JP2011048951A - Method of manufacturing active material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing an active material capable of improving the discharge capacity of a lithium ion secondary battery. <P>SOLUTION: The method of manufacturing the active material includes a hydrothermal synthesis step of heating a mixture containing a lithium source, a phosphate source, a vanadium source, water and a reducing agent to 200-300°C under pressure, and adjusts the ratio [P]/[V] of the number of moles [P] of phosphorous element contained in the mixture before heating to the number of moles [V] of vanadium element contained in the mixture before heating to 0.9-1.5. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for producing an active material.

Conventionally, a layered compound such as LiCoO ₂ or LiNi _1/3 Mn _1/3 Co _1/3 O ₂ or a spinel compound such as LiMn ₂ O ₄ has been used as a positive electrode material (positive electrode active material) of a lithium ion secondary battery. It was. In recent years, compounds having an olivine type structure typified by LiFePO ₄ have attracted attention. It is known that a positive electrode material having an olivine structure has high thermal stability at high temperatures and high safety. However, the lithium ion secondary battery using LiFePO ₄ has a drawback that its charge / discharge voltage is as low as about 3.5 V and the energy density is low. Therefore, as a phosphate-based positive electrode material capable of realizing a high charge-discharge voltage, such as LiCoPO4 and LiNiPO ₄ it has been proposed. However, the present situation is that a sufficient capacity is not obtained even in lithium ion secondary batteries using these positive electrode materials. LiVOPO ₄ is known as a compound that can realize a charge / discharge voltage of 4 V class among phosphoric acid positive electrode materials. However, even in a lithium ion secondary battery using LiVOPO ₄ , sufficient reversible capacity and rate characteristics are not obtained. Said positive electrode material is described in the following patent documents 1, 2, and the following nonpatent literatures 1-4, for example. Hereinafter, in some cases, a lithium ion secondary battery is referred to as a “battery”.

JP 2003-68304 A JP 2004-303527 A

J. et al. Solid State Chem. , 95, 352 (1991) N. Dupre et al. , Solid State Ionics, 140, pp. 209-221 (2001) N. Dupre et al. , J .; Power Sources, 97-98, pp. 532-534 (2001) J. et al. Baker et al. J. et al. Electrochem. Soc. , 151, A796 (2004)

  This invention is made | formed in view of the subject which the said prior art has, and aims at providing the manufacturing method of the active material which can improve the discharge capacity of a lithium ion secondary battery.

  In order to achieve the above object, the method for producing an active material according to the present invention is a hydrothermal method in which a mixture containing a lithium source, a phosphate source, a vanadium source, water and a reducing agent is heated to 200 to 300 ° C. under pressure. A synthesis process is provided. In the present invention, in the hydrothermal synthesis step, the ratio [P] / [ratio of the number of moles of phosphorus element [P] contained in the mixture before heating to the number of moles [V] of vanadium element contained in the mixture before heating. V] is adjusted to 0.9 to 1.5.

According to the present invention, LiVOPO ₄ can be obtained. And in the lithium ion secondary battery provided with LiVOPO ₄ obtained by the present invention as a positive electrode active material, the discharge capacity can be improved as compared with the lithium ion secondary battery using LiVOPO ₄ obtained by the conventional manufacturing method. It becomes possible.

  In the present invention, the ratio [Li] / [V] of the number of moles of lithium element [Li] and [V] contained in the mixture before heating may be adjusted to 0.9 to 1.5. Even when [Li] / [V] is larger than 1.5, the effects of the present invention can be obtained.

In the present invention, the lithium source is preferably at least one selected from the group consisting of LiOH, Li ₂ CO ₃ , CH ₃ COOLi, and Li ₃ PO ₄ . In the lithium ion secondary battery provided with LiVOPO ₄ obtained using these lithium sources, the discharge capacity and rate characteristics are compared with the lithium ion secondary battery provided with LiVOPO ₄ obtained using Li ₂ SO ₄ as the lithium source. Will improve.

  The present invention preferably includes a heat treatment step of further heating the mixture after the hydrothermal synthesis step. Thereby, the rate characteristic of a lithium ion secondary battery improves.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the active material which can improve the discharge capacity of a lithium ion secondary battery can be provided.

(Method for producing active material)
Below, the manufacturing method of the active material which concerns on one Embodiment of this invention is demonstrated.

<Hydrothermal synthesis process>
In the hydrothermal synthesis step, first, the above-described lithium source, phosphate source, vanadium source, water, and reducing agent are put into a reaction vessel (for example, an autoclave) having a function of heating and pressurizing the inside. A mixture (aqueous solution) in which is dispersed is prepared. In preparing the mixture, for example, first, a mixture of a phosphate source, a vanadium source, water and a reducing agent may be refluxed, and then a lithium source may be added thereto. By this reflux, a complex of a phosphate source and a vanadium source can be formed.

As the lithium source, at least one selected from the group consisting of LiNO ₃ , Li ₂ CO ₃ , LiOH, LiCl, Li ₂ SO ₄ and CH ₃ COOLi can be used.

The lithium source is preferably at least one selected from the group consisting of LiOH, Li ₂ CO ₃ , CH ₃ COOLi, and Li ₃ PO ₄ . Thus, as compared with the case of using the Li ₂ SO _4, thereby improving the discharge capacity and rate characteristics of a battery.

As the phosphoric acid source, at least one selected from the group consisting of H ₃ PO ₄ , NH ₄ H ₂ PO ₄ , (NH ₄ ) ₂ HPO ₄ and Li ₃ PO ₄ can be used.

As the vanadium source, at least one selected from the group consisting of V ₂ O ₅ and NH ₄ VO ₃ can be used.

  Two or more lithium sources, two or more phosphoric acid sources, or two or more vanadium sources may be used in combination.

As the reducing agent, for example, at least one of hydrazine (NH ₂ NH ₂ .H ₂ O) or hydrogen peroxide (H ₂ O ₂ ) can be used.

In the hydrothermal synthesis step, before heating the mixture under pressure, the ratio [P] / [V of the number of moles of phosphorus element [P] contained in the mixture to the number of moles [V] of vanadium element contained in the mixture. ] Is adjusted to 0.9 to 1.5. In a battery using LiVOPO ₄ obtained when [P] / [V] is adjusted outside the numerical range of 0.9 to 1.5, it is difficult to improve the discharge capacity. [P] / [V] may be adjusted by the blending ratio of the phosphate source and the vanadium source contained in the mixture.

  In the hydrothermal synthesis step, before heating the mixture under pressure, the ratio [Li] / [V] of the number of moles of lithium element contained in the mixture [Li] and [V] is set to 0.9 to 1.5. You may adjust to. Even when [Li] / [V] is larger than 1.5, the effects of the present invention can be obtained. [Li] / [V] may be adjusted by the blending ratio of the lithium source and the vanadium source contained in the mixture.

In the conventional LiVOPO ₄ production method, in order to suppress the occurrence of Li deficiency in the obtained LiVOPO ₄ , [Li] / [V] is a value larger than 1 which is the stoichiometric ratio of LiVOPO ₄ ( For example, it was necessary to adjust to 9). On the other hand, in this embodiment, even when [Li] / [V] is adjusted to 0.9 to 1.5, which is close to the stoichiometric ratio of LiVOPO ₄ , there is no defect of Li and the crystalline High LiVOPO ₄ can be obtained.

In the hydrothermal synthesis step, it is preferable to adjust the pH of the mixture to 7.5 or less before heating the mixture under pressure. Thereby, the β-type crystal phase of LiVOPO ₄ is likely to be generated, and the discharge capacity tends to be remarkably improved.

  Various methods can be adopted as a method for adjusting the pH of the mixture. For example, an acidic reagent or a basic reagent is added to the mixture. As the acidic reagent, nitric acid, hydrochloric acid, sulfuric acid or the like may be used. For example, an aqueous ammonia solution or the like may be used as the basic reagent. In addition, pH of a mixture changes according to the quantity of a mixture, the kind or compounding ratio of a lithium source, a phosphate source, and a vanadium source. Therefore, the addition amount of the acidic reagent or basic reagent may be appropriately adjusted according to the amount of the mixture, the types of lithium source, phosphoric acid source and vanadium source and the mixing ratio.

In the hydrothermal synthesis step, the hydrothermal reaction is allowed to proceed in the mixture by heating the mixture in the sealed reactor while applying pressure. Thus, LiVOPO ₄ is hydrothermally synthesized as an active material.

In the hydrothermal synthesis step, the mixture is heated to 200 to 300 ° C. under pressure. If the temperature of the mixture is too low, the formation of LiVOPO ₄ and crystal growth do not proceed sufficiently. As a result, the crystallinity of LiVOPO ₄ is lowered and the capacity density is reduced, so that it is difficult to improve the discharge capacity of the battery using LiVOPO ₄ . On the other hand, if the temperature of the mixture is too high, the crystal growth of LiVOPO ₄ proceeds excessively and the diffusibility of Li in the crystal decreases. Therefore, it becomes difficult to improve the discharge capacity of the battery using LiVOPO ₄ obtained. Moreover, when the temperature of a mixture is too high, high heat resistance is calculated | required by the reaction container, and the manufacturing cost of an active material will increase. By setting the temperature of the mixture within the above range, these tendencies can be suppressed.

The pressure applied to the mixture in the hydrothermal synthesis step is preferably 0.2 to 1 MPa. If the pressure applied to the mixture is too low, the crystallinity of LiVOPO ₄ finally obtained tends to be reduced, and the capacity density tends to decrease. If the pressure applied to the mixture is too high, the reaction vessel is required to have high pressure resistance, and the production cost of the active material tends to increase. By setting the pressure applied to the mixture within the above range, these tendencies can be suppressed.

<Heat treatment process>
In this embodiment, it is preferable to provide a heat treatment step for further heating the mixture after the hydrothermal synthesis step. By the heat treatment step, the reaction of the lithium source, the phosphate source, and the vanadium source that did not react in the hydrothermal synthesis step can be advanced, or the crystal growth of LiVOPO ₄ generated in the hydrothermal synthesis step can be promoted. As a result, the capacity density of LiVOPO ₄ is improved, and not only the discharge capacity of the battery using the same but also the rate characteristics are improved. In the present invention, since the mixture is heated at a sufficiently high temperature in the hydrothermal synthesis step, the effect of the present invention can be achieved without performing the heat treatment step after the hydrothermal synthesis step.

The heat treatment temperature of the mixture in the heat treatment step is preferably 400 to 700 ° C. When the heat treatment temperature is too low, the degree of crystal growth of LiVOPO ₄ tends to be small, and the degree of improvement in capacity density tends to be small. If the heat treatment temperature is too high, growth of the LiVOPO ₄ proceeds excessively, tend to particle size of LiVOPO ₄ is increased. As a result, the diffusion of lithium in the active material is slow, and the improvement in the capacity density of the active material tends to be small. By setting the heat treatment temperature within the above range, these tendencies can be suppressed.

  The heat treatment time of the mixture is preferably 3 to 20 hours. The heat treatment atmosphere of the mixture is preferably a nitrogen atmosphere, an argon atmosphere, or an air atmosphere.

In addition, you may pre-heat the mixture obtained at a hydrothermal synthesis process at about 60-150 degreeC for about 1 to 30 hours, before heating at a heat processing process. By preheating, the mixture becomes powder, and excess water and organic solvent are removed from the mixture. As a result, it is possible to prevent impurities from being taken into LiVOPO ₄ in the heat treatment step and to make the particle shape uniform.

LiVOPO ₄ obtained in the above-described embodiment is suitable as a positive electrode active material for a lithium ion secondary battery.

  A lithium ion secondary battery includes a power generation element including a plate-shaped negative electrode and a plate-shaped positive electrode facing each other, and a plate-shaped separator disposed adjacently between the negative electrode and the positive electrode, and lithium ions An electrolyte solution, a case for containing them in a sealed state, a negative electrode lead having one end electrically connected to the negative electrode and the other end protruding outside the case, and one end connected to the positive electrode And a positive electrode lead whose other end protrudes to the outside of the case.

  The negative electrode has a negative electrode current collector and a negative electrode active material layer formed on the negative electrode current collector. The positive electrode includes a positive electrode current collector and a positive electrode active material layer formed on the positive electrode current collector. The separator is located between the negative electrode active material layer and the positive electrode active material layer.

The positive electrode active material layer contains LiVOPO ₄ obtained by the manufacturing method described above.

In the battery including LiVOPO ₄ obtained by the manufacturing method according to the present embodiment as the positive electrode active material, the discharge capacity can be improved as compared with the battery using LiVOPO ₄ obtained by the conventional manufacturing method.

LiVOPO ₄ has a plurality of crystal structures such as triclinic crystal (α-type crystal) and orthorhombic crystal (β-type crystal), and is known to have different electrochemical characteristics depending on the crystal structure.

Since the LiVOPO ₄ β-type crystal has a linear and shorter ion conduction path than the α-type crystal, it has a characteristic of reversibly inserting and desorbing lithium ions (hereinafter, sometimes referred to as “reversible”). Excellent. Therefore, a battery using a LiVOPO ₄ β-type crystal as an active material has a large charge / discharge capacity and excellent rate characteristics as compared with a battery using an α-type crystal.

The present inventors think that LiVOPO ₄ obtained by the method for producing an active material according to the present embodiment is a single phase of β-type crystal, so that the discharge capacity of a battery using this is improved. In other words, in the method for producing an active material according to the present embodiment, it is considered that a β-type crystal of LiVOPO ₄ can be obtained with a higher yield than the conventional production method.

  As mentioned above, although suitable one Embodiment of the manufacturing method of the active material which concerns on this invention was described in detail, this invention is not limited to the said embodiment.

For example, in the hydrothermal synthesis step, carbon particles may be added to the mixture before heating. Thereby, at least a part of LiVOPO ₄ is generated on the surface of the carbon particles, and the LiVOPO ₄ can be supported on the carbon particles. As a result, it is possible to improve the electrical conductivity of the obtained active material. Examples of substances constituting the carbon particles include carbon black (graphite) such as acetylene black, activated carbon, hard carbon, and soft carbon.

The active material of the present invention can also be used as an electrode material for electrochemical devices other than lithium ion secondary batteries. As such an electrochemical element, other than lithium ion secondary batteries such as a metal lithium secondary battery (using the electrode containing LiVOPO ₄ obtained by the present invention as a cathode and using metal lithium as an anode) Examples include secondary batteries and electrochemical capacitors such as lithium capacitors. These electrochemical elements can be used for power sources such as self-propelled micromachines and IC cards, and distributed power sources arranged on or in a printed circuit board.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example.

Example 1
In the production of LiVOPO ₄ of Example 1, a mixed solution containing the following raw materials was prepared.

Lithium source: 8.48 g (0.20 mol) of LiOH.H ₂ O (molecular weight = 41.96, manufactured by Nacalai Tesque, special grade, purity 99% by weight).

Phosphoric acid source: 23.06 g (0.20 mol) of H ₃ PO ₄ (molecular weight = 98.00, manufactured by Kanto Chemical Co., Inc., deer grade 1, purity 85 wt%, manufactured by Nacalai Tesque Co., grade 1, purity: 85 wt. %).

Vanadium source: 18.37 g (0.10 mol) of V ₂ O ₅ (molecular weight = 181.88, manufactured by Nacalai Tesque, special grade, purity: 99% by weight).

  200 g of distilled water (manufactured by Nacalai Tesque, for HPLC (high performance liquid chromatography)). Separately, 30 g of distilled water was also used between the glass container and the autoclave.

Reducing agent: 2.58 g (0.05 mol) of NH ₂ NH ₂ .H ₂ O (molecular weight = 50.06, manufactured by Nacalai Tesque, special grade, purity: 98% by weight).

As apparent from the contents of the phosphoric acid source and the vanadium source, the ratio [P] of the number of moles of phosphorus element [P] contained in the mixed solution and the number of moles [V] of vanadium element contained in the mixed solution [P] ] / [V] was adjusted to 1. Further, as is clear from the contents of the above lithium source and vanadium source, the ratio [Li] / [V] of the number of moles [Li] and [V] of the lithium element contained in the mixed solution is adjusted to 1. did. Further, as apparent from the content of the lithium source and the amount of distilled water, the concentration of Li ^{+ in} the mixed solution was adjusted to 1.0 mol / L. Each amount of the raw materials is equivalent to a yield of about 33.78 g (0.2 mol) of LiVOPO ₄ when converted to LiVOPO ₄ (molecular weight: 168.85).

The above mixture was prepared by the following procedure. First, 23.06 g of H ₃ PO ₄ and 180 g of distilled water were placed in a 500 mL Meyer flask, and these were stirred with a magnetic stirrer. Then, after adding 18.37 g of V ₂ O ₅ to the flask and stirring was continued for about 2.5 hours, a yellow-orange suspension was obtained in the flask. While the suspension was vigorously stirred, 2.58 g of hydrazine monohydrate (NH ₂ NH ₂ .H ₂ O) was added dropwise to the suspension. When hydrazine monohydrate was added dropwise, the liquid phase of the suspension changed from yellow orange to dull green. In addition, since the suspension was vigorously stirred, foaming accompanying dropping was not confirmed. When the suspension was further stirred for 10 minutes, the suspension became a dull green fluid paste. The pH of this paste was 3. Stirring of the suspension was continued for about 60 minutes after adding hydrazine monohydrate. The liquid phase of the suspension was maintained in a mustard colored flowable paste. Subsequently, 8.48 g of LiOH.H ₂ O was added to the paste over about 10 minutes. The pH of the paste immediately after charging LiOH.H ₂ O was 7-8. 20 g of distilled water was added to this paste to obtain the above mixture. The pH of the obtained liquid mixture was 7.5.

  248.41 g of the mixed liquid containing 98.4% of the yield of 33.78 g expected at the time of charging the raw material was transferred into a 0.5 L autoclave glass container containing a 35 mm football rotor. . The glass container was sealed, and heating of the mixed liquid was started by predetermined PID control while stirring the mixed liquid in the glass container with the strong magnetic stirrer 7. The internal pressure in the sealed glass container was increased with heating. Thus, in the hydrothermal synthesis process, the liquid mixture in the glass container was heated under pressure for 48 hours. In the hydrothermal synthesis process, the temperature in the glass container was kept at 250 ° C. The pressure in the glass container was kept at 3.8 MPa.

  After stopping the heating, the mixed solution was taken out from the glass container after the temperature in the glass container dropped to 38 ° C. In addition, it took about 2 hours until the temperature in a glass container fell to 38 degreeC after stopping a heating. The mixed solution taken out from the glass container was a colorless and transparent solution containing a brown precipitate. The pH of the mixed solution was 6. The glass container was left still and the supernatant in the container was removed. Further, about 200 ml of distilled water was added to the container, and the inside of the container was stirred and washed. Immediately thereafter, a colorless transparent solution containing a brown precipitate, the removed supernatant, and all distilled water used for washing in the container were suction filtered, and the filtered precipitate was washed again with water to obtain a liquid. . The pH of the liquid was 6-7. The liquid was suction filtered again. Further, the brown precipitate contained in the liquid was washed with about 200 ml of acetone, and the liquid was suction filtered again. Thereby, the paste which was very sticky as a filtrate was obtained. The semi-dried filtrate was transferred to a stainless steel dish and vacuum dried at room temperature for 15.5 hours.

By the above hydrothermal synthesis process, 31.39 g of a brown solid was obtained as the active material of Example 1. It was confirmed that the weight of the brown solid converted to LiVOPO ₄ corresponds to 94.4% of the yield of 33.78 g assumed when the raw materials were charged.

(Example 2)
Of the brown dried solid obtained in the same manner as in Example 1, 1.00 g was placed in an alumina crucible. A heat treatment step was performed in which the solid in the alumina crucible was heated at 450 ° C. for 4 hours using a heating furnace. In the heat treatment step, the solid in the alumina crucible was heated in an Ar atmosphere. In the heat treatment step, the temperature in the furnace was raised from room temperature to 450 ° C. over 45 minutes. After heating the solid in the alumina crucible at 450 ° C. for 4 hours, the heating furnace was naturally cooled. By this heat treatment step, 1.00 g of green powder was obtained as the active material of Example 2. Since the weight of the solid did not change before and after the heat treatment step, the residual ratio of the solid after the heat treatment step was 100%.

(Examples 3 to 21)
In Examples 3 to 21, the compounds shown in Table 1 were used as the lithium source. In Examples 3 to 21, [Li] / [V] and [P] / [V] were adjusted to the values shown in Table 1, respectively. In the hydrothermal synthesis steps of Examples 3 to 21, the pH of the mixed solution immediately before heating in the autoclave was a value shown in Table 1. In Example 19, the pH of the mixed solution was adjusted using an aqueous ammonia solution. In the hydrothermal synthesis steps of Examples 3 to 21, the temperature in the glass container in which the mixed solution was sealed was maintained at the values shown in Table 1. In the heat treatment steps of Examples 3 to 21, the solid in the alumina crucible was heated in the atmosphere shown in Table 1. In Example 12, hydrogen peroxide was used as a reducing agent instead of hydrazine.

  Except for the above, the active materials of Examples 3 to 21 were obtained in the same manner as in Example 2.

(Comparative Example 1)
In the production of LiVOPO ₄ of Comparative Example 1, the following raw materials were used.

Lithium source: 5.95 g (0.14 mol) of LiOH.H ₂ O (molecular weight = 41.96, manufactured by Nacalai Tesque, special grade, purity 99% by weight).

Phosphoric acid source: 5.42 g (0.047 mol) of H ₃ PO ₄ (molecular weight = 98.00, manufactured by Nacalai Tesque, first grade, purity: 85% by weight).

Vanadium source: 1.43 g (0.0078 mol) of V ₂ O ₅ (molecular weight = 181.88, manufactured by Nacalai Tesque, special grade, purity: 99% by weight).

  200 g of distilled water (manufactured by Nacalai Tesque, for HPLC (high performance liquid chromatography)). Separately, 30 g of distilled water was also used between the glass container and the autoclave.

Reducing agent: 0.40 g (0.0080 mol) of NH ₂ NH ₂ .H ₂ O (molecular weight = 50.06, manufactured by Nacalai Tesque, special grade, purity: 98% by weight).

As is clear from the contents of the phosphoric acid source and the vanadium source, in Comparative Example 1, [P] / [V] was adjusted to 3. Moreover, [Li] / [V] was adjusted to 9 so that it might become clear from each content of said lithium source and vanadium source. Further, as apparent from the content of the lithium source and the amount of distilled water, the concentration of Li ^{+ in} the mixed solution was adjusted to 0.7 mol / L. Each amount of the raw materials is equivalent to a yield of about 2.63 g (0.0156 mol) of LiVOPO ₄ in terms of stoichiometry when converted to LiVOPO ₄ (molecular weight: 168.85).

H ₃ PO ₄ and distilled water were placed in a 0.5 L autoclave glass container, and these were stirred with a magnetic stirrer. Then, the addition of _V 2 _{O 5} in the glass container, to obtain a suspension. Furthermore, hydrazine monohydrate was dropped into the suspension while vigorously stirring the inside of the glass container. At this point, the liquid phase of the suspension changed from yellow-orange to green. Following the dropwise addition of hydrazine monohydrate, LiOH.H ₂ O was added to the suspension over about 10 minutes to obtain a mixed solution of Comparative Example 1. The pH of the mixture immediately after adding LiOH.H ₂ O was 7.5, and the color was dark green.

  The glass container was sealed, and stirring of the mixed liquid was started at a predetermined setting, and heating of the mixed liquid was started with predetermined PID control. The internal pressure in the sealed glass container was increased with heating. In this way, in the cold hydrothermal synthesis process of Comparative Example 1, the liquid mixture in the glass container was heated under pressure for 48 hours to keep the temperature in the glass container at 250 ° C. The pressure in the glass container was kept at 3.8 MPa.

  After stopping the heating, air cooling of the glass container was started. And after the temperature in a glass container fell to 25 degreeC, the liquid mixture was taken out. In addition, it took about 2 hours until the temperature in a glass container fell to 25 degreeC after stopping a heating. The mixed solution taken out from the glass container was a dark blue solution. The pH of the mixed solution was 8. After adding 100 ml of distilled water three times to the mixture, the mixture was spread on a vat. The mixture was dried at 100 ° C. for 24 hours to obtain 7.48 g of a dark blue solid.

  By applying a heat treatment step to the dark blue solid in the same manner as in Example 3, an active material of Comparative Example 1 was obtained.

(Comparative Examples 2 to 8)
In Comparative Examples 2 to 8, [Li] / [V] and [P] / [V] were adjusted to the values shown in Table 1, respectively. In the hydrothermal synthesis steps of Comparative Examples 2 to 8, the pH of the mixed solution immediately before heating using the autoclave was the value shown in Table 1. In the hydrothermal synthesis steps of Comparative Examples 2 to 8, the temperature in the glass container in which the mixed solution was sealed was maintained at the value shown in Table 1. In the heat treatment steps of Comparative Examples 2 to 8, the solid in the alumina crucible was heated in the atmosphere shown in Table 1. In Comparative Example 6, an active material was obtained without using a reducing agent.

  Except for the above, the active materials of Comparative Examples 2 to 8 were obtained in the same manner as in Comparative Example 1.

[Measurement of crystal structure]
From the results of Rietveld analysis based on powder X-ray diffraction (XRD), it was confirmed that each of the active materials of Examples 1 to 21 and Comparative Examples 1 to 8 contained a β-type crystal phase of LiVOPO ₄ .

[Production of evaluation cell]
A mixture of the active material of Example 1, polyvinylidene fluoride (PVDF) as a binder, and acetylene black was dispersed in N-methyl-2-pyrrolidone (NMP) as a solvent to prepare a slurry. The slurry was prepared so that the weight ratio of the active material, acetylene black, and PVDF was 84: 8: 8 in the slurry. This slurry was applied onto an aluminum foil as a current collector, dried, and then rolled to obtain an electrode (positive electrode) on which an active material layer containing the active material of Example 1 was formed.

Next, the obtained electrode and the Li foil as the counter electrode were laminated with a separator made of a polyethylene microporous film interposed therebetween to obtain a laminate (element body). This laminate was put in an aluminum laminator pack, and 1M LiPF ₆ solution was injected as an electrolyte into the aluminum laminate pack, followed by vacuum sealing to produce an evaluation cell of Example 1.

  In the same manner as in Example 1, evaluation cells were produced using each of the active materials of Examples 2 to 21 and Comparative Examples 1 to 8 alone.

[Measurement of discharge capacity]
Using the evaluation cell of Example 1, the discharge capacity (unit: mAh / unit) when the discharge rate is 0.01 C (current value at which discharge is completed in 100 hours when constant current discharge is performed at 25 ° C.) g) was measured. The measurement results are shown in Table 1. In addition, using the evaluation cell of Example 1, the discharge capacity (unit: unit) when the discharge rate is 0.1 C (current value at which discharge is completed in 10 hours when constant current discharge is performed at 25 ° C.). mAh / g) was measured. The measurement results are shown in Table 1.

  In the same manner as in Example 1, the discharge capacities of the evaluation cells in Examples 2 to 21 and Comparative Examples 1 to 8 were measured. The results are shown in Table 1.

[Evaluation of rate characteristics]
The rate characteristics (unit:%) of Example 1 were determined. The rate characteristic is a ratio of the discharge capacity at 0.1 C when the discharge capacity at 0.01 C is 100%. The results are shown in Table 1. Larger rate characteristics are preferable.

  In the same manner as in Example 1, the rate characteristics of the evaluation cells of Examples 2 to 21 and Comparative Examples 1 to 8 were measured. The results are shown in Table 1.

As apparent from Table 1, in Examples 1 to 21, a hydrothermal synthesis step of heating a mixed solution containing a lithium source, a phosphate source, a vanadium source, water, and a reducing agent to 200 to 300 ° C. under pressure. LiVOPO ₄ was obtained by the manufacturing method provided. Moreover, in Examples 1-21, [P] / [V] was adjusted to 0.9-1.5.

It was confirmed that the discharge capacity at 0.01 C of the evaluation cell using LiVOPO ₄ obtained in Examples 1 to 21 was larger than that of the comparative example. Moreover, it was confirmed that the discharge capacity at 0.1 C of the evaluation cells of Examples 1 to 21 is equal to or higher than the discharge capacity of each comparative example.

From the above, it is estimated that in Examples 1 to 21, the yield of β-type crystals of LiVOPO ₄ is higher than in Comparative Examples 1 to 8.

Discharge capacity and rate characteristics of the evaluation cell of Example 16 using the _Li 2 SO ₄ as the lithium source, confirmed that as compared with Examples 4,13～15 using lithium source other than _Li 2 SO ₄ small It was done.

  From the comparison between Example 1 and Examples 2 and 3, the rate characteristics of the evaluation cell using the active material that has undergone the heat treatment step are higher than those of the evaluation cell using the active material obtained without performing the heat treatment step. Was confirmed to be large.

  From the comparison between Example 3 and Example 19, in the hydrothermal synthesis step, the discharge capacity and rate characteristics of the evaluation cell were adjusted by adjusting the pH of the mixed solution immediately before heating using an autoclave to 7.5 or less. Has been confirmed to improve.

Claims (4)

Comprising a hydrothermal synthesis step of heating a mixture containing a lithium source, a phosphate source, a vanadium source, water and a reducing agent to 200 to 300 ° C. under pressure,
The ratio [P] / [V] of the number of moles of phosphorus element [P] contained in the mixture before heating to the number of moles [V] of vanadium element contained in the mixture before heating is 0.9-1. Adjust to 5,
A method for producing an active material. Adjusting the ratio [Li] / [V] of the number of moles of lithium element [Li] and [V] contained in the mixture before heating to 0.9 to 1.5;
The manufacturing method of the active material of Claim 1. The lithium source is at least one selected from the group consisting of LiOH, Li ₂ CO ₃ , CH ₃ COOLi and Li ₃ PO ₄ ;
The manufacturing method of the active material of Claim 1 or 2. A heat treatment step of further heating the mixture after the hydrothermal synthesis step;
The manufacturing method of the active material as described in any one of Claims 1-3.