SOLID ELECTROLYTE POWDER, ALL-SOLID-STATE LITHIUM ION SECONDARY BATTERY, AND METHOD OF MANUFACTURING SOLID ELECTROLYTE POWDER

Abstract

A solid electrolyte powder includes ion-conductive LATP powder that is obtained by heating and melting raw materials at a predetermined temperature to prepare molten LATP mixture, cooling the molten LATP mixture to prepare a crystalline material having a NASICON structure, crushing the crystalline material to prepare crystal powder having a particle size of 1 μm to 10 μm, and performing a heat treatment on the crystal powder in air at a temperature of 800° C. to 1000° C. for a predetermined period of time.

Claims

1. A solid electrolyte powder comprising: ion-conductive LATP powder that is obtained by heating and melting raw materials at a predetermined temperature to prepare molten LATP mixture, cooling the molten LATP mixture to prepare a crystalline material having a NASICON structure, crushing the crystalline material to prepare crystal powder having a particle size of 1 μm to 10 μm, and performing a heat treatment on the crystal powder in air at a temperature of 800° C. to 1000° C. for a predetermined period of time.

2. The solid electrolyte powder according to claim 1, wherein a crystallite size on a predetermined lattice plane of the LATP powder after the heat treatment is 500 nm or less.

3. The solid electrolyte powder according to claim 1, comprising: secondary powder having a particle size of 100 nm to 1000 nm that is obtained by crushing the LATP powder.

4. The solid electrolyte powder according to claim 3, comprising: tertiary powder that is obtained by performing a heat treatment again on the secondary powder at a temperature of 300° C. to 700° C. for a predetermined period of time.

5. The solid electrolyte powder according to claim 1, wherein a composition of the LATP powder is represented by Li.sub.1+xAl.sub.xTi.sub.2−x(PO.sub.4).sub.3, and x satisfies 0<x≦0.5.

6. The solid electrolyte powder according to claim 2, wherein a composition of the LATP powder is represented by Li.sub.1+xAl.sub.xTi.sub.2−x(PO.sub.4).sub.3, and x satisfies 0<x≦0.5.

7. The solid electrolyte powder according to claim 3, wherein a composition of the LATP powder is represented by Li.sub.1+xAl.sub.xTi.sub.2−x(PO.sub.4).sub.3, and x satisfies 0<x≦0.5.

8. The solid electrolyte powder according to claim 4, wherein a composition of the LATP powder is represented by Li.sub.1+xAl.sub.xTi.sub.2−x(PO.sub.4).sub.3, and x satisfies 0<x≦0.5.

9. An all-solid-state lithium ion secondary battery wherein that uses the solid electrolyte powder according to claim 1.

10. A method of manufacturing solid electrolyte powder comprising: heating and melting raw materials at a predetermined temperature to prepare molten LATP mixture; naturally cooling the molten LATP mixture to prepare a crystalline material having a NASICON structure; crushing the crystalline material to prepare crystal powder having a particle size of 1 μm to 10 μm; and performing a heat treatment on the crystal powder in air at a temperature of 800° C. to 1000° C. for a predetermined period of time to prepare ion-conductive LATP powder.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0023] FIG. 1 is a schematic diagram showing a configuration of an all-solid-state lithium ion secondary battery according to an embodiment of the present invention;

[0024] FIG. 2 is a graph showing the results of X-ray diffraction in Example 1;

[0025] FIG. 3 is a graph showing the results of X-ray diffraction in Example 2;

[0026] FIG. 4 is a graph showing the results of X-ray diffraction in Comparative Example 1;

[0027] FIG. 5 is a graph showing a relationship between a temperature of a heat treatment during the preparation of LATP powder and a crystallite size; and

[0028] FIG. 6 is a graph showing a relationship between a crystallite size and an ion conductance.

DETAILED DESCRIPTION OF THE DISCLOSURE

[0029] Hereinafter, a solid electrolyte powder, an all-solid-state lithium ion secondary battery, and a method of manufacturing solid electrolyte powder according to an embodiment of the present invention will be described with reference to the drawings.

Configuration of All-Solid-State Lithium Ion Secondary Battery

[0030] FIG. 1 is a schematic diagram showing a configuration of an all-solid-state lithium ion secondary battery 10 according to the embodiment. The all-solid-state lithium ion secondary battery 10 has a configuration in which a negative electrode layer 13, a solid electrolyte layer 14, and a positive electrode layer 15 are formed between a pair of a negative electrode current collector 11 and a positive electrode current collector 12 in order from the negative electrode current collector 11 to the positive electrode current collector 12. The negative electrode current collector 11 is connected to a negative electrode (not shown), and the positive electrode current collector 12 is connected to a positive electrode (not shown). Due to this configuration, chemical energy generated from the inside of the battery 10 can be extracted from the positive electrode and the negative electrode to the outside as electrical energy.

[0031] The negative electrode layer 13 has a configuration in which solid electrolyte particles 21 (solid electrolyte powder), an electrode active material 22, and conductive auxiliary agent particles 24 are mixed. The solid electrolyte layer 14 is formed of the solid electrolyte particles 21. The positive electrode layer 15 has a configuration in which the solid electrolyte particles 21, an electrode active material 23, and the conductive auxiliary agent particles 24 are mixed. A mixing ratio between the materials in each of the negative electrode layer 13 and the positive electrode layer 15 can be set based on the specification of the battery and the like.

[0032] As a material of the negative electrode current collector 11, for example, copper is used. As a material of the positive electrode current collector 12, for example, aluminum is used. In addition, as the electrode active material 22 of the negative electrode layer 13, for example, graphite, hard carbon, carbon nanotubes, fullerene, or other carbon materials can be used. As the electrode active material 23 of the positive electrode layer 15, for example, lithium nickel oxide, lithium cobalt oxide, or other lithium metal oxides can be used. As a material of the conductive auxiliary agent particle 24, for example, activated carbon, graphite particles, or carbon fibers can be used. The solid electrolyte particles 21 (solid electrolyte powder) will be described below in detail.

Configuration of Solid Electrolyte Particles 21 (Solid Electrolyte Powder) and Method of Manufacturing the Same

[0033] The solid electrolyte particle 21 will be described below in the manufacturing step order.

(1) Preparation of Molten LATP Mixture

[0034] As starting materials, for example, H.sub.3PO.sub.4, NH.sub.4H.sub.2PO.sub.4, Li.sub.2CO.sub.3, TiO.sub.2, Al(OH).sub.3, or Al.sub.2O.sub.3 can be used. In addition, from the viewpoint of uniformity of NASICON crystals, it is preferable that the starting materials do not include SiO.sub.2.

[0035] These raw materials are put into a heating container and are heated and melted at a temperature which are equal to or higher than melting points of the raw materials, for example, at 1500° C. for a predetermined period of time to prepare molten LATP mixture.

(2) Preparation of Crystalline Material

[0036] The molten LATP mixture prepared in (1) described above is cooled to prepare a crystalline material having a NASICON structure. Regarding the cooling, the molten LATP mixture is naturally cooled, for example, by bringing the heating container into contact with a metal plate (for example, a stainless steel plate) to radiate heat. Here, in general, the NASICON structure refers to a structure of a compound represented by M.sub.2(XO.sub.4).sub.3 where MO.sub.6 octahedra and XO.sub.4 tetrahedra sharing vertices are three-dimensionally arranged, M represents a transition metal, and X represents S, P, As, Mo, or W.

(3) Preparation of Crystal Powder

[0037] The crystalline material prepared in (2) described above is crushed using, for example, a mortar or a pestle to prepare crystal powder. The crushing is performed such that the average particle size of the crystalline material is in a range of 1 μm to 10 μm.

(4) Preparation of LATP Powder

[0038] The crystal powder prepared in (3) described above is put into a gas muffle furnace, and a heat treatment (hereinafter, also referred to as “primary heat treatment”) is performed on the crystal powder in air at a predetermined temperature for a predetermined period of time to prepare LATP powder. Due to this heat treatment, highly ion-conductive LATP powder can be obtained in which a crystallite size on a predetermined lattice plane (for example, a (134) plane) or a (300) plane) is 500 nm or less. With this LATP powder, solid electrolyte powder is formed.

[0039] Here, preferable conditions of the primary heat treatment are a temperature of higher than 700° C. and lower than 1000° C. and a time of 1 hour to 12 hours. The temperature of the primary heat treatment is more preferably 800° C. or higher.

[0040] A composition of the prepared LATP powder is represented by, for example, Li.sub.1+xAl.sub.xTi.sub.2−x(PO.sub.4).sub.3, in which x satisfies 0<x<0.5.

[0041] The solid electrolyte powder can be prepared through the above-described steps (1) to (4), and it is more preferable that the following steps (5) and (6) are performed from the viewpoint of increasing the ion conductivity.

(5) Preparation of Secondary Powder

[0042] The LATP powder prepared in (4) described above is crushed using, for example, a mortar or a pestle to prepare secondary powder having an average particle size of 100 nm to 1000 nm.

(6) Preparation of Tertiary Powder

[0043] A heat treatment (hereinafter, also referred to as “secondary heat treatment”) is performed again on the secondary powder prepared in (5) described above to prepare tertiary powder. After putting the secondary powder into, for example, a gas muffle furnace, the heat treatment is performed on the secondary powder in air at a predetermined temperature (for example, 300° C. to 700° C.) for a predetermined period of time (for example, 30 minutes to 12 hours). Due to this heat treatment, the ion conductivity can be further increased.

[0044] Hereinafter, Examples will be described. Preparation of Samples

(a) Starting materials of each Example were H.sub.3PO.sub.4, Li.sub.2CO.sub.3, TiO.sub.2, and Al.sub.2O.sub.3, and a composition of the respective components present in a mixture of the starting materials is as follows in terms of oxides. Here, “the composition in terms of oxides” represents a composition that represents, assuming that all the starting materials were decomposed and changed into oxides during melting, the contents of the respective components in the molten mixture with respect to 100 mol % of the total amount of all the produced oxides.
(a-1) Example 1

[0045] Li.sub.2O: 16.2 mol %

[0046] Al.sub.2O.sub.3: 3.8 mol %

[0047] TiO.sub.2: 42.5 mol %

[0048] P.sub.2O.sub.3: 37.5 mol %

[0049] SiO.sub.2: 0 mol %

(a-2) Example 2

[0050] Li.sub.2O: 18.3 mol %

[0051] Al.sub.2O.sub.3: 3.6 mol %

[0052] TiO.sub.2: 41.5 mol %

[0053] P.sub.2O.sub.3: 36.6 mol %

[0054] SiO.sub.2: 0 mol %

[0055] After the starting materials were mixed with each other using a mortar, a frit was prepared according to the following procedure.

[0056] The mixture was heated at 300° C. for 30 minutes and at 700° C. for 30 minutes, was further heated at 1100° C. for 15 minutes, and was extracted and naturally cooled.

(b) Conditions of Heating and Melting for Preparing Molten LATP Mixture

[0057] For pre-heating, the mixture was heated at 1100° C. for 20 minutes and then was heated at 1300° C. for 10 minutes.

[0058] Next, for main heating, the raw materials were heated at 1500° C., as a temperature at which the raw materials were melted, for 5 minutes.

(c) Conditions of Preparing Crystalline Material

[0059] The molten LP mixture of the heating container was cast on a stainless steel plate having a thickness of 20 mm and was naturally cooled.

(d) Preparation of Crystal Powder

[0060] The crystalline material was crushed using a mortar such that the average particle size of the crystalline material was in a range of 1 μm to 10 μm.

(e) Preparation of LATP Powder (Solid Electrolyte Powder)

[0061] Using a gas muffle furnace HPM-1G (manufactured by Matsuura Manufacture Co., Ltd.), a heat treatment was performed in air for 12 hours. The temperature of the heat treatment was set in a range of 700° C. to 950° C. After the heat treatment, the powder was naturally cooled.

[0062] Through the above-described steps, LATP powder according to Example 1 having a configuration represented by Li.sub.1.3Al.sub.0.3Ti.sub.1.7(PO.sub.4).sub.3 was obtained, and LATP powder according to Example 2 having a configuration represented by Li.sub.1.5Al.sub.0.3Ti.sub.1.7(PO.sub.4).sub.3 was obtained.

(f) Preparation of Comparative Examples

[0063] After performing the manufacturing steps (a) to (e) on the same starting materials as those in Example 1, the heat treatment of the step (e) was not performed. As a result, a sample according to Comparative Example 1 was prepared. After performing the manufacturing steps (a) to (e) on the same starting materials as those in Example 2, the heat treatment of the step (e) was not performed. As a result, a sample according to Comparative Example 2 was prepared.

Evaluation Method

(a) X-Ray Diffraction (XRD)

[0064] Using a focusing diffractometer, X-ray diffraction was performed under the following conditions.

[0065] Target: Cu

[0066] Tube Voltage: 45 kV

[0067] Tube Current: 40 mA

[0068] Measurement Range: 10° to 100°

[0069] Step Size: 0.016°

[0070] T/S: 0.5 s

[0071] Incidence Side: FDS

[0072] Detector Side: XC

[0073] Stage: flat sample

(b) Evaluation of Impedance Properties

[0074] Each of a sample having undergone the heat treatment (primary heat treatment) and a sample not having undergone the heat treatment was crushed using a mortar to prepare a powder pellet, and the powder pellet was interposed between copper plate electrodes to measure an impedance thereof. The measurement was performed in a dry nitrogen atmosphere at 25° C., and the ion conductance was calculated based on a drawing created from a Nyquist plot of the measurement result. Evaluation Results

(a) X-Ray Diffraction

[0075] FIG. 2 is a graph showing the results of X-ray diffraction in Example 1. FIG. 3 is a graph showing the results of X-ray diffraction in Example 2. FIG. 4 is a graph showing the results of X-ray diffraction in Comparative Example 1. In FIGS. 2 to 4, the horizontal axis represents an incidence angle, and the vertical axis represents a diffraction intensity. In addition, in FIG. 2, (A), (B), and (C) represent cases where the temperature of the primary heat treatment is 850° C., 875° C., and 925° C., respectively. In FIG. 3, (A), (B), (C), and (D) represent cases where the temperature of the primary heat treatment is 700° C., 800° C., 900° C., and 950° C., respectively.

[0076] Regarding (A) to (C) of FIG. 2, (A) to (D) of FIG. 3, and FIG. 4, the diffraction peak of LiTi.sub.2(PO.sub.4).sub.3 having a NASICON structure was measured. As a result, it was found that the NASICON structure was maintained before and after the heat treatment, and it was also found that, in at least a temperature range shown in FIGS. 2 and 3, the NASICON structure was maintained irrespective of the temperature of the heat treatment.

(b) Measurement of Impedance

[0077] FIG. 5 is a graph showing a relationship between a temperature of the heat treatment (primary heat treatment) during the preparation of LATP powder and a crystallite size.

[0078] FIG. 6 is a graph showing a relationship between a crystallite size and an ion conductance. Tables 1 and 2 show measured values of Examples 1 and 2 and Comparative Examples 1 and 2 in a case where the temperature of the heat treatment (primary heat treatment) was changed, and FIGS. 5 and 6 were created based on the measured values. In FIGS. 5 and 6, the crystallite size refers to a size (unit: nm) on a (134) plane. The ion conductance on the vertical axis of FIG. 6 refers to a natural logarithm of a measured ion conductance σ (unit: Siemens/cm).

TABLE-US-00001 TABLE 1 Heat Lattice Constant Unit Volume Crystallite Size Treatment a c V (nm) Temperature (ongstrom) (ongstrom) (ongstrom{circumflex over ( )}3) (113) (300) (134) Comparative Not 8.4974 20.7885 1299.9 740 900 500 Example 1 Performed Example 1 700° C. 8.5026 20.9257 1310.1 710 580 500 850° C. 8.4964 20.8012 1300.4 390 420 270 875° C. 8.4958 20.7815 1299.0 500 620 320 900° C. 8.4986 20.8023 1301.2 650 870 300 950° C. 8.4980 20.8010 1300.9 >Max 580 320 Comparative Not 8.4984 20.8021 1301.1 850 460 380 Example 2 Performed Example 2 850° C. 8.5004 20.8213 1302.9 850 550 210 900° C. 8.4969 20.7886 1299.8 850 350 230 925° C. 8.4973 20.7946 1300.3 900 320 240 950° C. 8.4968 20.7965 1300.3 >Max 460 250

TABLE-US-00002 TABLE 2 Heat Conductance Treatment Temperature σ [S/cm] log σ Comparative Example 1 Not Performed 4.03E−09 −8.395 Example 1 700° C. 7.47E−09 −8.127 850° C. 1.30E−08 −7.886 875° C. 1.82E−08 −7.740 900° C. 2.02E−08 −7.695 950° C. 9.39E−09 −8.027 Comparative Example 2 Not Performed 5.80E−09 −8.237 Example 2 850° C. 4.55E−09 −8.342 900° C. 1.20E−09 −8.921 925° C. 5.92E−09 −8.228 950° C. 4.56E−09 −8.341

[0079] As shown in Table 1, the crystallite size of Example 1 was less than that of Comparative Example 1, and the crystallite size of Example 2 was less than that of

[0080] Comparative Example 2. In addition, in Examples 1 and 2, the crystallite sizes on the (134) plane were 500 nm or less, which were obviously less than those in Comparative Examples 1 and 2 where the heat treatment was not performed at a heat treatment temperature of higher than 700° C.

[0081] Regarding the conductance, as shown in Table 2 and FIG. 6, the ion conductance was increased depending on the reduction in the crystallite size, and it can be seen that a sufficiently high for an all-solid-state lithium ion secondary battery was realized.

[0082] Regarding the lattice constant, as shown in Table 1, the numerical values of Examples 1 and 2 were substantially the same as those in Comparative Examples 1 and 2, and it can be seen that there were no changes depending on the heat treatment or depending on the temperature of the heat treatment.

[0083] The present invention has been described with reference to the above-described embodiment. However, the present invention is not limited to the above-described embodiment, and various improvements or modifications can be made for the purpose of improvements or within the scope of the present invention.

[0084] As described above, the solid electrolyte powder according to the present invention is small and thin and is practically useful for realizing a lithium ion battery having no possibility of liquid leakage or firing.

[0085] It should be understood by those skilled in the art that various modifications, combinations, sub-combinations and alterations may occur depending on design requirements and other factors insofar as they are within the scope of the appended claims of the equivalents thereof.