combined, improving both the discharge capacity and high-speed charge / discharge characteristics of the negative electrode active material. Tend to.

  The crystallinity of the monoclinic crystal containing Na, Ti and O in the negative electrode active material is preferably 30% by mass or more, 40% by mass or more, and particularly preferably 50% by mass or more. When the crystallinity of the monoclinic crystal containing Na, Ti and O is too low, the discharge capacity tends to decrease. In addition, although it does not specifically limit about an upper limit, In reality, it is 99 mass% or less.

  The crystallinity of the monoclinic crystal containing Na, Ti and O is the same as that of the crystalline diffraction line in the diffraction line profile of 10-60 ° in 2θ value obtained by powder X-ray diffraction measurement using CuKα ray. It is calculated | required by carrying out peak separation to a crystalline halo. Specifically, the integrated intensity obtained by peak-separating a broad diffraction line (amorphous halo) at 10 to 45 ° from the total scattering curve obtained by subtracting the background from the diffraction line profile is Ia, 10 Integral intensity obtained from peak separation of crystalline diffraction lines derived from monoclinic crystals containing Na, Ti and O detected at ˜60 ° is Ic, and integrated intensity obtained from other crystalline diffraction lines In the case where the total sum of I is Io, the crystal content Xc is obtained from the following equation.

    Xc = [Ic / (Ic + Ia + Io)] × 100 (%)

  The smaller the crystallite size of the monoclinic crystal containing Na, Ti and O, the smaller the average particle diameter of the negative electrode active material particles can be, and the electrical conductivity can be improved. Specifically, the crystallite size of the monoclinic crystal containing Na, Ti and O is preferably 100 nm or less, particularly preferably 80 nm or less. The lower limit is not particularly limited, but is actually 1 nm or more, and further 10 nm or more. The crystallite size is determined according to Scherrer's equation from the analysis result of powder X-ray diffraction.

  Furthermore, it is preferable that the negative electrode active material for an electricity storage device of the present invention is in the form of particles and the particle surfaces are coated with conductive carbon. When the particle surface is coated with conductive carbon, the electron conductivity is increased and the high-speed charge / discharge characteristics are easily improved.

  The average particle diameter of the negative electrode active material is preferably 0.1 to 20 μm, 0.3 to 15 μm, particularly preferably 0.5 to 10 μm. When the average particle diameter of the negative electrode active material is too small, the cohesive force between the negative electrode active material particles becomes strong and is difficult to disperse when formed into a paste. As a result, the internal resistance of the battery increases and the discharge voltage tends to decrease. In addition, the electrode density tends to decrease and the discharge capacity per unit volume of the battery tends to decrease. On the other hand, if the average particle diameter of the negative electrode active material is too large, the specific surface area of the negative electrode active material tends to be small, and lithium ion and sodium ion conductivity at the interface between the negative electrode active material and the electrolyte tends to decrease. Moreover, there exists a tendency to be inferior to the surface smoothness of an electrode.

  In addition, in this invention, an average particle diameter means D50 (volume basis average particle diameter), and shall mean the value measured by the laser diffraction scattering method.

  The negative electrode active material for an electricity storage device of the present invention has a carbon content of 0.01 to 20% by mass, 0.05 to 20% by mass, 1 to 20% by mass, 2 to 15% by mass, particularly 3 to 12% by mass. It is preferable that When the carbon content is too small, the coating with the carbon-containing layer becomes insufficient, and the electron conductivity tends to be inferior. On the other hand, when the carbon content is too large, the content of the negative electrode active material particles is relatively small, and the discharge capacity per unit mass of the negative electrode active material tends to be small.

Negative electrode active material for an electricity storage device of the present invention, the ratio of the peak intensity D of 1300～1400Cm ^-1 to the peak intensity G of 1550～1650Cm ^-1 in Raman spectroscopy (D / G) is 1 or less, especially 0.8 or less And the ratio (F / G) of the peak intensity F of 800 to 1100 cm ⁻¹ with respect to the peak intensity G is preferably 0.5 or less, particularly preferably 0.1 or less. When these peak intensity ratios satisfy the above range, the electronic conductivity of the negative electrode active material tends to increase.

The method for producing a negative electrode active material for an electricity storage device of the present invention includes (1) a step of preparing a batch containing TiO ₂ , Na ₂ O, and a network-forming oxide, and (2) a step of melting the batch to obtain molten glass. And (3) a step of cooling the molten glass to obtain a molten solidified product. By producing the negative electrode active material by such a melting method, it is easy to obtain a negative electrode active material in which each component is uniformly dispersed.

  What is necessary is just to adjust a melting temperature suitably so that a raw material batch may be fuse | melted uniformly. Specifically, it is preferably 700 ° C. or higher, particularly 900 ° C. or higher. Although an upper limit is not specifically limited, Since it will lead to an energy loss when too high, it is preferable that it is 1500 degrees C or less, especially 1400 degrees C or less.

  In addition to the steps described above, a sol-gel process, a chemical vapor synthesis process such as spraying a solution mist into a flame, a mechanochemical process, and the like can also be applied as a step for obtaining a melt-solidified body.

  Furthermore, the method for producing a negative electrode active material for an electricity storage device of the present invention includes (4) a step of pulverizing the obtained molten solidified body to obtain a molten solidified powder, and (5) 500 to 1000 ° C. of the molten solidified powder. It is preferable to include a step of baking to obtain crystallized glass powder.

  A method for pulverizing the melt-solidified body is not particularly limited, and a general pulverizing apparatus such as a ball mill, a bead mill, or an attritor can be used.

  The smaller the average particle size of the melt-solidified powder, the larger the specific surface area of the negative electrode active material as a whole, which is preferable because it facilitates the exchange of ions and electrons.

  The heat treatment temperature of the melt-solidified powder is not particularly limited because it varies depending on the composition of the melt-solidified body. The lower limit of the heat treatment temperature is preferably 500 ° C, 550 ° C, particularly 600 ° C or higher. If the heat treatment temperature is too low, precipitation of monoclinic crystals containing Na, Ti and O becomes insufficient, and the discharge capacity may be reduced. On the other hand, the upper limit of the heat treatment temperature is preferably 1000 ° C., 950 ° C., particularly 900 ° C. If the heat treatment temperature is too high, monoclinic crystals containing Na, Ti and O may be dissolved, which is not preferable.

  The heat treatment time is appropriately adjusted so that precipitation of monoclinic crystals containing Na, Ti and O sufficiently proceeds. Specifically, it is preferably 0.5 to 20 hours, 1 to 15 hours, particularly 8 to 12 hours.

  Furthermore, in the step (5), it is preferable to add an organic compound or conductive carbon or both to the melt-solidified powder, and perform firing in an inert or reducing atmosphere. Thereby, the negative electrode active material particle surface can be coat | covered with a carbon containing layer.

  Examples of the conductive carbon include graphite, acetylene black, and amorphous carbon. Note that it is preferable that amorphous carbon does not substantially detect a C—O bond peak or a C—H bond peak that causes a decrease in conductivity of the negative electrode active material in the FT-IR analysis. Examples of the organic compound include carboxylic acids such as aliphatic carboxylic acids and aromatic carboxylic acids, glucose and organic binders, surfactants, and the like.

  The amount of the organic compound and / or conductive carbon added is preferably 0.01 to 50 parts by mass, and 0.1 to 50 parts by mass with respect to 100 parts by mass of the precursor glass powder. More preferably, it is 1-30 mass parts, More preferably, it is 5-20 mass parts. When the addition amount of the organic compound and / or the conductive carbon is too small, it becomes difficult to sufficiently cover the surface of the negative electrode active material particles with the carbon-containing layer. When the addition amount of the organic compound and / or the conductive carbon is too large, the thickness of the carbon-containing layer is increased, the movement of lithium ions and sodium ions is hindered, and the discharge capacity tends to decrease.

  The negative electrode for an electricity storage device of the present invention is a slurry obtained by adding a conductive additive and a binder to the negative electrode active material described above, and suspending them in a solvent such as water or N-methylpyrrolidone. Is applied to a current collector such as an aluminum foil or a copper foil, dried and pressed to form a strip.

  A conductive support agent is a component added in order to achieve rapid charging / discharging. Specific examples include highly conductive carbon black such as acetylene black and ketjen black, graphite, coke and the like. Among them, it is preferable to use highly conductive carbon black that exhibits excellent conductivity when added in a very small amount.

  Examples of the binder include thermoplastic linear polymers such as polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), fluorine-based rubber, and styrene-butanediene rubber (SBR); thermosetting polyimide, polyamide Thermosetting resins such as imide, polyamide, phenolic resin, epoxy resin, urea resin, melamine resin, unsaturated polyester resin, polyurethane; carboxymethylcellulose (including carboxymethylcellulose salts such as carboxymethylcellulose sodium; the same shall apply hereinafter), hydroxypropylmethylcellulose , Cellulose derivatives such as hydroxypropyl cellulose, hydroxyethyl cellulose, ethyl cellulose and hydroxymethyl cellulose, polyvinyl alcohol, polyacrylamide, polyvinyl pyro It includes pyrrolidone and water-soluble polymers of the copolymers.

  The compounding ratio of the negative electrode active material, the conductive assistant and the binder is preferably in the range of 70 to 95% by weight of the negative electrode active material, 3 to 20% by weight of the conductive assistant and 2 to 20% by weight of the binder.

  As the current collector, for example, an aluminum foil, an aluminum alloy foil, or a copper foil can be used. Examples of the aluminum alloy include alloys made of aluminum and elements such as magnesium, zinc, and silicon.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to this Example.

The negative electrode active materials of Examples 1 and 2 were produced as follows. Sodium carbonate (Na ₂ CO ₃ ), titanium oxide (TiO ₂ ), and boric anhydride (B ₂ O ₃ ) are used as raw materials, and raw material powders are prepared so as to have the composition shown in Table 1, at 1300 ° C. Melting was performed in an air atmosphere for 1 hour. Then, molten glass was poured into a pair of rolls, and a molten solidified body was produced by forming into a film shape while rapidly cooling.

  The obtained melt-solidified product was pulverized with a ball mill for 20 hours, and air classified to obtain a melt-solidified powder having an average particle size of 2 μm.

  The obtained melt-solidified powder was heat-treated at 800 ° C. for 1 hour in an air atmosphere to obtain a negative electrode active material. When the powder X-ray diffraction pattern was confirmed, diffraction lines derived from the crystals described in Table 1 were confirmed. The X-ray diffraction pattern of the negative electrode active material of Example 1 is shown in FIG.

The negative electrode active material of Example 3 was produced as follows. Sodium carbonate (Na ₂ CO ₃ ), titanium oxide (TiO ₂ ), and boric anhydride (B ₂ O ₃ ) are used as raw materials, and raw material powders are prepared so as to have the composition shown in Table 1, at 1300 ° C. Melting was performed in an air atmosphere for 1 hour. Then, molten glass was poured into a pair of rolls, and a molten solidified body was produced by forming into a film shape while rapidly cooling.

  The obtained melt-solidified product was pulverized with a ball mill for 20 hours and air classified to obtain a negative electrode active material having an average particle size of 2 μm. When the powder X-ray diffraction pattern was confirmed, the diffraction line derived from a crystal | crystallization was not confirmed but it was amorphous.

The negative electrode active material of Comparative Example 1 was produced as follows. Sodium carbonate (Na ₂ CO ₃ ) and titanium oxide (TiO ₂ ) are used as raw materials, and raw material powders are prepared so as to have the composition shown in Table 1, pulverized and mixed by a ball mill, and then pelletized. The solid phase reaction was carried out at 800 ° C. for 20 hours. Then, the negative electrode active material was obtained by performing each process of the grinding | pulverization by a ball mill, pelletization, and solid-phase reaction for 20 hours at 800 degreeC in air | atmosphere again. When the powder X-ray diffraction pattern was confirmed, diffraction lines derived from the crystals described in Table 1 were confirmed.

Weigh PVDF as a binder and Ketjen black as a conductive additive, and negative electrode active material: binder: conductive auxiliary = 80: 15: 5 (mass ratio) with respect to the negative electrode active material for the electricity storage device. These were dispersed in N-methylpyrrolidone (NMP), and then sufficiently stirred with a rotation / revolution mixer to form a slurry. Next, using a doctor blade with a gap of 100 μm, the obtained slurry was coated on a copper foil having a thickness of 20 μm as a negative electrode current collector, dried at 80 ° C. with a dryer, and then between a pair of rotating rollers. The electrode sheet was obtained by pressing at 1 t / cm ² . The electrode sheet was punched to a diameter of 11 mm with an electrode punching machine and dried at 140 ° C. for 6 hours to obtain a circular working electrode.

Next, a separator made of a polypropylene porous film having a diameter of 16 mm (Hoechst) was placed on the lower lid of the coin cell, and the obtained working electrode was placed with the copper foil surface facing down and dried under reduced pressure at 60 ° C. for 8 hours. Celagard's Celgard # 2400) and metallic sodium as a counter electrode were laminated to produce a sodium ion secondary battery. As the electrolytic solution, 1M NaPF ₆ solution / EC (ethylene carbonate): DEC (diethyl carbonate) = 1: 1 (volume ratio) was used. The test battery was assembled in an environment with a dew point temperature of −70 ° C. or lower.

  A charge / discharge test was performed at 30 ° C. using the obtained battery, and a discharge capacity and a discharge capacity retention rate were measured. The results are shown in Table 1.

  In the charge / discharge test, charging (occluding sodium ions in the negative electrode active material) is performed by CC (constant current) charging from 2 V to 0 V, and discharging (release of sodium ions from the negative electrode active material) is 0 V. To 2 V by CC discharge. The C rate was 0.1C. The discharge capacity maintenance rate in a sodium ion secondary battery refers to the ratio of the discharge capacity at the 20th cycle to the initial discharge capacity.

In addition, a separator and a counter electrode made of a polypropylene porous film having a diameter of 16 mm, which was placed on the lower lid of the coin cell with the obtained working electrode facing the copper foil surface and dried under reduced pressure at 60 ° C. for 8 hours. A certain lithium metal was laminated to produce a lithium ion secondary battery. As the electrolytic solution, 1M LiPF ₆ solution / EC: DEC = 1: 1 (volume ratio) was used. The test battery was assembled in an environment with a dew point temperature of −40 ° C. or lower.

  A charge / discharge test was performed at 30 ° C. using the obtained battery, and a discharge capacity and a discharge capacity retention rate were measured. The results are shown in Table 1.

  In the charge / discharge test, charging (occlusion of lithium ions into the negative electrode active material) is performed by CC (constant current) charging from 2.5 V to 1.2 V, and discharging (release of sodium ions from the negative electrode active material). ) Was performed by CC discharge from 1.2V to 2.5V. The C rate was 0.1C. The discharge capacity maintenance rate in a lithium ion secondary battery refers to the ratio of the discharge capacity at the 10th cycle to the initial discharge capacity.

As described above, the negative electrode active material produced in Example 1 to 3, for containing _B 2 _{O 3} is a network forming oxide, the discharge capacity in the sodium ion secondary battery as high as 87～122MAhg ^-1 Also, the discharge capacity maintenance rate was as high as 72 to 92%. Moreover, the discharge capacity in a lithium ion secondary battery was 48-51 mAhg- ¹ , and the discharge capacity maintenance factor was as high as 96-98%. On the other hand, since the negative electrode active material produced in Comparative Example 1 did not contain B ₂ O ₃ , the discharge capacity in the sodium ion secondary battery was as high as 112 mAhg ⁻¹ , but the discharge capacity maintenance rate was as low as 25%. . Moreover, the discharge capacity | capacitance in a lithium ion secondary battery was 45 mAhg- ¹ , the discharge capacity maintenance factor was 75%, and all were low.

Claims (9)

A negative electrode for a sodium ion secondary battery characterized by containing 10 to 75% of TiO ₂ , 10 to 50% of Na ₂ O, and 0.1 to 50% of a network forming oxide in terms of mol% in terms of oxide. A negative electrode active material for a sodium ion secondary battery, which is an active material, wherein the network-forming oxide is B ₂ O ₃ , SiO ₂ , P ₂ O ₅ or GeO ₂ .   2. The negative electrode active material for a sodium ion secondary battery according to claim 1, comprising a monoclinic crystal containing Na, Ti and O. 3. The negative electrode active material for a sodium ion secondary battery according to claim 2, wherein the monoclinic crystal is a crystal belonging to a space group P2 ₁ / m.   The negative electrode active material for sodium ion secondary batteries according to claim 1, comprising an amorphous phase. _{5. The} negative electrode active material for a sodium ion secondary battery according to claim 1, further comprising 0.1 to 25% of ZnO + SnO + MnO ₂ + Nb ₂ O ₅ + Sb ₂ O ₃ + Bi ₂ O _3. .   The negative electrode active material for a sodium ion secondary battery according to any one of claims 1 to 5, wherein the negative electrode active material is in the form of particles and the particle surface is coated with conductive carbon. (1) a step of preparing a batch containing TiO ₂ , Na ₂ O, and a network-forming oxide, (2) a step of melting the batch to obtain a molten glass, and (3) cooling the molten glass to obtain a molten solidified body. The manufacturing method of the negative electrode active material for sodium ion secondary batteries characterized by including the process to obtain.   And (4) pulverizing the obtained melt-solidified material to obtain a melt-solidified powder, and (5) firing the melt-solidified powder at 500 to 1000 ° C. to obtain a crystallized glass powder. The manufacturing method of the negative electrode active material for sodium ion secondary batteries of Claim 7 characterized by the above-mentioned.   9. The sodium ion secondary according to claim 8, wherein in the step (5), an organic compound and / or conductive carbon is added to the melt-solidified powder, and firing is performed in an inert or reducing atmosphere. The manufacturing method of the negative electrode active material for batteries.