CN112533872A - Garnet-type composite metal oxide and method for producing same - Google Patents
Garnet-type composite metal oxide and method for producing same Download PDFInfo
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Abstract
An object is to provide a method for producing a composite metal oxide having excellent crystallinity by a mechanochemical method. The present invention is a method for producing a garnet-type composite metal oxide containing Li, La, Zr, and O, wherein a mixture containing a raw material powder containing a Li source powder, a La source powder, and a Zr source powder and a flux is treated by a mechanochemical method to react the raw material powder. The raw material powder preferably further contains at least 1 of Al source powder and Ga source powder.
Description
Technical Field
The present invention relates to a garnet-type composite metal oxide and a method for producing the same.
Background
Complex metal oxides containing a plurality of metals have fluorescent properties, strong dielectric properties, superconducting properties, ion conductivity and other properties, and are used in various fields according to the properties. As a method for producing a composite metal oxide, a method is known in which raw materials such as a metal oxide and a metal carbonate are prepared for each metal element, and the raw materials of each metal element are mixed and sintered. On the other hand, patent document 1 discloses a YAG phosphor (Y) as a composite metal oxide3Al5O12Ce) discloses that a YAG phosphor (Y) can be produced by treating a metal oxide powder as a raw material with a flux by a mechanochemical method3Al5O12:Ce)。
Documents of the prior art
Patent document
Patent document 1: WO2017/002467
Disclosure of Invention
Problems to be solved by the invention
According to the aforementioned patent document 1, it is described that a mixture containing raw material powders and a flux can be treated by a mechanochemical method, thereby allowing the raw material powders to react with each other without subsequent sintering. However, the present inventors have studied and found that, in the YAG phosphor disclosed in patent document 1, a YAG crystal can be produced by a mechanochemical method without fail, but a YAG crystal obtained by a mechanochemical treatment alone has room for improvement in crystallinity.
Accordingly, an object of the present invention is to provide a method for producing a composite metal oxide having excellent crystallinity by a mechanochemical method.
Means for solving the problems
The present inventors have studied composite metal oxides of various compositions, focused on a composite metal oxide containing Li, La, Zr, and O having a garnet structure similar to a YAG crystal, and found that: when the raw material powder and flux are treated by a mechanochemical method to produce the above-mentioned composite metal oxide, a garnet-type composite metal oxide having a crystallinity better than that of a YAG crystal produced by a mechanochemical method can be produced, and the present invention has been completed. The present invention is as follows.
[1] A method for producing a garnet-type composite metal oxide containing Li, La, Zr and O, characterized in that a mixture containing a raw material powder containing a Li source powder, a La source powder and a Zr source powder and a flux is treated by a mechanochemical method to react the raw material powder.
[2] The production method according to [1], wherein the raw material powder further contains at least one of an Al source powder and a Ga source powder.
[3] The production method according to [1] or [2], wherein the crystallite diameter of the garnet-type composite metal oxide is 30nm or more.
[4] The production method according to [2] or [3], wherein the crystal system of the garnet-type composite metal oxide is a cubic crystal.
[5] The production method according to any one of [1] to [4], comprising:
a bottomed cylindrical container, and
a rotor having a front end blade having a curvature smaller than an inner circumference of the vessel;
a predetermined gap is provided between the front end blade and the inner periphery of the vessel,
the rotor is rotated to shear the mixture containing the raw material powder and the flux in the gap while compressing the mixture.
[6] The production method according to [5], wherein the power of the rotor is 0.05kW/g or more based on the total amount of the raw material powder, and the rotor is rotated for 10 minutes or more.
[7] The production method according to any one of [1] to [6], wherein heating by an external heat source is not performed.
[8] A garnet-type composite metal oxide comprising Li, La, Zr and O,
the diameter of the microcrystal is more than 30nm,
the particles have a particle assembly structure, and the major axis of 90% or more of the primary particles on a number basis is 3 μm or less.
[9] A garnet-type composite metal oxide comprising Li, La, Zr and O,
the BET specific surface area diameter is 1.5 μm or less.
[10] The garnet-type composite metal oxide according to [8] or [9], which further comprises at least one of Al and Ga, and the crystal system is cubic.
[11] A solid electrolyte material for a secondary battery comprising the garnet-type composite metal oxide of [10 ].
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, which produces a garnet-type composite metal oxide containing Li, La, Zr, and O by a mechanochemical method, a composite metal oxide having good crystallinity can be provided.
Drawings
Fig. 1 (a) is a cross-sectional view perpendicular to the rotation axis of a grinding mill that can be used in the mechanochemical process, and fig. 1 (b) is a cross-sectional view a-a' of fig. 1 (a).
Figure 2 is the XRD diffractogram of examples 1 and 2.
FIG. 3 is a substitute photograph for drawing showing an SEM observation image of LLZ obtained in example 1.
Figure 4 is the XRD diffractogram of examples 4, 5.
FIG. 5 is a photograph substitute for drawing showing cross-sectional STEM observation images of LLZ obtained in examples 4 and 5.
Detailed Description
The present invention relates to a method for producing a garnet-type composite metal oxide containing Li, La, Zr, and O by a mechanochemical process. Garnet structures are generally represented by A3B2C3O12In the garnet-type composite metal oxide of the present invention containing Li, La, Zr and O, La3+Zr occupying the position of A in the above composition formula4+Occupying the position of B, Li+Occupy the C position and the intercrystalline position, and can be represented by Li7La3Zr2O12The compositional formula (2) of (a). In a preferred embodiment, Li7La3Zr2O12Li in (1)+Part of the sites being optionally substituted with Al3+And/or Ga3+And (4) substitution. Hereinafter, in this specification, Li is also included+Part of the site is covered with Al3+And/or Ga3+Among the substitution patterns, the garnet-type composite metal oxide containing Li, La, Zr, and O is referred to as "LLZ". In addition, in the LLZ of the present invention, La is also allowed3+Part of the sites is replaced by Ce, Eu and other dopants.
In the present invention, Li source powder, La source powder, and Zr source powder are used as raw materials, and a mixture containing these raw material powders and a flux is processed by a mechanochemical method to cause a reaction between the raw material powders, thereby producing LLZ. More specifically, the mechanochemical method may be carried out by compressing a mixture containing a raw material powder under a dry condition and shearing the mixture, and strain energy is accumulated in the raw material powder, and the accumulated energy is released by itself to be thermal energy, or consumed by surface modification, crystal structure conversion, or solid-phase reaction. In the present invention, the raw material powders are subjected to mechanochemical treatment in the presence of a flux, and the generated energy is used to generate a liquid phase on the surface of the raw material, thereby promoting the reaction between the raw material powders. Therefore, by the present invention, the target inorganic compound can be obtained in a very short time by only mechanochemical treatment without performing heat treatment at high temperature. In addition, according to the present invention for producing LLZ, when compared after mechanochemical treatment (and without sintering), a compound having higher crystallinity than the YAG crystal disclosed in patent document 1 can be obtained.
As the raw material powder, Li source powder, La source powder, and Zr source powder are used, and preferably at least 1 of Al source powder and Ga source powder is further used. By using at least 1 of the Al source powder and the Ga source powder, the cubic LLZ can be stabilized, and the crystal system of the LLZ can be made cubic.
As the Li source powder, La source powder, Zr source powder, Al source powder, and Ga source powder, for example, oxides, carbonates, hydroxides, chlorides, alkoxides, and the like of each metal (Li, La, Zr, Al, or Ga) can be used. The Li source powder is preferably Li oxide or Li carbonate, the La source powder is preferably La oxide or La hydroxide, the Zr source powder is preferably Zr oxide or Zr hydroxide, the Al source powder is preferably Al oxide or Al hydroxide, and the Ga source powder is preferably Ga oxide or Ga hydroxide. The Li source powder, the La source powder, and the Zr source powder are preferably oxide (Li oxide, La oxide, and Zr oxide) powders of the respective metals, and when at least 1 of the Al source powder and the Ga source powder is used, the Al source powder and the Ga source powder are also preferably oxide (Al oxide, Ga oxide) powders.
The use ratio of the Li source powder, La source powder, Zr source powder, Al source powder, and Ga source powder may be set to the stoichiometric ratio of the target composition. In particular, when the Al source powder and/or the Ga source powder is used, the total amount of Al and Ga in the raw material powder with respect to the amount of Li is preferably 0.05 or more in terms of a molar ratio, and the crystal system of the LLZ thus obtained may be made cubic. The molar ratio is more preferably 0.06 or more, and still more preferably 0.08 or more, and the upper limit is not limited, but is, for example, 0.2 or less.
It is also preferable that each raw material powder has its powder characteristics properly adjusted, for example, its specific surface area S based on the BET methodw(m2The preferred concentration is 0.5 to 25 m/g)2(ii) in terms of/g. In addition, it can be determined by the specific surface area SwUsing the following formula to calculateSpecific surface area diameter dBET(nm)。
dBET＝6/(ρ·Sw)
(in the above formula, ρ represents the theoretical density)
Preferred specific surface area diameter dBET(nm) 500 to 2000nm for Li source powder, 400 to 700nm for La source powder, 20 to 100nm for Zr source powder, 80 to 200nm for Al source powder, and 20 to 100nm for Ga source powder.
Examples of the flux include a metal hydroxide, a metal oxide, and a metal halide. These have an effect of generating a liquid phase between the raw material powders to increase the contact area, and the use of such a flux enables a reaction between the raw material powders by a mechanochemical method. Examples of the metal hydroxide include Al (OH)3、Ga(OH)3、KOH、Sr(OH)2、NaOH、Ba(OH)2、Mg(OH)2LiOH and La (OH)3Etc., at least 1 of these may be used. Preferred metal hydroxides are Al (OH)3. Examples of the metal oxide include PbO and B2O3And the like. The metal halide is preferably a metal fluoride or a metal chloride, and examples of the metal include alkali metals, alkaline earth metals, Y, Al, Pb, Bi, Zn, and the like. The metal fluoride is preferably selected from the group consisting of BaF2、YF3、AlF3And SrF3At least 1 of the group, particularly preferably BaF2. The metal chloride is preferably an alkali metal chloride, and more preferably LiCl. As the metal halide, a metal fluoride is preferable. The melting point of the flux is, for example, 200 to 1400 ℃, preferably 400 to 1300 ℃, and the specific surface area diameter d obtained from the BET specific surface areaBETFor example, 50nm or more, more preferably 80nm or more, further preferably 100nm or more, and the specific surface area diameter dBETThe upper limit of (B) is preferably 2000nm or less, more preferably 1600nm or less, still more preferably 200nm or less, and particularly preferably 150nm or less. The amount of flux can be appropriately set in consideration of the balance between the amount of flux and the type of raw material powder used and the conditions of mechanochemical treatment, and examples thereofFor example, 4 to 15% by mass based on the total amount of the raw material powder.
As described above, the mechanochemical method can be more specifically performed by compressing a mixture containing a raw material powder under dry conditions and shearing the mixture. An example of the method is explained using the drawings. Fig. 1 is a schematic view of an attrition mill capable of imparting a compressive force and a shearing force to a mixture of raw material powders, fig. 1 (a) is a cross-sectional view perpendicular to a rotation axis, and fig. 1 (b) is a cross-sectional view a-a' of fig. 1 (a). The grinding mill of fig. 1 includes a bottomed cylindrical container 1 and a rotor 2. The rotor 2 has a tip blade 3 having a curvature smaller than the inner periphery of the bottomed cylindrical container 1, and a gap 4 is provided between the tip blade 3 and the inner periphery of the bottomed cylindrical container 1. Then, by rotating the rotor 2, the mixture 5 of the raw material powder and the flux receives a compressive force and a shearing force in the gap 4.
The conditions of the mechanochemical treatment are not preferable because when the reaction conditions are too weak, the raw material powders do not react with each other, and when the reaction conditions are too strong, crystals are once formed and are amorphized. When the conditions of the mechanochemical treatment are not suitable, the conditions may be appropriately changed depending on the reason (non-reaction, amorphization, etc.), the kind and amount of the raw material, the kind and amount of the flux, and the like, for example, as described below.
The range of the gap may vary depending on the amount of the raw material powder, the difference between the curvature of the tip blade of the rotor and the curvature of the inner periphery of the container, the processing power of the rotor, and the like, and is preferably less than 1mm, for example. In this way, a compressive force and a shearing force can be sufficiently applied to the mixture of the raw material powders, and the reaction between the raw material powders can be promoted. The gap is preferably 0.9mm or less, more preferably 0.8mm or less. The lower limit of the gap is, for example, 100 μm or more, preferably 0.5mm or more.
The power for rotating the rotor is, for example, 0.05kW/g or more based on the total mass of the raw material powder. By increasing the rotational power, the solid-phase reaction between the raw material powders is promoted. The power of the rotation is preferably 0.06kW/g or more, more preferably 0.08kW/g or more, and particularly preferably 0.1kW/g or more. The upper limit of the power for the rotation is not particularly limited, and is, for example, 0.5 kW/g. The number of rotations of the rotor may vary depending on the size of the apparatus, the shape of the rotor, and the like, and the rotational power in the above range is, for example, 2000 to 6000rpm, preferably 3000 to 5000 rpm.
The rotation time of the rotor may be set as appropriate in accordance with the rotational power of the rotor, and is, for example, 5 minutes or more, preferably 10 minutes or more, and more preferably 20 minutes or more. By rotating the rotor for 5 minutes or more (preferably 10 minutes or more), the raw material powder can be sufficiently given a compressive force and a shearing force, and thus the solid phase reaction of the raw material powder advances, and LLZ can be obtained. The upper limit of the rotation time of the rotor is not particularly limited, and if it is too long, the crystallinity of the target compound is rather lowered, and excessive energy is consumed, and therefore, it is preferably 30 minutes or less.
In the mechanochemical treatment, strain energy is accumulated in the raw material powder by shearing, and the energy is released by itself as thermal energy, and thus heat is generated. Therefore, the manufacturing method of the present invention may be carried out without heating by an external heat source. The mechanochemical treatment may be performed in a state of generating heat, or may be performed by cooling with water cooling or the like. In the mechanochemical treatment, the reaching temperature of the cylindrical container may be, for example, 50 ℃ or higher, preferably 130 ℃ or higher, or 500 ℃ or lower.
The atmosphere for the mechanochemical treatment is not particularly limited, and may be an oxygen-containing atmosphere such as the atmosphere, an inert gas atmosphere, or a reducing gas atmosphere. Examples of the inert gas include nitrogen, helium, argon, and the like (particularly, nitrogen gas is preferable), and examples of the reducing gas include a mixed gas of the inert gas (particularly, nitrogen gas) and 3 to 5% hydrogen gas.
The material of the bottomed cylindrical container is not particularly limited, and examples thereof include stainless steel such as SUS304, carbon steel, and the like. Alternatively, coating for preventing impurities from being mixed into the resultant LLZ may be performed. The inner diameter of the container is, for example, 50 to 500 mm. The number of the tip blades may be 1 or more, preferably 2 or more, and usually 8 or less.
The LLZ obtained by mechanochemical treatment using a flux can be sintered after mechanochemical treatment for the purpose of further improving crystallinity or the like. However, since good crystallinity is exhibited even without sintering after the mechanochemical treatment, the sintering temperature can be lowered or the sintering time can be shortened as compared with patent document 1 described above. For example, the sintering temperature is 1300 ℃ or lower (lower limit is, for example, 500 ℃ or higher), and the sintering time is 20 hours or lower (lower limit is, for example, 30 minutes or longer). Further, there is an advantage that composition variation due to volatilization of Li can be suppressed when sintering is not performed or sintering conditions can be alleviated.
In the present invention, the flux may be removed by an acid after the raw material powder is reacted by mechanochemical treatment. As the acid, inorganic acids such as hydrochloric acid and sulfuric acid can be used. In the present invention, as described above, the LLZ synthesized by the mechanochemical method may be further sintered, and when sintering is not performed, it is preferable to remove the flux by an acid particularly after reacting the metal oxide powder by mechanochemical treatment. When sintering is performed after mechanochemical treatment, sintering may be performed in the presence of a flux, and the flux may be removed after sintering. Sintering in the presence of a flux is preferable because a solid-liquid phase reaction at the time of sintering is promoted. The acid treatment may be performed, for example, for 1 to 3 hours, and it is preferable that the acid treatment is followed by washing with pure water and then heating at about 100 to 400 ℃ (preferably 200 to 300 ℃) for 1 hour or more (preferably 2 hours or more, more preferably 3 hours or more, further preferably 4 hours or more, and usually 10 hours or less) to sufficiently remove water.
Among the above-mentioned production methods of the present invention, LLZ obtained without sintering after mechanochemical treatment is a garnet-type composite metal oxide containing Li, La, Zr, and O, and if necessary, at least 1 of Al and Ga, and has good crystallinity, and an aggregate structure of particles (microparticles) is observed by Electron microscopy such as sem (scanning Electron microscope) or stem (scanning Transmission Electron microscope).
Good crystallinity can be expressed by a crystallite diameter calculated from the half-value width of an X-ray diffraction peak by the Scherrer equation shown in the following equation (1).
Dc＝Kλ/βcosθ···(1)
Dc: crystallite diameter, λ: wavelength of X-ray, K: scherrer constant, β: half-value width, θ: bragg angle
The LLZ of the present invention has a crystallite diameter of 30nm or more, preferably 35nm or more, more preferably 40nm or more, and usually 50nm or less.
When the LLZ of the present invention is observed at about 1000 to 5000 times with an electron microscope such as SEM or STEM, for example, the aggregate structure of particles (particles) originating from the particle shape of the raw material powder is observed without sintering at a high temperature. In addition, in the LLZ of the present invention, when observing the major axes of the particles having a particle assembly structure, the major axes of 90% or more of the primary particles are 3 μm or less (preferably 2 μm or less, more preferably 1.5 μm or less, still more preferably 1.3 μm or less, and particularly preferably 1.2 μm or less) on a number basis. More preferably, 100% by number of the particles, that is, all the particles satisfy the above-described range (including the preferable range) of the major axis of the primary particles. On the other hand, the LLZ obtained by the conventional sintering method is different from the LLZ of the present invention in that the interface of the raw material powder disappears to form coarse particles or does not have a particle aggregate structure because the raw material is solid-dissolved at a high temperature, and the particle structure of fine particles such as the LLZ of the present invention cannot be observed. The primary particle is the smallest unit of particles observed, and the longest line segment among line segments passing through the center (center of gravity) of the particle and being divided by the outer periphery of the particle may be the major axis of the primary particle.
When the surface of the LLZ of the present invention is covered with the molten and solidified material, the cross section of the LLZ of the present invention cut at an arbitrary plane is observed with an electron microscope, and the aggregate structure of the particles is observed in the cross section, and the major axes of the particles (minimum units) constituting the aggregate structure are also measured in the cross section.
The LLZ of the present invention may be a garnet-type composite metal oxide containing Li, La, Zr and O, and has a BET specific surface area of 1.5 μm or less. The BET specific surface area diameter of LLZ of the present invention is preferably 1.3 μm or less, more preferably 1.0 μm or less, even more preferably 800nm or less, and the lower limit is, for example, 150nm or more. It is particularly preferable that the LLZ of the present invention not covered with the melt-solidified material satisfies the BET specific surface area diameter. The BET specific surface area diameter of the LLZ of the present invention can be calculated by the same numerical expression as that described in the above-mentioned specific surface area diameter of the raw material powder.
In addition, although the garnet-type composite metal oxide containing Li, La, Zr, and O is generally stable in tetragonal form at room temperature, in the LLZ of the present invention further containing at least 1 of Al and Ga, the crystal system can be made cubic by the cubic stabilization effect of Al and Ga. In addition, when the final product obtained by the production method of the present invention is measured by XRD, the maximum peak area of LLZ is compared with the maximum peak area of La source powder (La is used)2O3As a source of La, La2O3Maximum peak area) to the total of the maximum peak areas of the LLZ is, for example, 20% to 60%.
The LLZ of the present invention can be suitably used as a solid electrolyte material for secondary batteries because of its ion conductivity, and can also be used as a fluorescent material when a part of La sites is substituted with Ce, Eu, or the like.
The application claims priority based on Japanese patent application No. 2018-147004 applied at 8/3/2018 and Japanese patent application No. 2018-161931 applied at 8/30/2018. The entire contents of the specifications of Japanese patent application No. 2018-147004 applied at 8/3/2018 and Japanese patent application No. 2018-161931 applied at 8/30/2018 are incorporated herein by reference.
Examples
The present invention will be described in more detail with reference to examples. The present invention is not limited to the following examples, and it is needless to say that the present invention can be carried out with appropriate modifications within a range that can be adapted to the gist described above and below, and these are included in the technical scope of the present invention.
Example 1
As Li6.25Al0.25La3Zr2O12With the composition of the produced composite metal oxide being Li6.25Al0.25La3Zr2O12Respectively, Li is weighed in a stoichiometric ratio meter2O (purity: 99%, specific surface area S, manufactured by Kabushiki Kaisha high purity chemical research Co., Ltd.)w：2.1m2Per g, specific surface area diameter dBET：1421nm)、La2O3(purity: 99.9%, specific surface area S, manufactured by Kabushiki Kaisha high-purity chemical research Co., Ltd.)w：1.7m2Per g, specific surface area diameter dBET：543nm)、ZrO2(purity: 98%, specific surface area S, manufactured by Kabushiki Kaisha high purity chemical research Co., Ltd.)w：18.4m2Per g, specific surface area diameter dBET：57nm)、Al2O3(purity: 99.99%, specific surface area S, manufactured by Kabushiki Kaisha high-purity chemical research Co., Ltd.)w：11.3m2Per g, specific surface area diameter dBET: 134nm) of the above-mentioned raw materials, and 10 parts by mass of BaF based on 100 parts by mass of the total amount of the raw materials2(purity: 99.99%, specific surface area S)w：9m2Per g, specific surface area diameter dBET: 137nm, melting point: 1280 deg.C) into the grinder shown in FIG. 1. The bottomed cylindrical container 1 was made of SUS304, and had an inner diameter of 80mm, and the gap 4 between the inner periphery of the container 1 and the tip vane 3 of the rotor 2 was set to 0.8 mm. The mechanical chemical treatment was carried out by rotating the mill at 4500rpm for 20 minutes with a power of 3 kW. Note that the arrival temperature of the container was about 260 ℃.
The crystal structure of the obtained sample was analyzed by using an XRD (X-ray Diffraction analysis) apparatus manufactured by Bruker. The measurement is performed with CuK α rays, where λ is 1.5418nm and θ is 10 to 50 °. As a result, tetragonal LLZ in which a part of Li sites was replaced with Al was generated in the obtained sample. Further, the crystallite diameter was determined from the half-value width of the diffraction peak indicating the maximum intensity of XRD based on scherrer equation, and as a result, it was 41 nm. In XRD of the obtained sample, the maximum peak area of LLZ was related to La2O3Maximum peak area of (2) and maximum peak of LLZThe ratio of the total area was 54%.
Example 2
As Li6.25Ga0.25La3Zr2O12With the composition of the produced composite metal oxide being Li6.25Ga0.25La3Zr2O12Respectively, Li is weighed in a stoichiometric ratio meter2O (purity: 99%, specific surface area S, manufactured by Kabushiki Kaisha high purity chemical research Co., Ltd.)w：2.1m2Per g, specific surface area diameter dBET：1421nm)、La2O3(purity: 99.9%, specific surface area S, manufactured by Kabushiki Kaisha high-purity chemical research Co., Ltd.)w：1.7m2Per g, specific surface area diameter dBET：543nm)、ZrO2(purity: 98%, specific surface area S, manufactured by Kabushiki Kaisha high purity chemical research Co., Ltd.)w：18.4m2Per g, specific surface area diameter dBET：57nm)、Ga2O3(purity: 99.99%, specific surface area S, manufactured by Kabushiki Kaisha high-purity chemical research Co., Ltd.)w：10.4m2Per g, specific surface area diameter dBET: 90nm) of the powder amounted to 30 g. Then, these raw materials and 10 parts by mass of BaF per 100 parts by mass of the total amount of these raw materials were mixed2(purity: 99.99%, specific surface area S)w：9m2Per g, specific surface area diameter dBET: 137nm, melting point: 1280 deg.C) into the grinder shown in FIG. 1. The conditions of the mill were the same as in example 1, and mechanochemical treatment was performed. Note that the arrival temperature of the container was about 260 ℃.
The crystal structure of the obtained sample was measured in the same manner as in example 1, and as a result, in the obtained sample, tetragonal LLZ in which a part of Li sites was substituted with Ga was generated. Further, the crystallite diameter was determined from the half-value width of the diffraction peak indicating the maximum intensity of XRD based on scherrer equation, and as a result, it was 39 nm. In XRD of the obtained sample, the maximum peak area of LLZ was related to La2O3The ratio of the maximum peak area of (a) to the total of the maximum peak areas of LLZ was 43%.
Using MICROMERICS ASAP2010, the obtained sample was sampledThe specific surface area is calculated from the nitrogen adsorption amount of (2), and the specific surface area diameter is determined from the BET specific surface area and the density of the sample. As a result, the specific surface area was 1.8m2The specific surface area is 652 nm.
Example 3
Except that the composition of the resulting composite metal oxide is Li5.5Ga0.5La3Zr2O12The mechanochemical treatment was carried out in the same manner as in example 2 except that the raw material powder was weighed by the stoichiometric ratio meter and the power of the grinding mill was 2.5 kW. Note that the arrival temperature of the container was about 260 ℃.
The crystal structure of the obtained sample was measured in the same manner as in example 1, and as a result, in the obtained sample, LLZ of cubic crystal in which a part of Li sites was substituted with Ga was generated. Further, the crystallite diameter was determined from the half-value width of the diffraction peak indicating the maximum intensity of XRD based on scherrer equation, and as a result, it was 31 nm. In XRD of the obtained sample, the maximum peak area of LLZ was related to La2O3The ratio of the maximum peak area of (a) to the total of the maximum peak areas of LLZ was 24%.
The specific surface area was calculated from the nitrogen adsorption amount of the obtained sample using MICROMERITICS ASAP2010, and the specific surface area diameter was determined from the BET specific surface area and the density of the sample. As a result, the specific surface area was 4.2m2In terms of a specific surface area of 280nm in diameter.
Example 4
As Li5.5Ga0.5La3Zr2O12With the composition of the produced composite metal oxide being Li5.5Ga0.5La3Zr2O12Respectively, Li is weighed in a stoichiometric ratio meter2O (purity: 99%, specific surface area S, manufactured by Kabushiki Kaisha high purity chemical research Co., Ltd.)w：2.1m2Per g, specific surface area diameter dBET：1421nm)、La2O3(purity: 99.9%, specific surface area S, manufactured by Kabushiki Kaisha high-purity chemical research Co., Ltd.)w：1.7m2Per g, specific surface area diameter dBET：543nm)、ZrO2(Kabushiki Kaisha)High purity chemical research system, purity: 98% of specific surface area Sw：18.4m2Per g, specific surface area diameter dBET：57nm)、Ga2O3(purity: 99.99%, specific surface area S, manufactured by Kabushiki Kaisha high-purity chemical research Co., Ltd.)w：10.4m2Per g, specific surface area diameter dBET: 90nm) of the powder amounted to 30 g. Next, these raw materials and LiCl (purity: 99.99%, specific surface area S) in an amount of 10 parts by mass based on 100 parts by mass of the total amount of these raw materials were mixedw：1.9m2Per g, specific surface area diameter dBET: 1504nm, melting point: 613 deg.C) was charged into the attritor shown in FIG. 1. The bottomed cylindrical container 1 was made of SUS304, and its inner diameter was 80mm, and the gap 4 between the inner periphery of the container 1 and the tip vane 3 of the rotor 2 was set to 0.8 mm. The mill was rotated at 4274rpm and 3kW of required power for 6 minutes to conduct mechanochemical treatment. Note that the arrival temperature of the container was about 65 ℃.
The crystal structure of the obtained sample was analyzed by using an XRD (X-ray Diffraction analysis) apparatus manufactured by Bruker. The measurement is performed with CuK α rays, where λ is 1.5418nm and θ is 10 to 50 °. As a result, as shown in fig. 4, cubic LLZ (a part of Li sites is substituted by Ga) was generated in the obtained sample. Further, from the XRD pattern, the area of the maximum peak of LLZ relative to the area of the maximum peak of LLZ and La were calculated2O3The ratio of the total of the maximum peak areas of (a) to (b) was 29%. Further, the crystallite diameter was determined from the half-value width of the diffraction peak indicating the maximum intensity of LLZ based on the Shehler equation, and was found to be 33.6 nm.
When the obtained LLZ was cut into a cross section (magnification: 15000 times) by STEM (HD-2700) manufactured by Hitachi High-Technologies Corporation, it was confirmed that the structure was a particle aggregate structure and the major axis of the primary particles constituting the particles was 3 μm or less as shown in FIG. 5 (a). In fig. 5, the portion having a high contrast (black or gray) is a melt-solidified material.
Example 5
Mechanochemical treatment (4446 rpm) was carried out under the same conditions as in example 4, except that the rotation time of the attritor was set to 20 minutes. The container of the grinding mill reaches a temperature of about 290 ℃.
The crystal structure and the ratio of formation of LLZ of the obtained sample were evaluated in the same manner as in example 4, and as a result, LLZ of cubic crystal in which a part of Li sites was replaced with Ga was formed (fig. 4), and the maximum peak area of LLZ relative to the maximum peak area of LLZ and La were observed2O3The ratio of the total of the maximum peak areas of (a) to (b) is 37%. Further, from the half width of the diffraction peak showing the maximum intensity of LLZ, the crystallite diameter calculated based on the Sheer equation was 32.5 nm.
When the obtained LLZ was cut into a cross section (magnification: 25000 times) by STEM (HD-2700) manufactured by Hitachi High-Technologies Corporation, it was confirmed that the structure was a particle aggregate structure and the major axis of the primary particles constituting the particles was 3 μm or less as shown in FIG. 5 (b).
Comparative example 1
Except without using BaF2Except for this, mechanochemical treatment was performed in the same manner as in example 1. The crystal structure of the obtained sample was measured in the same manner as in example 1, and as a result, only diffraction peaks attributable to the raw material powder were detected, and LLZ could not be obtained.
Comparative example 2
As Y2.97Al5O12:Ce3+ 0.03With the composition of the phosphor produced as Y2.97Al5O12:Ce3+ 0.03Respectively weighing Y2O3、CeO2、Al2O3(all raw materials were manufactured by high purity chemical research of Kabushiki Kaisha) in total of 30 g. Then, these raw materials and 6 parts by mass of BaF per 100 parts by mass of the total amount of these raw materials were mixed2And (4) putting into a grinder. The bottomed cylindrical container 1 was made of SUS304, and had an inner diameter of 80mm, and a gap 4 between the inner periphery of the container 1 and the tip blade of the rotor 2 was set to 1.0 mm. The mechanical chemical treatment was carried out by rotating the mill at 4500rpm for 10 minutes with a power of 3 kW.
The crystal structure of the obtained sample was analyzed by using an XRD apparatus manufactured by Bruker. The measurement is performed with CuK α rays, where λ is 1.5418nm and θ is 10 to 50 °. As a result, a YAG phase was obtained in the crystal of the obtained sample. The crystallite size was determined from the half-value width of the XRD diffraction peak of the YAG phase, and was found to be 26 nm.
The results of the above examples and comparative examples are shown in table 1.
[ Table 1]
In addition, XRD diffractograms of examples 1 and 2 are shown in fig. 2, and XRD diffractograms of examples 4 and 5 are shown in fig. 4.
As is clear from Table 1, in examples 1 to 5 in which LLZ was produced by mechanochemical treatment using a flux, LLZ having excellent crystallinity, that is, having a crystallite diameter of 30nm or more, could be produced. As can be seen from fig. 2 and 4, LLZ was formed in examples 1, 2, 4 and 5. Further, fig. 3 shows SEM observation images of LLZ obtained in example 1, and fig. 5 shows cross-sectional STEM observation images of LLZ obtained in examples 4 and 5. As is clear from FIGS. 3 and 5, LLZ of the present invention has a particle assembly structure, and the major axis of the primary particles is 3 μm or less. On the other hand, in comparative example 1 in which no flux was used, the powder remained as the raw material powder after the mechanochemical treatment, and no LLZ was produced. In comparative example 2 in which the YAG phosphor was produced by the mechanochemical treatment, the YAG phase was obtained, but the good crystallinity as in the present invention could not be achieved.
Industrial applicability
The garnet-type composite metal oxide of the present invention can be suitably used as a solid electrolyte material for a secondary battery, a fluorescent material, or the like.
Description of the reference numerals
1 bottomed cylindrical container
2 rotor
3 front end blade
4 gap
5 mixture of raw material powder and flux
Claims (11)
1. A process for producing a garnet-type composite metal oxide, which comprises Li, La, Zr and O,
wherein a mixture containing a raw material powder containing a Li source powder, a La source powder, and a Zr source powder and a flux is treated by a mechanochemical method to react the raw material powder.
2. The manufacturing method according to claim 1, wherein the raw material powder further contains at least one of an Al source powder and a Ga source powder.
3. The production method according to claim 1 or 2, wherein the crystallite diameter of the garnet-type composite metal oxide is 30nm or more.
4. The production method according to claim 2 or 3, wherein a crystal system of the garnet-type composite metal oxide is a cubic crystal.
5. The manufacturing method according to any one of claims 1 to 4, comprising:
a bottomed cylindrical container, and
a rotor having a front end blade having a curvature smaller than an inner circumference of the vessel;
a predetermined gap is provided between the front end blade and the inner periphery of the vessel,
by rotating the rotor, the mixture containing the raw material powder and the flux is sheared while being compressed in the gap.
6. The production method according to claim 5, wherein the rotor is rotated for 10 minutes or longer while the power of the rotor is 0.05kW/g or more relative to the total amount of the raw material powder.
7. The production method according to any one of claims 1 to 6, wherein heating by an external heat source is not performed.
8. A garnet-type composite metal oxide comprising Li, La, Zr and O,
the diameter of the microcrystal is more than 30nm,
the particles have a particle assembly structure, and the major axis of 90% or more of the primary particles on a number basis is 3 μm or less.
9. A garnet-type composite metal oxide comprising Li, La, Zr and O,
the BET specific surface area diameter is 1.5 μm or less.
10. The garnet-type composite metal oxide according to claim 8 or 9, further comprising at least one of Al and Ga, and the crystal system is cubic.
11. A solid electrolyte material for a secondary battery comprising the garnet-type composite metal oxide as set forth in claim 10.
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