阅读说明：本技术 卤化物的制造方法 (Method for producing halide ) 是由 久保敬 西尾勇祐 酒井章裕 宫崎晃畅 于 2019-06-26 设计创作，主要内容包括：本公开的卤化物的制造方法,包括将混合材料在惰性气体气氛下进行烧成的烧成工序,所述混合材料是混合有LiCl和YCl-3的材料。在所述烧成工序中,所述混合材料在200℃以上且650℃以下被烧成。(The disclosed method for producing a halide comprises a firing step of firing a mixed material in which LiCl and YCl are mixed in an inert gas atmosphere 3 The material of (1). In the firing step, the mixed material is fired at 200 ℃ to 650 ℃.)

1. A process for the production of a halide compound,

comprises a firing step of firing the mixed material in an inert gas atmosphere,

the mixed material is mixed with LiCl and YCl₃The material (a) of (b) is,

in the firing step, the mixed material is fired at 200 ℃ to 650 ℃.

2. The manufacturing method according to claim 1, wherein the substrate is a glass substrate,

in the firing step, the mixed material is fired at 400 ℃ or higher and 650 ℃ or lower.

3. The manufacturing method according to claim 2, wherein the substrate is a glass substrate,

in the firing step, the mixed material is fired at 480 ℃ or higher.

4. The manufacturing method according to claim 2 or 3,

in the firing step, the mixed material is fired at 600 ℃ or lower.

5. The production method according to any one of claims 1 to 4,

in the firing step, the mixed material is fired for 1 hour to 24 hours.

6. The manufacturing method according to the above-mentioned claim 5,

in the firing step, the mixed material is fired for 10 hours or less.

7. The production method according to any one of claims 1 to 6,

the mixed material is also mixed with M_αA_βThe material (a) of (b) is,

the M contains at least one element selected from the group consisting of Na, K, Ca, Mg, Sr, Ba, Zn, In, Sn, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu,

a is at least one element selected from Cl, Br and I,

alpha > 0 and beta > 0 are satisfied.

8. The production method according to any one of claims 1 to 7,

the mixed material is also mixed with LiF and YF₃A material of at least one of (1).

Technical Field

The present invention relates to a method for producing a halide.

Background

Patent document 1 discloses a method for producing a halide solid electrolyte.

Prior art documents

Patent document 1: international publication No. 2018/025582

Disclosure of Invention

Problems to be solved by the invention

In the prior art, it has been desired to produce a halide by a method having a high industrial productivity.

Means for solving the problems

A method for manufacturing a halide according to one aspect of the present disclosure includes a firing step of firing a mixed material in which LiCl and YCl are mixed in an inert gas atmosphere₃In the firing step, the mixed material is fired at 200 ℃ to 650 ℃.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present disclosure, a halide can be produced by a method with high industrial productivity.

Drawings

Fig. 1 is a flowchart showing an example of the manufacturing method in embodiment 1.

Fig. 2 is a flowchart showing an example of the manufacturing method in embodiment 1.

Fig. 3 is a flowchart showing an example of the manufacturing method in embodiment 1.

Fig. 4 is a schematic diagram showing an evaluation method of ion conductivity.

Fig. 5 is a graph showing the evaluation results of ion conductivity by AC impedance measurement.

Detailed Description

Hereinafter, embodiments will be described with reference to the drawings.

(embodiment mode 1)

Fig. 1 is a flowchart showing an example of the manufacturing method in embodiment 1.

The manufacturing method in embodiment 1 includes a firing step S1000.

The firing step S1000 is a step of firing the mixed material in an inert gas atmosphere. Here, the mixed material fired in the firing step S1000 is a mixture of LiCl (i.e., lithium chloride) and YCl₃(i.e., yttrium chloride). In the firing step S1000, the mixed material is fired at 200 ℃ to 650 ℃.

According to the above technical configuration, the halide can be produced by a method with high industrial productivity (for example, a method capable of mass production at low cost). That is, chlorides containing Li (i.e., lithium) and Y (i.e., yttrium) can be produced by a simple production method (i.e., firing in an inert gas atmosphere) without using a vacuum sealed tube or a planetary ball mill.

In the firing step S1000, for example, the powder of the mixed material may be put into a container (e.g., a crucible) and fired in a heating furnace. In this case, the mixed material is heated to "200 ℃ or higher and 650 ℃ or lower" in an inert gas atmosphere, and may be maintained for a predetermined time or longer. The firing time may be a time of such a length that composition variation of the fired product due to volatilization of a halide or the like does not occur (that is, ion conductivity of the fired product is not impaired).

As the inert gas, helium, nitrogen, argon, or the like can be used.

After the firing step S1000, the fired material may be taken out of the container (e.g., crucible) and pulverized. At this time, the fired product can be pulverized by a pulverizer (e.g., a mortar, a mixer, or the like).

Further, the mixed material in the present disclosure may be only mixed with LiCl and YCl₃The materials of these two materials. Alternatively, the hybrid materials in the present disclosure may also be other than LiCl andYCl₃in addition, LiCl and YCl are mixed₃Different materials of other materials.

Further, in the present disclosure, the mixed material may be further mixed with M_αA_βThe material of (1). Here, M contains at least one element selected from the group consisting of Na, K, Ca, Mg, Sr, Ba, Zn, In, Sn, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu. Further, A is at least one element selected from Cl, Br and I. In addition, α > 0 and β > 0 are satisfied.

According to the above technical configuration, the characteristics (e.g., ion conductivity) of the halide produced by the production method of the present disclosure can be improved.

When "α" is 1, "2 ≦ β ≦ 5 may be satisfied.

Further, in the present disclosure, the mixed material may be further mixed with LiF and YF₃A material of at least one of (1).

According to the above technical configuration, the characteristics (e.g., ion conductivity) of the halide produced by the production method of the present disclosure can be improved.

Further, in the present disclosure, the mixed material may be a mixture of a portion of Li (or YCl) in LiCl substituted with a substituting cation species (e.g., M described above)₃A part of Y) of the material. In addition, the mixed material may be one in which a part of Cl (or YCl) in LiCl is substituted by F (i.e., fluorine)₃A portion of Cl) in the composition.

Fig. 2 is a flowchart showing an example of the manufacturing method in embodiment 1. As shown in fig. 2, the manufacturing method in embodiment 1 may further include a mixing step S1100.

The mixing step S1100 is performed before the firing step S1000.

The mixing step S1100 is a step of mixing LiCl and YCl as raw materials to obtain a mixed material (i.e., a material fired in the firing step S1000).

In the mixing step S1100, LiCl and YCl may be weighed and mixed in a desired molar ratio. As a method for mixing the raw materials, a method using a generally known mixing device (for example, a mortar, a stirrer, a ball mill, etc.) can be used. For example, in the mixing step S1100, powders of the respective raw materials may be prepared and mixed. In this case, in the firing step S1000, the powdery mixture may be fired. The powdery mixture obtained in the mixing step S1100 may be formed into pellets by uniaxial pressing. At this time, in the firing step S1000, the granulated mixture is fired to produce a halide.

In addition, in the mixing step S1100, LiCl and YCl may be excluded₃In addition, LiCl and YCl were mixed₃Various other materials (e.g. M as described above)_αA_β、LiF、YF₃Etc.) to obtain a mixed material.

In the mixing step S1100, the "raw material mainly composed of LiCl" and the "YCl" may be mixed₃The raw materials as the main components are "mixed to obtain a mixed material.

Fig. 3 is a flowchart showing an example of the manufacturing method in embodiment 1. As shown in fig. 3, the manufacturing method in embodiment 1 may further include a preparation step S1200.

The preparation step S1200 is a step performed before the mixing step S1100.

The preparation step S1200 is to prepare LiCl and YCl₃And (d) the raw materials (i.e., the materials mixed in the mixing step S1100).

In the preparation step S1200, LiCl and YCl can be obtained by performing material synthesis₃And the like. Alternatively, in the preparation step S1200, a generally known commercially available product (for example, a material having a purity of 99% or more) can be used. Further, as the raw material, a dried material may be used. In addition, as the raw material, a crystalline, massive, flaky, powdery, or the like raw material can be used. In the preparation step S1200, a raw material in a crystalline form, a bulk form, or a flake form may be pulverized to obtain a powdery raw material.

In the preparation step S1200, M may be added_αA_β(wherein M is selected from Na, K, Ca, Mg, Sr, Ba. Zn, In, Sn, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu, A is at least one element selected from Cl, Br and I, and "2. ltoreq. beta. ltoreq.5", LiF, YF, In the case where "alpha. 1" is satisfied₃Any one or more of. This improves the properties (e.g., ion conductivity) of the halide obtained by the production method of the present disclosure.

In the preparation step S1200, a substitution cation species (for example, M) may be prepared by substituting a part of Li (or YCl) in LiCl with a substitution cation species (for example, M described above)₃A part of Y) in the reaction mixture. In the preparation step S1200, a part of Cl (or YCl) in LiCl may be replaced with F (i.e., fluorine)₃A portion of Cl) in the reaction mixture.

Further, the halide produced by the production method of the present disclosure can be used as a solid electrolyte material. In this case, the solid electrolyte material may be, for example, a lithium ion conductive solid electrolyte. In this case, the solid electrolyte material can be used, for example, as a solid electrolyte material used for an all-solid lithium secondary battery.

(embodiment mode 2)

Embodiment 2 will be described below. The description overlapping with embodiment 1 above is appropriately omitted.

The production method according to embodiment 2 has the following features in addition to the features of the production method according to embodiment 1.

In the firing step S1000 of the production method of embodiment 2, LiCl and YCl are mixed₃The mixed material of (2) is fired at 400 ℃ or higher and 650 ℃ or lower.

According to the above technical constitution, a chloride having a high ionic conductivity can be produced by an industrially high-productivity method. That is, LiCl and YCl can be formed by setting the firing temperature to 400 ℃ or higher₃And (4) fully reacting. Further, by setting the firing temperature to 650 ℃ or lower, thermal decomposition of chloride generated by a solid-phase reaction can be suppressed. This can improve the ionic conductivity of the chloride as a burned product. That is, for example, a solid electrolyte capable of obtaining a high-quality chloride。

In the firing step S1000 of the production method of embodiment 2, the mixed material may be fired at 480 ℃ or higher (for example, 480 ℃ or higher and 650 ℃ or lower).

According to the above technical constitution, a chloride having a high ionic conductivity can be produced by an industrially high-productivity method. That is, by setting the firing temperature to 480 ℃ or higher, the crystallinity of the chloride as the fired product can be further improved. This can further improve the ionic conductivity of the chloride as a burned product. Namely, for example, a solid electrolyte capable of obtaining a higher-quality chloride.

In the firing step S1000 in the production method of embodiment 2, the mixed material may be fired at 600 ℃ or lower (for example, 400 ℃ to 600 ℃ inclusive, or 480 ℃ to 600 ℃ inclusive).

According to the above technical constitution, a chloride having a higher ionic conductivity can be produced by an industrially high-productivity method. That is, by setting the firing temperature to 600 ℃ or less, firing can be performed at a temperature lower than the melting point of LiCl (i.e., 605 ℃), and decomposition of LiCl (further, YCl) can be suppressed₃Has a melting point of about 720 deg.C, and can inhibit YCl₃Decomposition of (d). This can further improve the ionic conductivity of the chloride as a burned product. Namely, for example, a solid electrolyte capable of obtaining a higher-quality chloride.

In the firing step S1000 of the production method of embodiment 2, the mixed material may be fired for 1 hour to 24 hours.

According to the above technical constitution, a chloride having a higher ionic conductivity can be produced by an industrially high-productivity method. That is, by setting the firing time to 1 hour or more, LiCl and YCl can be made₃And (4) fully reacting. Further, by setting the firing time to 24 hours or less, volatilization of chloride as a fired product can be suppressed, and chloride having a desired composition ratio of the constituent elements can be obtained (that is, variation in composition can be suppressed). This can further improve the ionic conductivity of the chloride as a burned product. I.e. e.g.A solid electrolyte of chloride of higher quality can be obtained.

In the firing step S1000 of the production method of embodiment 2, the mixed material may be fired for 10 hours or less (for example, 1 hour or more and 10 hours or less).

According to the above technical configuration, by setting the firing time to 10 hours or less, volatilization of chloride as a fired product can be further suppressed, and chloride having a desired composition ratio of the constituent elements can be obtained (that is, variation in composition can be suppressed). This can further suppress a decrease in the ionic conductivity of the chloride as a burned product due to the composition variation.

In the mixing step S1100 of the production method of embodiment 2, LiCl and YCl can be mixed₃Weighing and mixing the mixture at a desired molar ratio to adjust LiCl and YCl₃The mixing molar ratio of (a).

For example, in embodiment 2, LiCl and YCl₃YCl can be added as LiCl₃The molar ratio of "4.2: 0.6" to "2.4: 1.2" was mixed. Alternatively, LiCl and YCl₃YCl can be added as LiCl₃The molar ratio of "3: 1" to "2.7: 1.1" was mixed.

In the mixing step S1100 of the manufacturing method of embodiment 2, LiCl and YCl may be excluded₃In addition to M_αCl_β(that is, M in embodiment 1 above_αA_βA compound in which "a" of (a) is Cl) to obtain a mixed material. In this case, in the preparation step S1200 of the manufacturing method of embodiment 2, M may be prepared_αCl_βAs one of the raw materials.

(examples)

Hereinafter, the details of the present disclosure will be described with reference to examples and reference examples. These are merely examples and do not limit the disclosure.

In the following examples, the halide produced by the production method of the present disclosure was produced and evaluated as a solid electrolyte material.

< example 1 >

(preparation of solid electrolyte Material)

Subjecting LiCl and YCl to condensation reaction under argon atmosphere with dew point below-60 deg.C₃Using LiCl to YCl₃The molar ratio was 3: 1. They were pulverized with an agate mortar and mixed. Then, the mixture was put into an alumina crucible, and heated to 500 ℃ in an argon atmosphere and held for 1 hour. After firing, the mixture was pulverized in an agate mortar to prepare a solid electrolyte material of example 1.

The Li content per unit weight in the entire solid electrolyte material of example 1 was measured by atomic absorption spectrometry, the Y content was measured by ICP emission spectrometry, and the Li/Y content was converted to a molar ratio. The ratio of Li to Y is 3:1 as the feed.

(evaluation of ion conductivity)

Fig. 4 is a schematic diagram showing an evaluation method of ion conductivity.

The press mold 200 is composed of a frame 201 made of electrically insulating polycarbonate, and an upper punch 203 and a lower punch 202 made of electrically conductive stainless steel.

Using the structure shown in fig. 4, the ion conductivity was evaluated by the following method.

A solid electrolyte powder 100, which is a powder of the solid electrolyte material of example 1, was filled in a press-molding die 200 in a dry atmosphere having a dew point of-60 ℃ or lower, and uniaxially pressed at 300MPa to prepare a conductivity cell of example 1.

Lead wires were led out from the upper part 203 and the lower part 202 of the punch press under pressure, respectively, and connected to a potentiostat (Princeton Applied Research, VersaSTAT4) equipped with a frequency response analyzer, and the ionic conductivity at room temperature was measured by electrochemical impedance measurement.

Fig. 5 is a graph showing the evaluation results of the ion conductivity measured by the AC impedance method. The Cole-Cole line graph of the impedance measurement results is shown in FIG. 5.

In fig. 5, the real part value of the impedance at the measurement point (arrow in fig. 5) where the absolute value of the phase of the complex impedance is the smallest is regarded as the resistance value with respect to ion conduction of the solid electrolyte of example 1. The ionic conductivity was calculated by the following formula (1) using the resistance value of the electrolyte.

σ＝(R_SE×S/t)^-1···· (1)

Where σ is the ionic conductivity, S is the electrolyte area (the inner diameter of the frame 201 in FIG. 4), and R is_SEIs the resistance value of the solid electrolyte in the impedance measurement described above, and t is the thickness of the electrolyte (the thickness of the solid electrolyte powder 100 in fig. 4).

The ionic conductivity of the solid electrolyte material of example 1 measured at 22 ℃ was 1.5X 10^-4S/cm。

< examples 2 to 30 >

(preparation of solid electrolyte Material)

In examples 2 to 30, LiCl and YCl were reacted in an argon atmosphere having a dew point of-60 ℃ or lower in the same manner as in example 1₃Using LiCl to YCl₃The molar ratio of x to 6-3x was weighed. In each example, the "value of x" is shown in table 1 described later.

They were crushed with an agate mortar and mixed. Then, the mixture is put into an alumina crucible, and the temperature is raised to 400 to 650 ℃ in an argon atmosphere and kept for 1 to 24 hours. The "firing temperature" and "firing time" in each example are shown in table 1 described below.

After firing under each firing condition, the mixture was pulverized in an agate mortar, and the solid electrolyte materials of examples 2 to 30 were produced.

(evaluation of ion conductivity)

Conductivity measurement cells of examples 2 to 30 were produced in the same manner as in example 1, and the ion conductivity was measured.

< reference examples 1 and 2 >

(preparation of solid electrolyte Material)

In reference example 1, LiCl and YCl were reacted under an argon atmosphere having a dew point of-60 ℃ or lower₃Using LiCl to YCl₃The molar ratio was 3: 1. In reference example 2, LiCl and YCl were reacted under an argon atmosphere having a dew point of-60 ℃ or lower₃Using LiCl to YCl₃The molar ratio was 2.7: 1.1. They were pulverized with an agate mortar and mixed. Then, the mixture was put into an alumina crucible, and heated to 300 ℃ in an argon atmosphere and held for 1 hour.

After firing, the resultant was pulverized in an agate mortar to prepare solid electrolyte materials of reference examples 1 and 2, respectively.

(evaluation of ion conductivity)

Conductivity measurement cells of reference examples 1 and 2 were prepared in the same manner as in example 1, and the ion conductivity was measured.

< reference examples 3 and 4 >

In reference example 3, LiCl and YCl were reacted under an argon atmosphere having a dew point of-60 ℃ or lower₃Using LiCl to YCl₃The molar ratio was 3: 1. In reference example 4, LiCl and YCl were reacted under an argon atmosphere having a dew point of-60 ℃ or lower₃Using LiCl to YCl₃The molar ratio was 2.7: 1.1. They were pulverized with an agate mortar and mixed. Then, the mixture was put into an alumina crucible, and heated to 500 ℃ in an argon atmosphere and held for 60 hours.

After firing, the resultant was pulverized in an agate mortar to prepare solid electrolyte materials of reference examples 3 and 4, respectively.

(evaluation of ion conductivity)

Conductivity measurement cells of reference examples 3 and 4 were prepared in the same manner as in example 1, and the ion conductivity was measured.

The configurations and evaluation results of examples 1 to 30 and reference examples 1 to 4 are shown in Table 1.

[ Table 1]

< investigation >)

As in reference examples 1 and 2, the sintered body showed 10 at a temperature of about room temperature at a sintering temperature of 300 ℃^-7Low ionic conductivity on the order of S/cm. As in reference examples 3 and 4, the firing time was set toUp to 60 hours, it showed 10^-9～10^-8Low ion conductivity of S/cm. In contrast, examples 1 to 30 exhibited 1X 10 at around room temperature^-6High ion conductivity of S/cm or more. This is considered to be because the solid-phase reaction is insufficient when the firing temperature is 300 ℃. Further, it is considered that the halide volatilizes when the firing temperature is as long as 60 hours, and there is a possibility that the composition may vary.

The firing temperature is in the range of 480-600 ℃, and the material shows higher ion conductivity. This is considered to be due to the realization of a solid electrolyte with high crystallinity. For example, if the same raw material mixing ratio and firing time are compared, in example 4 where the firing temperature is 450 ℃, the ionic conductivity is 6.8X 10^-6S/cm, and in contrast, in example 5 in which the firing temperature was 480 ℃, the ionic conductivity was 1.4X 10^-4S/cm. In example 9 having a firing temperature of 600 ℃, the ionic conductivity was 8.5X 10^-5S/cm, and in contrast, in example 10 in which the firing temperature was 650 ℃, the ionic conductivity was 4.0X 10^-5S/cm. This is considered to be because the firing is carried out at a temperature higher than the melting point of LiCl, and therefore LiCl is in contact with YCl₃Decomposition occurs before the reaction of (1) is completed.

As can be seen from the above, the solid electrolyte material synthesized by the production method of the present disclosure exhibits high lithium ion conductivity. The production method of the present disclosure is a simple method and has high industrial productivity.

Industrial applicability

The production method of the present disclosure is useful, for example, for a production method of a solid electrolyte material. The solid electrolyte material produced by the production method of the present disclosure can be used, for example, in an all-solid lithium secondary battery or the like.

Description of the reference numerals

100 solid electrolyte powder

200 press molding die

201 frame

202 punch press lower part

203 punch press.