Method of producing LTP or LATP crystal particle

Abstract

The present disclosure is to provide a method of producing a LTP or LATP crystal particle that has reduced impurity contamination, high crystallinity, and excellent dispersibility. The method of producing a LTP or LATP crystal particle according to the present disclosure includes: preparing glass containing, in molar ratio, 1+x of Li.sub.2O, where 0x1, x of Al.sub.2O.sub.3, 42x of TiO.sub.2, 3+y of P.sub.2O.sub.5, where 1y4, and from more than y to less than 3y of ZnO; subjecting, after the preparation of glass, the glass to thermal treatment for crystallization; and selectively eluting a substance other than a LTP or LATP crystal through acid treatment.

Claims

1. A method of producing a crystal of lithium-based composite oxide represented by Formula (I) shown below
Li.sub.1+xAl.sub.xTi.sub.2x(PO.sub.4).sub.3(0x1.0)(I) the method comprising: mixing and heating glass materials to produce melt; rapidly cooling the melt to obtain a granulated glass containing, in molar ratio, 1+x of Li.sub.2O, where 0x1, x of Al.sub.2O.sub.3, 42x of TiO.sub.2, 3+y of P.sub.2O.sub.5, where 1y4, and more than y and less than 3y of ZnO; thermally treating the granulated glass to obtain a crystallized glass which includes a crystal of lithium-based composite oxide and a crystal of zinc pyrophosphate; immersing the crystallized glass in an acid solution to elute a substance which includes the crystal of zinc pyrophosphate and is other than the crystal of lithium-based composite oxide, and separating the crystal of lithium-based composite oxide from the acid solution containing the eluted substance.

2. The method according to claim 1, wherein the molar ratio of ZnO in the glass is more than y and 2y or less.

3. The method according to claim 1, wherein the crystal of lithium-based composite oxide separated from the acid solution is a single-phase crystal of lithium-based composite oxide.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) In the accompanying drawings:

(2) FIG. 1 illustrates an X-ray diffraction pattern of crystallized glass in a process of preparing a LATP crystal particle of Example 1;

(3) FIG. 2 illustrates an X-ray diffraction pattern of crystallized glass in a process of preparing a LATP crystal particle of Example 2;

(4) FIG. 3 illustrates an X-ray diffraction pattern of crystallized glass in a process of preparing a LATP crystal particle of Example 3;

(5) FIG. 4 illustrates an X-ray diffraction pattern of crystallized glass in a process of preparing a LATP crystal particle of Comparative Example 1;

(6) FIG. 5 illustrates an X-ray diffraction pattern of crystallized glass in a process of preparing a LATP crystal particle of Comparative Example 2;

(7) FIG. 6 illustrates an X-ray diffraction pattern of crystallized glass in a process of preparing a LATP crystal particle of Comparative Example 3;

(8) FIG. 7 illustrates an X-ray diffraction pattern of a LATP crystal particle of Example 1;

(9) FIG. 8 illustrates an X-ray diffraction pattern of a LATP crystal particle of Example 2;

(10) FIG. 9 illustrates an X-ray diffraction pattern of a LATP crystal particle of Example 3;

(11) FIG. 10 illustrates an X-ray diffraction pattern of a LATP crystal particle of Comparative Example 1;

(12) FIG. 11 illustrates an X-ray diffraction pattern of a LATP crystal particle of Comparative Example 2;

(13) FIG. 12 illustrates an X-ray diffraction pattern of a LATP crystal particle of Comparative Example 3;

(14) FIG. 13 illustrates a backscattered electron image of a LATP crystal particle of Example 1;

(15) FIG. 14 illustrates a backscattered electron image of a LATP crystal particle of Example 2;

(16) FIG. 15 illustrates a backscattered electron image of a LATP crystal particle of Example 3;

(17) FIG. 16 illustrates a backscattered electron image of a LATP crystal particle of Comparative Example 1;

(18) FIG. 17 illustrates a backscattered electron image of a LATP crystal particle of Comparative Example 2;

(19) FIG. 18 illustrates a backscattered electron image of a LATP crystal particle of Comparative Example 3;

(20) FIG. 19 illustrates an EDS spectrum of a LATP crystal particle of Example 1;

(21) FIG. 20 illustrates an EDS spectrum of a LATP crystal particle of Example 2;

(22) FIG. 21 illustrates an EDS spectrum of a LATP crystal particle of Example 3;

(23) FIG. 22 illustrates an EDS spectrum of a LATP crystal particle of Comparative Example 1;

(24) FIG. 23 illustrates an EDS spectrum of a LATP crystal particle of Comparative Example 2; and

(25) FIG. 24 illustrates an EDS spectrum of a LATP crystal particle of Comparative Example 3.

DETAILED DESCRIPTION

(26) A description is given in detail below of a method of producing a LTP or LATP crystal particle according to one of embodiments of the present disclosure.

(27) The method of producing a LTP or LATP crystal particle according to the present embodiment uses respective materials, such as oxide, hydroxide, carbonate, nitrate, and phosphate, that, when vitrified, correspond to components given as Li.sub.2O, Al.sub.2O.sub.3, TiO.sub.2, P.sub.2O.sub.5, and ZnO.

(28) <Li.sub.2O>

(29) Li.sub.2O is a component that constitutes a LTP or LATP crystal, and the molar ratio of Li.sub.2O, when vitrified, is 1+x. Due to the relation with Al.sub.2O.sub.3 and TiO.sub.2, x ranges from 0 to 1 inclusive. When x is more than 1, the LATP crystal structure may collapse. Preferably, x is 0.8 or less. More preferably, x is 0.6 or less. As materials of the Li.sub.2O component, phosphate, such as LiPO.sub.3, and carbonate, such as Li.sub.2CO.sub.3, are used, for example.

(30) <Al.sub.2O.sub.3>

(31) Al.sub.2O.sub.3 is a component that constitutes a LATP crystal, and the molar ratio of Al.sub.2O.sub.3, when vitrified, is x. As materials of the Al.sub.2O.sub.3 component, phosphate, such as Al(PO.sub.3).sub.3, and hydroxide, such as Al(OH).sub.3, are used, for example.

(32) <TiO.sub.2>

(33) TiO.sub.2 is a component that constitutes a LTP or LATP crystal, and the molar ratio of TiO.sub.2, when vitrified, is 42x. As materials of the TiO.sub.2 component, phosphate, such as TiP.sub.2O.sub.7, and oxide, such as TiO.sub.2, are used, for example.

(34) <P.sub.2O.sub.5>

(35) P.sub.2O.sub.5 is a component that constitutes a LTP or LATP crystal and that also constitutes zinc pyrophosphate, which is precipitated during thermal treatment performed after vitrification. The molar ratio of P.sub.2O.sub.5, when vitrified, is 3+y. Due to the relation with Li.sub.2O, Al.sub.2O.sub.3, and TiO.sub.2, y ranges from 1 to 4 inclusive. When y is less than 1, vitrification is difficult. When y is more than 4, glass loses stability, and precipitation of a crystal through thermal treatment, performed after vitrification, is difficult. Preferably, y ranges from 1.5 to 3.5 inclusive. More preferably, y ranges from 2 to 3 inclusive. As materials of the P.sub.2O.sub.5 component, the aforementioned phosphate, acid, such as H.sub.3PO.sub.4, and oxide, such as P.sub.2O.sub.5, are used, for example.

(36) <ZnO>

(37) ZnO is a component that constitutes zinc pyrophosphate, which is precipitated during thermal treatment performed after vitrification, and the molar ratio of ZnO, when vitrified, ranges from more than y to less than 3y. When the molar ratio of ZnO is y or less, in addition to a LTP or LATP crystal, a titanium pyrophosphate crystal, which is not eluted by acid, may be precipitated during thermal treatment performed after vitrification. When the molar ratio of ZnO is 3y or more, although a zinc phosphate crystal and a zinc pyrophosphate crystal, which may be eluted by acid, are precipitated during thermal treatment performed after vitrification, Zn may be partially introduced into a LTP or LATP crystal and remain as an impurity. Preferably, the molar ratio of ZnO ranges from more than y to 2y or less. By setting the molar ratio of ZnO to be 2y or less, a sub-phase other than a zinc pyrophosphate crystal is reduced at the stage of crystallized glass, and impurities are less likely to remain in a LTP or LATP crystal particle. As materials of the ZnO component, phosphate, such as Zn(PO.sub.3).sub.2, and oxide, such as ZnO, are used, for example.

(38) <Preparation of Glass>

(39) As glass materials, oxide, hydroxide, carbonate, nitrate, phosphate, or the like, which are the materials corresponding to the components, are weighed according to predetermined percentages and mixed fully. Subsequently, the mixed materials are introduced into, for example, a platinum crucible that is not reactive the glass materials and others, are stirred timely while melt by heating the materials to from 1200 to 1500 C. in an electric furnace, and after that, are clarified and homogenized in the electric furnace. Then, the melt is poured into a tank filled with sufficient water and granulated and rapidly cooled. Thus, glass is prepared.

(40) <Thermal Treatment>

(41) Subsequently, the prepared glass is subject to thermal treatment in two steps each conducted for from 10 to 30 hours, with first step at from 400 to 600 C. and the second step at from 700 to 900 C. The thermal treatment is conducted to obtain crystallized glass inside which a LTP or LATP crystal particle and mainly a zinc pyrophosphate crystal as an eluted phase are precipitated, and after acid treatment which is described below, a LTP or LATP crystal particle having a diameter of from 0.1 to 10 m is obtained.

(42) <Acid Treatment>

(43) Furthermore, the obtained crystallized glass is subject to acid treatment by immersing the crystallized glass in 1 to 5N nitric acid or 1 to 5N hydrochloric acid at from 30 to 90 C. for 3 to 24 hours. During the immersion, stirring with a stirrer or the like is preferably conducted. By the acid treatment, an eluted phase, other than a LTP or LATP crystal, that is mainly composed of a zinc pyrophosphate crystal is eluted. After the acid treatment, a LTP or LATP crystal is separated from an acid solution with use of a filter paper or the like, and thus, a LTP or LATP crystal particle having a diameter of from 0.1 to 10 m is obtained.

(44) According to the method of manufacturing a LTP or LATP crystal particle of the present embodiment configured as above, since mainly the zinc pyrophosphate crystal is precipitated as the eluted phase at the time of vitrification, solubility of the eluted phase with respect to acid is higher than before, and this prevents residual components to be eluted in the acid treatment. Accordingly, impurity contamination is reduced, and manufacturing of a LTP or LATP crystal particle having high crystallinity and excellent dispersibility is allowed.

(45) Furthermore, according to the method of manufacturing a LTP or LATP crystal particle of the present embodiment, when the molar ratio of ZnO in the glass materials ranges from more than y to 2y or less, impurities are even less likely to remain in a LTP or LATP crystal particle.

EXAMPLES

(46) A description is given below of a method of manufacturing a LTP or LATP crystal particle according to the present disclosure with reference to Examples and Comparative Examples. However, the present disclosure is not limited to these Examples.

Example 1

(47) By using LiPO.sub.3, Al(PO.sub.3).sub.3, Zn(PO.sub.3).sub.2, TiO.sub.2, and ZnO as materials, glass composed, in molar ratio, of 1.2 of Li.sub.2O, 0.2 of Al.sub.2O.sub.3, 3.6 of TiO.sub.2, 6 of P.sub.2O.sub.5, and 6 of ZnO was prepared. That is to say, glass according to the above embodiment in which x=0.2, y=3, and ZnO was 2y in molar ratio was prepared. Subsequently, the prepared glass was subject to thermal treatment in two steps, the first step at 520 C. for 20 hours and the second step at 850 C. for 20 hours, and thus, crystallized glass was obtained. The crystallized glass was subject to acid treatment by immersing the crystallized glass in 5N nitric acid at 60 C. for 12 hours, and subsequently, particles were collected by filtering to obtain LATP crystal particles of Example 1.

Example 2

(48) By using LiPO.sub.3, Al(PO.sub.3).sub.3, Zn(PO.sub.3).sub.2, TiO.sub.2, and ZnO as materials, glass composed, in molar ratio, of 1.3 of Li.sub.2O, 0.3 of Al.sub.2O.sub.3, 3.4 of TiO.sub.2, 5 of P.sub.2O.sub.5, and 4 of ZnO was prepared. That is to say, glass according to the above embodiment in which x=0.3, y=2, and ZnO was 2y in molar ratio was prepared. Subsequently, the prepared glass was subject to thermal treatment in two steps, the first step at 480 C. for 20 hours and the second step at 820 C. for 20 hours, and thus, crystallized glass was obtained. The crystallized glass was subject to acid treatment by immersing the crystallized glass in 3N hydrochloric acid at 60 C. for 12 hours, and subsequently, particles were collected by filtering to obtain LATP crystal particles of Example 2.

Example 3

(49) By using LiPO.sub.3, Al(PO.sub.3).sub.3, Zn(PO.sub.3).sub.2, TiO.sub.2, and ZnO as materials, glass composed, in molar ratio, of 1.4 of Li.sub.2O, 0.4 of Al.sub.2O.sub.3, 3.2 of TiO.sub.2, 6 of P.sub.2O.sub.5, and 7 of ZnO was prepared. That is to say, glass according to the above embodiment in which x=0.4, y=3, and ZnO was 2.3y in molar ratio was prepared. Subsequently, the prepared glass was subject to thermal treatment in two steps, the first step at 470 C. for 20 hours and the second step at 790 C. for 20 hours, and thus, crystallized glass was obtained. The crystallized glass was subject to acid treatment by immersing the crystallized glass in 3N hydrochloric acid at 60 C. for 12 hours, and subsequently, particles were collected by filtering to obtain LATP crystal particles of Example 3.

Comparative Example 1

(50) By using LiPO.sub.3, Al(PO.sub.3).sub.3, Ca(PO.sub.3).sub.2, TiO.sub.2, and CaCO.sub.3 as materials, glass composed, in molar ratio, of 1.3 of Li.sub.2O, 0.3 of Al.sub.2O.sub.3, 3.4 of TiO.sub.2, 5.2 of P.sub.2O.sub.5, and 6.6 of CaO was prepared. Subsequently, the prepared glass was subject to thermal treatment in two steps, the first step at 580 C. for 20 hours and the second step at 700 C. for 12 hours, and thus, crystallized glass was obtained. The crystallized glass was subject to acid treatment by immersing the crystallized glass in 5N nitric acid at 60 C. for 12 hours, and subsequently, filtering was conducted to obtain a porous body. The obtained porous body was milled in a ball mill for 12 hours, and LATP crystal particles of Comparative Example 1 were obtained.

Comparative Example 2

(51) By using LiPO.sub.3, Al(PO.sub.3).sub.3, Zn(PO.sub.3).sub.2, TiO.sub.2, and ZnO as materials, glass composed, in molar ratio, of 1.4 of Li.sub.2O, 0.4 of Al.sub.2O.sub.3, 3.2 of TiO.sub.2, 6 of P.sub.2O.sub.5, and 9 of ZnO was prepared. That is to say, glass according to the above embodiment in which x=0.4, y=3, and ZnO was 3y in molar ratio was prepared. Subsequently, the prepared glass was subject to thermal treatment in two steps, the first step at 460 C. for 20 hours and the second step at 810 C. for 20 hours, and thus, crystallized glass was obtained. The crystallized glass was subject to acid treatment by immersing the crystallized glass in 5N nitric acid at 60 C. for 12 hours, and subsequently, particles were collected by filtering to obtain LATP crystal particles of Comparative Example 2.

Comparative Example 3

(52) By using LiPO.sub.3, Al(PO.sub.3).sub.3, Zn(PO.sub.3).sub.2, TiP.sub.2O.sub.7, and TiO.sub.2 as materials, glass composed, in molar ratio, of 1.4 of Li.sub.2O, 0.4 of Al.sub.2O.sub.3, 3.2 of TiO.sub.2, 6 of P.sub.2O.sub.5, and 3 of ZnO was prepared. That is to say, glass according to the above embodiment in which x=0.4, y=3, and ZnO was y in molar ratio was prepared. Subsequently, the prepared glass was subject to thermal treatment in two steps, the first step at 440 C. for 20 hours and the second step at 790 C. for 20 hours, and thus, crystallized glass was obtained. The crystallized glass was subject to acid treatment by immersing the crystallized glass in 5N nitric acid at 60 C. for 12 hours, and subsequently, particles were collected by filtering to obtain LATP crystal particles of Comparative Example 3.

Comparative Example 4

(53) By using LiPO.sub.3, Al(PO.sub.3).sub.3, Zn(PO.sub.3).sub.2, TiO.sub.2, and ZnO as materials, glass composed, in molar ratio, of 1.2 of Li.sub.2O, 0.2 of Al.sub.2O.sub.3, 3.6 of TiO.sub.2, 8 of P.sub.2O.sub.5, and 12 of ZnO was prepared. That is to say, glass according to the above embodiment in which x=0.2, y=5, and ZnO was 2.4y in molar ratio was prepared. Although the prepared glass was subject to thermal treatment at a melting point or less, no crystal was precipitated.

Comparative Example 5

(54) By using LiPO.sub.3, Al(PO.sub.3).sub.3, Zn(PO.sub.3).sub.2, TiP.sub.2O.sub.7, and TiO.sub.2 as materials, a melt composed, in molar ratio, of 1.1 of Li.sub.2O, 0.1 of Al.sub.2O.sub.3, 3.8 of TiO.sub.2, 3.5 of P.sub.2O.sub.5, and 1 of ZnO was prepared. Although granulated and rapidly cooled, the prepared melt was not vitrified. That is to say, with the molar ratio of x=0.1, y=0.5, and ZnO was 2y in the above embodiment, glass was not prepared.

(55) <X-Ray Diffraction Spectra of Crystallized Glass>

(56) By using an X-ray diffractometer Ultima IV (manufactured by Rigaku Co., Ltd.), X-ray diffraction spectra of crystallized glass in the process of preparing the LATP crystal particles of Examples 1 to 3 and Comparative Examples 1 to 3 were measured. FIGS. 1 to 3 and FIGS. 4 to 6 respectively illustrate the X-ray diffraction spectra of Examples 1 to 3 and Comparative Examples 1 to 3. As illustrated in FIGS. 1 and 2, it has been found that LATP crystals and zinc pyrophosphate crystals are precipitated in Examples 1 and 2. As illustrated in FIG. 3, it has been found that LATP crystals, zinc pyrophosphate crystals, and partially, sub-phases are precipitated in Example 3. As illustrated in FIG. 4, it has been found that LATP crystals, calcium phosphate crystals, and sub-phases are precipitated in Comparative Example 1. As illustrated in FIG. 5, it has been found that LATP crystals, zinc phosphate crystals, and sub-phases are precipitated in Comparative Example 2. As illustrated in FIG. 6, it has been found that LATP crystals, titanium pyrophosphate crystals, and sub-phases are precipitated in Comparative Example 3.

(57) <X-Ray Diffraction Spectra of LATP Crystal Particles>

(58) By using the X-ray diffractometer Ultima IV (manufactured by Rigaku Co., Ltd.), X-ray diffraction spectra of LATP crystal particles of Examples 1 to 3 and Comparative Examples 1 to 3 were measured. FIGS. 7 to 9 and FIGS. 10 to 12 respectively illustrate the X-ray diffraction spectra of Examples 1 to 3 and Comparative Examples 1 to 3. As illustrated in FIGS. 7 to 9, it has been found that the LATP crystal particles of Examples 1 to 3 are single-phase LATP crystals. As illustrated in FIGS. 10 and 11, it has been found that sub-phase peaks are observed in the LATP crystal particles of Comparative Examples 1 and 2 and that these LATP crystal particles are not single-phase LATP crystals. As illustrated in FIG. 12, it has been found that a titanium pyrophosphate peak and a sub-phase peak are observed in the LATP crystal particles of Comparative Example 3 and that these LATP crystal particles are not single-phase LATP crystals.

(59) <Backscattered Electron Images of LATP Crystal Particles>

(60) By using a scanning electron microscope S-3400N (manufactured by Hitachi High Technologies Co., Ltd.), backscattered electron images of the LATP crystal particles of Examples 1 to 3 and Comparative Examples 1 to 3 were studied. FIGS. 13 to 15 and FIGS. 16 to 18 respectively illustrate the backscattered electron images of Examples 1 to 3 and Comparative Examples 1 to 3. As illustrated in FIGS. 13 to 15, the LATP crystal particles of Examples 1 to 3 have a quadrangular prism-like shape having high crystallinity, with no agglomeration observed. As illustrated in FIG. 16, the LATP crystal particles of Comparative Example 1 have a shape having no sharp edges and having low crystallinity, with partial agglomeration observed. As illustrated in FIG. 17, the LATP crystal particles of Comparative Example 2 are observed to have a shape having no sharp edges and having low crystallinity. As illustrated in FIG. 18, the LATP crystal particles of Comparative Example 3 are generally observed to have a shape having no sharp edges and having low crystallinity, although partially observed to have a shape having high crystallinity.

(61) <EDS Spectra of LATP Crystal Particles>

(62) By using an energy-dispersive X-ray analysis device INCA Energy manufactured by Oxford Instruments Plc.), EDS spectra of the LATP crystal particles of Examples 1 to 3 and Comparative Examples 1 to 3 were measured. FIGS. 19 to 21 and FIGS. 22 to 24 respectively illustrate the EDS spectra of Examples 1 to 3 and Comparative Examples 1 to 3. As illustrated in FIGS. 19 to 21, in the LATP crystal particles of Examples 1 to 3, an element other than the elements constituting the LATP crystals is not detected. As illustrated in FIG. 22, in the LATP crystal particles of Comparative Example 1, in addition to the elements constituting the LATP crystals, Ca is detected. As illustrated in FIGS. 23 and 24, in the LATP crystal particles of Comparative Examples 2 and 3, in addition to the elements constituting the LATP crystals, Zn is detected.

(63) Although the present disclosure has been described based on the drawings and the embodiment, it is to be noted that a variety of changes and modifications may be made by a person skilled in the art. It is therefore to be noted that these changes and modifications are included in the scope of the present disclosure.