# Patent

## Title
Sulfide solid electrolyte material, battery, and producing method for sulfide solid electrolyte material

## Abstract

The object of the present invention is to provide a sulfide solid electrolyte material with favorable ion conductivity. The present invention attains the object by providing a sulfide solid electrolyte material including an M1 element (such as a Li element), an M2 element (such as a Ge element and a P element), a S element and an O element, and having a peak at a position of 2θ=29.58°±0.50° in an X-ray diffraction measurement using a CuKα ray, characterized in that when a diffraction intensity at the peak of 2θ=29.58°±0.50° is regarded as IA and a diffraction intensity at a peak of 2θ=27.33°±0.50° is regarded as IB, a value of IB/IA is less than 0.50.

## Background
TECHNICAL FIELD
The present invention relates to a sulfide solid electrolyte material with favorable ion conductivity.
BACKGROUND ART
In accordance with a rapid spread of information relevant apparatuses and communication apparatuses such as a personal computer, a video camera and a portable telephone in recent years, the development of a battery to be utilized as a power source thereof has been emphasized. The development of a high-output and high-capacity battery for an electric automobile or a hybrid automobile has been advanced also in the automobile industry. A lithium battery has been presently noticed from the viewpoint of a high energy density among various kinds of batteries.
Liquid electrolyte containing a flammable organic solvent is used for a presently commercialized lithium battery, so that the installation of a safety device for restraining temperature rise during a short circuit and the improvement in structure and material for preventing the short circuit are necessary therefor. On the contrary, a lithium battery all-solidified by replacing the liquid electrolyte with a solid electrolyte layer is conceived to intend the simplification of the safety device and be excellent in production cost and productivity for the reason that the flammable organic solvent is not used in the battery.
A sulfide solid electrolyte material is known as a solid electrolyte material used for an all solid lithium battery. For example, in Non Patent Literature 1, a Li ion conductor (a sulfide solid electrolyte material) having a composition of Li(4-x)Ge(1-x)PxS4 is disclosed. Also, in Patent Literature 1, an LiGePS-based sulfide solid electrolyte material having a specific peak in X-ray diffraction measurement is disclosed. In addition, in Non Patent Literature 2, an LiGePS-based sulfide solid electrolyte material is disclosed.
CITATION LIST
Patent Literature
Patent Literature 1: WO 2011/118801
Non Patent Literature 
Non Patent Literature 1: Ryoji Kanno et al., “Lithium Ionic Conductor Thio-LISICON The Li2S—GeS2—P2S5 System”, Journal of The Electrochemical Society, 148 (7) A742-A746 (2001)
Non Patent Literature 2: Noriaki Kamaya et al., “A lithium superionic conductor”, Nature Materials, Advanced online publication, 31 Jul. 2011, DOI:10.1038/NMAT3066
SUMMARY OF INVENTION
Technical Problem
A solid electrolyte material with favorable ion conductivity is demanded from the viewpoint of achieving higher output of a battery. The present invention has been made in view of the above-mentioned actual circumstances, and the main object thereof is to provide a sulfide solid electrolyte material with favorable ion conductivity.
Solution to Problem
In order to solve the above-mentioned problems, the present invention provides a sulfide solid electrolyte material comprising an M1 element, an M2 element, a S element and an O element, characterized in that the above-mentioned M1 contains at least Li; the above-mentioned M2 is at least one kind selected from the group consisting of P, Sb, Si, Ge, Sn, B, Al, Ga, In, Zr, V and Nb; and having a peak at a position of 2θ=29.58°±0.50° in an X-ray diffraction measurement using a CuKα ray, characterized in that when a diffraction intensity at the above-mentioned peak of 2θ=29.58°±0.50° is regarded as IA and a diffraction intensity at a peak of 2θ=27.33°±0.50° is regarded as IB, a value of IB/IA is less than 0.50.
According to the present invention, the ratio of a crystal phase having a peak in the vicinity of 2θ=29.58° is so high as to allow the sulfide solid electrolyte material with favorable ion conductivity. In addition, the introduction of the O element into the sulfide solid electrolyte material comprising the M1 element, the M2 element and the S element allows the sulfide solid electrolyte material with ion conductivity further improved.
Also, the present invention provides a sulfide solid electrolyte material comprising an M1 element, an M2 element, a S element and an O element, characterized in that the above-mentioned M1 contains at least Li and the above-mentioned M2 is at least one kind selected from the group consisting of P, Sb, Si, Ge, Sn, B, Al, Ga, In, Ti, Zr, V and Nb; and having a peak at a position of 2θ=29.58°±0.50° in an X-ray diffraction measurement using a CuKα ray, characterized by not having a peak at a position of 2θ=27.33°±0.50° in the X-ray diffraction measurement using the CuKα ray, or characterized in that when a diffraction intensity at the above-mentioned peak of 2θ=29.58°±0.50° is regarded as IA and a diffraction intensity at the above-mentioned peak of 2θ=27.33°±0.50° is regarded as IB in the case of having a peak at the above-mentioned position of 2θ=27.33°±0.50°, a value of IB/IA is less than 0.50.
According to the present invention, the ratio of a crystal phase having a peak in the vicinity of 2θ=29.58° is so high as to allow the sulfide solid electrolyte material with favorable ion conductivity. In addition, the introduction of O element into the sulfide solid electrolyte material comprising the M1 element, the M2 element and the S element allows the sulfide solid electrolyte material with ion conductivity further improved.
Also, the present invention provides a sulfide solid electrolyte material comprising an octahedron O composed of an M1 element and a S element, a tetrahedron T1 composed of an M2a element and a S element, and a tetrahedron T2 composed of an M2b element and a S element, characterized in that the above-mentioned tetrahedron T1 and the above-mentioned octahedron O share an edge, the above-mentioned tetrahedron T2 and the above-mentioned octahedron O contain a crystal structure sharing a corner as the main body; the above-mentioned M1 contains at least Li; the above-mentioned M2a and the above-mentioned M2b are each independently at least one kind selected from the group consisting of P, Sb, Si, Ge, Sn, B, Al, Ga, In, Ti, Zr, V and Nb; and at least one of the above-mentioned octahedron O, the above-mentioned tetrahedron T1 and the above-mentioned tetrahedron T2 is such that a part of the above-mentioned S element is substituted with an O element.
According to the present invention, the octahedron O, the tetrahedron T1 and the tetrahedron T2 have a predetermined crystal structure (a three-dimensional structure), so as to allow the sulfide solid electrolyte material with favorable ion conductivity. At least one of the octahedron O, the tetrahedron T1 and the tetrahedron T2 is such that a part of the S element is substituted with O element, so as to allow the sulfide solid electrolyte material with ion conductivity further improved.
In the above-mentioned invention, it is preferable that the sulfide solid electrolyte material comprises at least a Li element, a Ge element, a P element, the S element and the O element, and the ratio of the above-mentioned O element to the total of the above-mentioned S element and the above-mentioned O element is 25% or less. The reason therefor is to allow the sulfide solid electrolyte material having higher ion conductivity.
In the above-mentioned invention, it is preferable that the sulfide solid electrolyte material comprises at least a Li element, a Si element, a P element, the S element and the O element, and the ratio of the above-mentioned O element to the total of the above-mentioned S element and the above-mentioned O element is 10% or less. The reason therefor is to allow the sulfide solid electrolyte material having higher ion conductivity.
Also, the present invention provides a battery containing a cathode active material layer containing a cathode active material, an anode active material layer containing an anode active material, and an electrolyte layer formed between the above-mentioned cathode active material layer and the above-mentioned anode active material layer, characterized in that at least one of the above-mentioned cathode active material layer, the above-mentioned anode active material layer and the above-mentioned electrolyte layer contains the above-mentioned sulfide solid electrolyte material.
According to the present invention, the use of the above-mentioned sulfide solid electrolyte material allows the high-output battery.
Also, the present invention provides a producing method for a sulfide solid electrolyte material having the above-mentioned peak intensity ratio, comprising steps of: an ion conductive material synthesizing step of synthesizing an amorphized ion conductive material by mechanical milling while using a raw material composition containing the above-mentioned M1 element, the above-mentioned M2 element, the above-mentioned S element and the above-mentioned O element, and a heating step of obtaining the above-mentioned sulfide solid electrolyte material by heating the above-mentioned amorphized ion conductive material.
According to the present invention, amorphization is performed in the ion conductive material synthesizing step to thereafter perform the heating step, so as to allow the sulfide solid electrolyte material such that the ratio of a crystal phase having a peak in the vicinity of 2θ=29.58° is high. Thus, the sulfide solid electrolyte material with favorable ion conductivity may be obtained. In addition, the inclusion of the O element in the raw material composition allows the sulfide solid electrolyte material with ion conductivity further improved.
Also, the present invention provides a producing method for a sulfide solid electrolyte material having the above-mentioned crystal structure, the method comprising steps of: an ion conductive material synthesizing step of synthesizing an amorphized ion conductive material by mechanical milling while using a raw material composition containing the above-mentioned M1 element, the above-mentioned M2a element, the above-mentioned M2b element, the above-mentioned S element and the above-mentioned O element, and a heating step of obtaining the above-mentioned sulfide solid electrolyte material by heating the above-mentioned amorphized ion conductive material.
According to the present invention, amorphization is performed in the ion conductive material synthesizing step to thereafter perform the heating step, so as to allow the sulfide solid electrolyte material such that the octahedron O, the tetrahedron T1 and the tetrahedron T2 have a predetermined crystal structure (a three-dimensional structure). Thus, the sulfide solid electrolyte material with favorable ion conductivity may be obtained. In addition, the inclusion of the O element in the raw material composition allows the sulfide solid electrolyte material with ion conductivity further improved.
Advantageous Effects of Invention
The present invention produces the effect such as to allow a sulfide solid electrolyte material with favorable ion conductivity.



BRIEF DESCRIPTION OF DRAWINGS
FIG. 1 is an X-ray diffraction spectrum explaining a difference between a sulfide solid electrolyte material with high ion conductivity and a sulfide solid electrolyte material with low ion conductivity.
FIG. 2 is a perspective view explaining an example of a crystal structure of a sulfide solid electrolyte material of the present invention.
FIG. 3 is a plan view explaining ion conduction in the present invention.
FIG. 4 is a schematic cross-sectional view showing an example of a battery of the present invention.
FIG. 5 is an explanatory view showing an example of a producing method for a sulfide solid electrolyte material of the present invention.
FIG. 6 is an X-ray diffraction spectrum of a sulfide solid electrolyte material obtained in Example 1.
FIG. 7 is an X-ray diffraction spectrum of a sulfide solid electrolyte material obtained in Example 2.
FIG. 8 is an X-ray diffraction spectrum of a sulfide solid electrolyte material obtained in Example 3.
FIG. 9 is an X-ray diffraction spectrum of a sulfide solid electrolyte material obtained in Comparative Example 1.
FIG. 10 is a result of measuring Li ion conductance of a sulfide solid electrolyte material obtained in each of Examples 1 to 3 and Comparative Example 1.
FIG. 11 is an X-ray diffraction spectrum of a sulfide solid electrolyte material obtained in Example 4.
FIG. 12 is an X-ray diffraction spectrum of a sulfide solid electrolyte material obtained in Example 5.
FIG. 13 is aft X-ray diffraction spectrum of a sulfide solid electrolyte material obtained in Example 6.
FIG. 14 is an X-ray diffraction spectrum of a sulfide solid electrolyte material obtained in Comparative Example 2.
FIG. 15 is a result of measuring Li ion conductance of a sulfide solid electrolyte material obtained in each of Examples 4 to 6 and Comparative Example 2.



DESCRIPTION OF EMBODIMENTS
A sulfide solid electrolyte material, a battery and a producing method for a sulfide solid electrolyte material of the present invention are hereinafter described in detail.
A. Sulfide Solid Electrolyte Material
First, a sulfide solid electrolyte material of the present invention is described. The sulfide solid electrolyte material of the present invention may be roughly divided into two embodiments. Then, the sulfide solid electrolyte material of the present invention is described while divided into a first embodiment and a second embodiment.
1. First Embodiment 
A sulfide solid electrolyte material of a first embodiment contains an M1 element, an M2 element, a S element and an O element, characterized in that the M1 contains at least Li and the M2 is at least one kind selected from the group consisting of P, Sb, Si, Ge, Sn, B, Al, Ga, In, Ti, Zr, V and Nb, and has a peak at a position of 2θ=29.58°±0.50° in an X-ray diffraction measurement using a CuKα ray, and characterized in that when a diffraction intensity at the above-mentioned peak of 2θ=29.58°±0.50° is regarded as IA and a diffraction intensity at a peak of 2θ=27.33°±0.50° is regarded as IB, a value of IB/IA is less than 0.50.
According to the first embodiment, the ratio of a crystal phase having a peak in the vicinity of 2θ=29.58° is so high as to allow the sulfide solid electrolyte material with favorable ion conductivity. In addition, the introduction of the O element into the sulfide solid electrolyte material having the M1 element, the M2 element and the S element allows the sulfide solid electrolyte material with ion conductivity further improved. Thus, the use of the sulfide solid electrolyte material of the first embodiment allows a high-output battery. The reason why ion conductivity is improved is conceived to be that the introduction of the O element causes the size of a tunnel through which an Li ion passes (a tunnel existing in a crystal) to change into a size for allowing easier conduction.
FIG. 1 is an X-ray diffraction spectrum explaining a difference between a sulfide solid electrolyte material with high ion conductivity and a sulfide solid electrolyte material with low ion conductivity. Incidentally, both of the two sulfide solid electrolyte materials in FIG. 1 have a composition of Li3.25Ge0.25P0.75S4. In FIG. 1, the sulfide solid electrolyte material with high ion conductivity has a peak at a position of 2θ=29.58°±0.50° and a position of 2θ=27.33°±0.50°. Also, in FIG. 1, the sulfide solid electrolyte material with low ion conductivity has the same peak. Here, it is conceived that a crystal phase having a peak in the vicinity of 2θ=29.58° and a crystal phase having a peak in the vicinity of 2θ=27.33° are crystal phases different from each other. Incidentally, in the first embodiment, the crystal phase having a peak in the vicinity of 2θ=29.58° and the crystal phase having a peak in the vicinity of 2θ=27.33° are occasionally referred to as ‘crystal phase A’ and ‘crystal phase B’, respectively. Incidentally, this sulfide solid electrolyte material with high ion conductivity has the same crystal structure as the sulfide solid electrolyte material of the first embodiment, as described later.
Both of the crystal phases A and B are crystal phases exhibiting ion conductivity, which is different. The crystal phase A is conceived to be remarkably high in ion conductivity as compared with the crystal phase A conventional synthesis method (such as a solid-phase method) has not been capable of decreasing the ratio of the crystal phase B with low ion conductivity, and has not been capable of sufficiently heightening ion conductivity. On the contrary, in the first embodiment, the crystal phase A with high ion conductivity may be precipitated so positively as to allow the sulfide solid electrolyte material with high ion conductivity.
Also, in the first embodiment, in order to distinguish from the sulfide solid electrolyte material with low ion conductivity, a diffraction intensity at a peak in the vicinity of 2θ=29.58° is regarded as IA and a diffraction intensity at a peak in the vicinity of 2θ=27.33° is regarded as IB, and a value of IB/IA is prescribed at less than 0.50. Incidentally, it is conceived that a conventional synthesis method has not allowed the sulfide solid electrolyte material such that a value of IB/IA is less than 0.50. Also, from the viewpoint of ion conductivity, the sulfide solid electrolyte material in the first embodiment is preferably high in the ratio of the crystal phase A with high ion conductivity. Thus, a value of IB/IA is preferably smaller; specifically, preferably 0.45 or less, more preferably 0.25 or less, far more preferably 0.15 or less, and particularly preferably 0.07 or less. Also, a value of IB/IA is preferably 0. In other words, it is preferable that the sulfide solid electrolyte material of the first embodiment does not have a peak in the vicinity of 2θ=27.33° as a peak of the crystal phase B.
The sulfide solid electrolyte material of the first embodiment has a peak in the vicinity of 2θ=29.58°. This peak is one of the peaks of the crystal phase A with high ion conductivity, as described above. Here, 2θ=29.58° is an actual measurement value, and a crystal lattice changes somewhat due to material composition, or the like so that a position of the peak occasionally shifts somewhat from 2θ=29.58°. Thus, in the first embodiment, the above-mentioned peak of the crystal phase A is defined as a peak at a position of 2θ=29.58°±0.50°. The crystal phase A is ordinarily conceived to have peaks of 2θ=17.38°, 20.18°, 20.44°, 23.56°, 23.96°, 24.93°, 26.96°, 29.07°, 29.58°, 31.71°, 32.66° and 33.39°. Incidentally, also these peak positions occasionally shift in a range of ±0.50°.
On the other hand, the peak in the vicinity of 2θ=27.33° is one of the peaks of the crystal phase B with low ion conductivity, as described above. Here, 2θ=27.33° is an actual measurement value, and a crystal lattice changes somewhat due to material composition or the like, so that a position of the peak occasionally shifts somewhat from 2θ=27.33°. Thus, in the first embodiment, the above-mentioned peak of the crystal phase B is defined as a peak at a position of 2θ=27.33°±0.50°. The crystal phase B is ordinarily conceived to have peaks of 2θ=17.46°, 18.12°, 19.99°, 22.73°, 25.72°, 27.33°, 29.16° and 29.78°. Incidentally, also these peak positions occasionally shift in a range of ±0.50°.
Also, the sulfide solid electrolyte material of the first embodiment comprises an M1 element, an M2 element, a S element and an O element. The above-mentioned M1 is not particularly limited if the M1 contains at least Li, but may be only Li or a combination of Li and another element. Another element is, for example, preferably a monovalent or divalent element, specifically, preferably at least one kind selected from the group consisting of Na, K, Mg, Ca and Zn. Also, the above-mentioned M1 may be a monovalent element (such as Li, Na and K), which is partially substituted with a divalent or more element (such as Mg, Ca and Zn). Thus, a monovalent element moves so easily as to improve ion conductivity.
On the other hand, the above-mentioned M2 is preferably a trivalent, tetravalent or pentavalent element. Examples of the above-mentioned M2 include one kind selected from the group consisting of P, Sb, Si, Ge, Sn, B, Al, Ga, In, Ti, Zr, V and Nb. Above all, in the first embodiment, the above-mentioned M2 preferably contains at least one kind selected from the group consisting of P, Si, Ge, Al, Zr, Sn and B, and contains at least P and Ge or at least P and Si more preferably.
Also, the sulfide solid electrolyte material of the first embodiment contains the S element and the O element. The ratio of the O element contained in the sulfide solid electrolyte material is preferably a ratio such as to allow higher ion conductivity than ion conductivity of the same sulfide solid electrolyte material except for adjusting valence number with S without containing the O element (a sulfide solid electrolyte material as comparison purpose). Incidentally, the sulfide solid electrolyte material as comparison purpose corresponds to Li3.35Ge0.35P0.65S4 in the case where the sulfide solid electrolyte material of the first embodiment is Li3.35Ge0.35P0.65(S1-yOy)4, for example. Here, the ratio of the O element to the total of the S element and the O element is, for example, preferably 0.1% or more, more preferably 0.5% or more, and far more preferably 1% or more. On the other hand, the above-mentioned ratio of the O element is, for example, preferably 25% or less. The reason therefor is to allow the sulfide solid electrolyte material having higher ion conductivity. Also, the above-mentioned ratio of the O element may be determined by XPS and EDX, for example.
Also, in the after-mentioned examples, an LiGePSO-based sulfide solid electrolyte material is really synthesized and X-ray diffraction measurement of an obtained sample is performed to confirm that TB/IA is a predetermined value or less. This LiGePSO-based sulfide solid electrolyte material is such that the M1 element corresponds to the Li element and the M2 element corresponds to the Ge element and the P element in the above-mentioned general formula. On the other hand, the sulfide solid electrolyte material of the first embodiment ordinarily has a specific crystal structure described in the after-mentioned second embodiment. It is guessed that an optional combination of the M1 element and the M2 element may offer the same crystal structure as the LiGePSO-based sulfide solid electrolyte material. Thus, it is conceived that any optional combination of the M1 element and the M2 element allows the sulfide solid electrolyte material with favorable ion conductivity. Also, a position of a peak in X-ray diffraction depends on a crystal structure, so that it is conceived that a similar XRD pattern is obtained irrespective of kinds of the M1 element and the M2 element if the sulfide solid electrolyte material has the above-mentioned crystal structure.
Also, the sulfide solid electrolyte material of the first embodiment preferably contains at least a Li element, a Ge element, a P element, a S element and an O element. In this case, as described above, the ratio of the O element to the total of the S element and the O element is, for example, preferably 0.1% or more, more preferably 0.5% or more, and far more preferably 1% or more. On the other hand, the above-mentioned ratio of O element is, for example, preferably 25% or less.
The composition of the LiGePSO-based sulfide solid electrolyte material is not particularly limited if the composition is a composition such as to allow a predetermined value of IB/IA, but is preferably a composition of Li(4-x)Ge(1-x)Px(S1-yOy)4 (“x” satisfies 0<x<1 and “y” satisfies 0<y≦0.25). The reason therefor is to allow the sulfide solid electrolyte material with high ion conductivity. Here, a composition of Li(4-x)Ge(1-x)PxS4 not having O element corresponds to a composition of a solid solution of Li3PS4 and Li4GeS4. That is to say, this composition corresponds to a composition on a tie line of Li3PS4 and Li4GeS4. Incidentally, both Li3PS4 and Li4GeS4 correspond to an ortho-composition and have the advantage that chemical stability is high. The sulfide solid electrolyte material having such a composition of Li(4-x)Ge(1-x)PxS4 has been conventionally known as thio-LISICON, and the sulfide solid electrolyte material of the first embodiment may be identical with conventional thio-LISICON in composition. However, as described above, the ratio of a crystal phase contained in the sulfide solid electrolyte material of the first embodiment is entirely different from the ratio of a conventional crystal phase. In addition, the sulfide solid electrolyte material of the first embodiment has the advantage that ion conductivity is further high by reason of containing the O element.
Also, “x” in Li(4-x)Ge(1-x)Px(S1-yOy)4 is not particularly limited if the “x” is a value such as to allow a predetermined value of IB/IA, but satisfies preferably 0.4≦x, and more preferably 0.5≦x, for example. On the other hand, the above-mentioned x satisfies preferably x≦0.8, and more preferably x≦0.75. The reason therefor is that such a range of “x” allows a value of IB/IA to be further decreased. The above-mentioned “y” satisfies preferably 0.001≦y, more preferably 0.005≦y, and far more preferably 0.01≦y. On the other hand, the above-mentioned y preferably satisfies y≦0.25. Thus, the sulfide solid electrolyte material with further favorable ion conductivity may be obtained. Also, the sulfide solid electrolyte material of the first embodiment is preferably obtained by using at least Li2S, P2S5 and GeS2.
Also, the sulfide solid electrolyte material of the first embodiment preferably contains at least the Li element, the Si element, the P element, the S element and the O element. In this case, the ratio of the O element to the total of the S element and the O element is, for example, preferably 0.1% or more, more preferably 0.5% or more, and far more preferably 1% or more. On the other hand, the above-mentioned ratio of the O element is, for example, preferably 20% or less, more preferably 15% or less, and far more preferably 10% or less.
In addition, the composition of the LiSiPSO-based sulfide solid electrolyte material is not particularly limited if the composition is a composition such as to allow a predetermined value of IB/IA, but is preferably a composition of Li(4-x)Si(1-x)Px(S1-yOy) (“x” satisfies 0<x<1 and y satisfies 0<y≦0.25). The reason therefor is to allow the sulfide solid electrolyte material with high ion conductivity. Here, a composition of Li(4-x)Si(1-x)PxS4 not having O element corresponds to a composition of a solid solution of Li3PS4 and Li4SiS4. That is to say, this composition corresponds to a composition on a tie line of Li3PS4 and Li4SiS4. Incidentally, both Li3PS4 and Li4SiS4 correspond to an ortho-composition and have the advantage that chemical stability is high.
Also, “x” in Li(4-x)Si(1-x)Px(S1-yOy)4 is not particularly limited if the “x” is a value such as to allow a predetermined value of IB/IA, but satisfies preferably 0.4≦x, and more preferably 0.5≦x, for example. On the other hand, the above-mentioned “x” satisfies preferably x≦0.8, and more preferably x≦0.75. The reason therefor is that such a range of “x” allows a value of IB/IA to be further decreased. The above-mentioned “y” satisfies preferably 0.001≦y, more preferably 0.005≦y, and far more preferably 0.01≦y. On the other hand, the above-mentioned “y” preferably satisfies y≦0.2, more preferably y≦0.15, and far more preferably y≦0.1. Also, the sulfide solid electrolyte material of the first embodiment is preferably obtained by using at least Li2S, P2S5 and SiS2.
The sulfide solid electrolyte material of the first embodiment is ordinarily a crystalline sulfide solid electrolyte material. Also, the sulfide solid electrolyte material of the first embodiment is preferably high in ion conductivity, and ion conductivity of the sulfide solid electrolyte material at 25° C. is preferably 1.0×10−3 S/cm or more, and more preferably 2.3×10−3 S/cm or more. Also, the shape of the sulfide solid electrolyte material of the first embodiment is not particularly limited but examples thereof include a powdery shape. In addition, the average particle diameter of the powdery sulfide solid electrolyte material is preferably within a range of 0.1 μm to 50 μm, for example.
The sulfide solid electrolyte material of the first embodiment has so high ion conductivity as to be capable of being used for optional uses in which ion conductivity is required. Above all, the sulfide solid electrolyte material of the first embodiment is preferably used for a battery. The reason therefor is to be capable of greatly contributing to achieving higher output of a battery. Also, a producing method for the sulfide solid electrolyte material of the first embodiment is described in detail in the after-mentioned ‘C. Producing method for sulfide solid electrolyte material’. Also, the sulfide solid electrolyte material of the first embodiment may also have characteristics of the after-mentioned second embodiment together.
Incidentally, the first embodiment may provide a sulfide solid electrolyte material comprising the M1 element, the M2 element, the S element and the O element, characterized in that the above-mentioned M1 contains at least Li and the above-mentioned M2 is at least one kind selected from the group consisting of P, Sb, Si, Ge, Sn, B, Al, Ga, In, Ti, Zr, V and Nb, and having a peak at a position of 2θ=29.58°±0.50° in an X-ray diffraction measurement using a CuKα ray, characterized by not having a peak at a position of 2θ=27.33°±0.50° in an X-ray diffraction measurement using a CuKα ray, or characterized in that when a diffraction intensity at the above-mentioned peak of 2θ=29.58°±0.50° is regarded as IA and a diffraction intensity at the above-mentioned peak of 2θ=27.33°±0.50° is regarded as IB in the case of having a peak at the above-mentioned position of 2θ=27.33°±0.50°, a value of IB/IA is less than 0.50. It is obvious from the above-mentioned description that the sulfide solid electrolyte material of the first embodiment includes the case of not having a peak in the vicinity of 2θ=27.33° as a peak of the crystal phase B; this expression allows the case of not having a peak in the vicinity of 2θ=27.33° to be prescribed further definitely.
2. Second Embodiment
Next, a second embodiment of a sulfide solid electrolyte material of the present invention is described. The sulfide solid electrolyte material of the second embodiment has an octahedron O composed of an M1 element and a S element, a tetrahedron T1 composed of an M2a element and a S element, and a tetrahedron T2 composed of an M2b element and a S element, characterized in that the above-mentioned tetrahedron T1 and the above-mentioned octahedron O share an edge, the above-mentioned tetrahedron T2 and the above-mentioned octahedron O contain a crystal structure sharing a corner as the main body, the above-mentioned M1 contains at least Li, the above-mentioned M2a and the above-mentioned M2b are each independently at least one kind selected from the group consisting of P, Sb, Si, Ge, Sn, B, Al, Ga, In, Ti, Zr, V and Nb, and at least one of the above-mentioned octahedron O, the above-mentioned tetrahedron T1 and the above-mentioned tetrahedron T2 is such that part of the above-mentioned S element is substituted with an O element.
According to the second embodiment, the octahedron O, the tetrahedron T1 and the tetrahedron T2 have a predetermined crystal structure (a three-dimensional structure), so as to allow the sulfide solid electrolyte material with favorable ion conductivity. At least one of the octahedron O, the tetrahedron T1 and the tetrahedron T2 is such that part of the S element is substituted with the O element, so as to allow the sulfide solid electrolyte material with ion conductivity further improved. Thus, the use of the sulfide solid electrolyte material of the second embodiment allows a high-output battery.
FIG. 2 is a perspective view explaining an example of a crystal structure of the sulfide solid electrolyte material of the second embodiment. In the crystal structure shown in FIG. 2, the octahedron O has M1 as the central element, and has six pieces of S (incidentally, part of S may be substituted with O) at the corner of the octahedron; typically, LiS6-xOx (0≦x<6) octahedron. The tetrahedron T1 has M2a as the central element, and has four pieces of S (incidentally, part of S may be substituted with O) at the corner of the tetrahedron; typically, both GeS4-xOx (0≦x<4) tetrahedron and PS4-xOx (0≦x<4) tetrahedron. The tetrahedron T2 has M2b as the central element, and has four pieces of S (incidentally, part of S may be substituted with O) at the corner of the tetrahedron; typically, PS4-xOx (0≦x<4) tetrahedron. With regard to the sulfide solid electrolyte material of the second embodiment, at least one of the octahedron O, the tetrahedron T1 and the tetrahedron T2 is such that part of the S element is substituted with O element. Incidentally, it may be confirmed by XRD pattern analysis and neutron diffraction through Rietveld method that part of the S element is substituted with the O element. In addition, the tetrahedron T1 and the octahedron O share an edge, and the tetrahedron T2 and the octahedron O share a corner.
FIG. 3 is a plan view explaining ion conduction in the second embodiment. In FIG. 3, an Li ion conducts in c-axis direction (a vertical direction to the paper plane) through the inside (tunnel T) of the crystal structure composed of the octahedron O, the tetrahedron T1 and the tetrahedron T2. Incidentally, an Li ion is disposed somewhat in a zigzag. The size of the tunnel T is determined by the size of the corner element and the central element of each of the polyhedrons. In the second embodiment, it is conceived that part of the S element as the corner element of the polyhedrons is substituted with small-sized O element, so that a tunnel size for allowing easy conduction of an Li ion is formed and ion conductivity of the sulfide solid electrolyte material is improved.
The sulfide solid electrolyte material of the second embodiment is greatly characterized by comprising the above-mentioned crystal structure as the main body. The ratio of the above-mentioned crystal structure in the whole crystal structure of the sulfide solid electrolyte material is not particularly limited but is preferably higher. The reason therefor is to allow the sulfide solid electrolyte material with high ion conductivity. The ratio of the above-mentioned crystal structure is, specifically, preferably 70 wt % or more, and more preferably 90 wt % or more. Incidentally, the ratio of the above-mentioned crystal structure may be measured by radiated light XRD, for example. In particular, the sulfide solid electrolyte material of the second embodiment is preferably a single-phase material of the above-mentioned crystal structure. The reason therefor is to allow ion conductivity to be extremely heightened.
Incidentally, the M1 element, the M2 element (the M2a element and the M2b element), and other items in the second embodiment are the same as the above-mentioned first embodiment; therefore, the description here is omitted.
B. Battery
Next, a battery of the present invention is described. The battery of the present invention is a battery comprising a cathode active material layer containing a cathode active material, an anode active material layer containing an anode active material, and an electrolyte layer formed between the above-mentioned cathode active material layer and the above-mentioned anode active material layer, characterized in that at least one of the above-mentioned cathode active material layer, the above-mentioned anode active material layer and the above-mentioned electrolyte layer contains the above-mentioned sulfide solid electrolyte material.
According to the present invention, the use of the above-mentioned sulfide solid electrolyte material allows the high-output battery.
FIG. 4 is a schematic cross-sectional view showing an example of the battery of the present invention. A battery 10 shown in FIG. 4 comprises a cathode active material layer 1 containing a cathode active material, an anode active material layer 2 containing an anode active material, an electrolyte layer 3 formed between the cathode active material layer 1 and the anode active material layer 2, a cathode current collector 4 for collecting the cathode active material layer 1, an anode current collector 5 for collecting the anode active material layer 2, and a battery case 6 for storing these members. In the present invention, at least one of the cathode active material layer 1, the anode active material layer 2 and the electrolyte layer 3 is greatly characterized by containing the sulfide solid electrolyte material described in the above-mentioned ‘A. Sulfide solid electrolyte material’.
The battery of the present invention is hereinafter described in each constitution.
1. Electrolyte Layer
The electrolyte layer in the present invention is a layer formed between the cathode active material layer and the anode active material layer. The electrolyte layer is not particularly limited if the layer is a layer such as to allow ion conduction, but is preferably a solid electrolyte layer composed of a solid electrolyte material. The reason therefor is to allow the battery with high safety as compared with a battery using a liquid electrolyte. In addition, in the present invention, a solid electrolyte layer preferably contains the above-mentioned sulfide solid electrolyte material. The ratio of the above-mentioned sulfide solid electrolyte material contained in a solid electrolyte layer is preferably, for example, within a range of 10% by volume to 100% by volume, above all, within a range of 50% by volume to 100% by volume. In particular, in the present invention, a solid electrolyte layer is preferably composed of only the above-mentioned sulfide solid electrolyte material. The reason therefor is to allow the high-output battery. The thickness of a solid electrolyte layer is preferably within a range of 0.1 μm to 1000 μm, for example, and within a range of 0.1 μm to 300 μm, above all. Also, examples of a method for forming a solid electrolyte layer include a method for compression-molding a solid electrolyte material.
Also, the electrolyte layer in the present invention may be a layer composed of a liquid electrolyte. The case of using a liquid electrolyte allows the higher-output battery though safety needs to be further considered as compared with the case of using a solid electrolyte layer. Also, in this case, ordinarily, at least one of the cathode active material layer and the anode active material layer contains the above-mentioned sulfide solid electrolyte material. A liquid electrolyte ordinarily contains a lithium salt and an organic solvent (a nonaqueous solvent). Examples of the lithium salt include inorganic lithium salts such as LiPF6, LiBF4, LiClO4 and LiAsF6, and organic lithium salts such as LiCF3SO3, LiN(CF3SO2)2, LiN(C2F5SO2)2 and LiC(CF3SO2)3. Examples of the above-mentioned organic solvent include ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethylmethyl carbonate (EMC) and butylene carbonate (BC).
2. Cathode Active Material Layer
The cathode active material layer in the present invention is a layer containing at least a cathode active material, and may contain at least one of a solid electrolyte material, a conductive material and a binder, as required. In particular, in the present invention, the cathode active material layer contains a solid electrolyte material, which is preferably the above-mentioned sulfide solid electrolyte material. The reason therefor is to allow the cathode active material layer with high ion conductivity. The ratio of the above-mentioned sulfide solid electrolyte material contained in the cathode active material layer varies with kinds of a battery and is preferably, for example, within a range of 0.1% by volume to 80% by volume, above all, within a range of 1% by volume to 60% by volume, and particularly, within a range of 10% by volume to 50% by volume. Also, examples of a cathode active material include LicoO2, LiMnO2, Li2NiMn3O8, LiVO2, LiCrO2, LiFePO4, LiCoPO4, LiNiO2 and LiNi1/3Co1/3Mn1/3O2.
The cathode active material layer in the present invention may further contain a conductive material. The addition of the conductive material allows conductivity of the cathode active material layer to be improved. Examples of the conductive material include acetylene black, Ketjen Black and carbon fiber. Also, the cathode active material layer may contain a binder. Examples of kinds of the binder include a fluorine-containing binder such as polytetrafluoroethylene (PTFE). Also, the thickness of the cathode active material layer is preferably within a range of 0.1 μm to 1000 μm, for example.
3. Anode Active Material Layer
Next, an anode active material layer in the present invention is described. The anode active material layer in the present invention is a layer containing at least an anode active material, and may contain at least one of a solid electrolyte material, a conductive material and a binder, as required. In particular, in the present invention, the anode active material layer contains a solid electrolyte material, which is preferably the above-mentioned sulfide solid electrolyte material. The reason therefor is to allow the anode active material layer with high ion conductivity. The ratio of the above-mentioned sulfide solid electrolyte material contained in the anode active material layer varies with kinds of a battery and is preferably, for example, within a range of 0.1% by volume to 80% by volume, above all, within a range of 1% by volume to 60% by volume, and particularly, within a range of 10% by volume to 50% by volume. Also, examples of an anode active material include a metal active material and a carbon active material. Examples of the metal active material include In, Al, Si, and Sn. On the other hand, examples of the carbon active material include mesocarbon microbeads (MCMB), high orientation property graphite (HOPG), hard carbon and soft carbon. Incidentally, a conductive material and a binder used for the anode active material layer are the same as the case of the above-mentioned cathode active material layer. Also, the thickness of the anode active material layer is preferably within a range of 0.1 μm to 1000 μm, for example.
4. Other Constitutions
The battery of the present invention comprises at least the above-mentioned electrolyte layer, cathode active material layer and anode active material layer, ordinarily further comprising a cathode current collector for collecting the cathode active material layer and an anode current collector for collecting the anode active material layer. Examples of a material for the cathode current collector include SUS, aluminum, nickel, iron, titanium and carbon, and preferably SUS among them. On the other hand, examples of a material for the anode current collector include SUS, copper, nickel and carbon, and preferably SUS among them. Also, the thickness and shape of the cathode current collector and the anode current collector are preferably selected properly in accordance with factors such as uses of a battery. Also, a battery case of a general battery may be used for a battery case used for the present invention. Examples of the battery case include a battery case made of SUS.
5. Battery
The battery of the present invention may be a primary battery or a secondary battery, and preferably a secondary battery among them. The reason therefor is to be repeatedly charged and discharged and be useful as a car-mounted battery, for example. Examples of the shape of the battery of the present invention include a coin shape, a laminate shape, a cylindrical shape and a rectangular shape. Also, a producing method for the battery of the present invention is not particularly limited if the method is a method such as to allow the above-mentioned battery, but the same method as a producing method for a general battery may be used. For example, in the case where the battery of the present invention is an all solid state battery, examples of a producing method therefor include a method such that a material composing a cathode active material layer, a material composing a solid electrolyte layer and a material composing an anode active material layer are sequentially pressed to thereby produce a power generating element and this power generating element is stored inside a battery case, which is crimped.
C. Producing Method for Sulfide Solid Electrolyte Material
Next, a producing method for a sulfide solid electrolyte material of the present invention is described. The producing method for a sulfide solid electrolyte material of the present invention may be roughly divided into two embodiments. Then, the producing method for a sulfide solid electrolyte material of the present invention is described while divided into a first embodiment and a second embodiment.
1. First Embodiment
The producing method for the sulfide solid electrolyte material of the first embodiment is a producing method for the sulfide solid electrolyte material described in A. Sulfide solid electrolyte material 1. First embodiment′, comprising steps of: an ion conductive material synthesizing step of synthesizing an amorphized ion conductive material by mechanical milling while using a raw material composition containing the above-mentioned M1 element, the above-mentioned M2 element, the above-mentioned S element and the above-mentioned O element, and a heating step of obtaining the above-mentioned sulfide solid electrolyte material by heating the above-mentioned amorphized ion conductive material.
According to the first embodiment, amorphization is performed in the ion conductive material synthesizing step to thereafter perform the heating step, so as to allow the sulfide solid electrolyte material such that the ratio of a crystal phase having a peak in the vicinity of 2θ=29.58° is high. Thus, the sulfide solid electrolyte material with favorable ion conductivity may be obtained. In addition, the inclusion of the O element in the raw material composition allows the sulfide solid electrolyte material with ion conductivity further improved.
FIG. 5 is an explanatory view showing an example of the producing method for the sulfide solid electrolyte material of the first embodiment. In the producing method for the sulfide solid electrolyte material in FIG. 5, first, a raw material composition is produced by mixing Li2S, Li2O, P2S5 and GeS2. On this occasion, in order to prevent the raw material composition from being deteriorated due to moisture in the air, the raw material composition is preferably produced under an inert gas atmosphere. Next, ball mill is performed for the raw material composition to obtain an amorphized ion conductive material. Next, the amorphized ion conductive material is heated for improving crystallinity to thereby obtain a sulfide solid electrolyte material.
The first embodiment allows the sulfide solid electrolyte material such that the ratio of a crystal phase having a peak in the vicinity of 2θ=29.58° is high; below, the reason therefor is described. In the first embodiment, the amorphized ion conductive material is once synthesized unlike a solid-phase method as a conventional synthesis method. Thus, it is conceived that an environment such that the crystal phase A with high ion conductivity (the crystal phase having a peak in the vicinity of 2θ=29.58°) is easily precipitated is brought and the crystal phase A may be precipitated so positively by the heating step thereafter as to allow a value of IB/IA to become less than 0.50, which has been conventionally impossible. The reason why an environment such that the crystal phase A is easily precipitated is brought by amorphizing is not completely clear, but it is conceived that there is a possibility that a solution range in the ion conductive material is changed by mechanical milling and an environment such that the crystal phase A is precipitated with difficulty changes into an environment such that the crystal phase A is easily precipitated.
The producing method for the sulfide solid electrolyte material of the first embodiment is hereinafter described in each step.
(1) Ion Conductive Material Synthesizing Step
First, an ion conductive material synthesizing step in the first embodiment is described. The ion conductive material synthesizing step in the first embodiment is a step of synthesizing an amorphized ion conductive material by mechanical milling while using a raw material composition containing the above-mentioned M1 element, the above-mentioned M2 element, the above-mentioned S element and the above-mentioned O element.
The raw material composition in the first embodiment is not particularly limited if the raw material composition is such as to contain the M1 element, the M2 element, the S element and the O element. Incidentally, the M1 element and the M2 element in the raw material composition are the same as the items described in the above-mentioned ‘A. Sulfide solid electrolyte material’. A compound containing the M1 element is not particularly limited but examples thereof include a simple substance of M1 and a sulfide of M1. Examples of the sulfide of M1 include Li2S, Na2S, K2S, MgS, CaS and ZnS. A compound containing M2 element is not particularly limited but examples thereof include a simple substance of M2 and a sulfide of M2. Examples of the sulfide of M2 include Me2S3 (Me is a trivalent element such as Al, B, Ga, In and Sb), NeS2 (Me is a tetravalent element such as Ge, Si, Sn, Zr, Ti and Nb) and Me2S5 (Me is a pentavalent element such as P and V).
A compound containing the S element is not particularly limited but may be a simple substance or a sulfide. Examples of the sulfide include a sulfide containing the above-mentioned M1 element or M2 element. A compound containing the O element is ordinarily an oxide. Kinds of the oxide are not particularly limited but are preferably an oxide containing the above-mentioned M1 element or M2 element. The reason therefor is not to produce an unnecessary side reaction. Examples of the above-mentioned oxide include Me2O3 (Me is a trivalent element such as Al, B, Ga, In and Sb), MeO2 (Me is a tetravalent element such as Ge, Si, Sn, Zr, Ti and Nb), Me2O5 (Me is a pentavalent element such as P and V), Li5MeO4 (Me is a trivalent element such as Al, B, Ga, In and Sb), Li4MeO4 (Me is a tetravalent element such as Ge, Si, Sn, Zr, Ti and Nb) and Li3MeO4 (Me is a pentavalent element such as P and V).
In addition, the raw material composition preferably has a composition of Li(4-x)Ge(1-x)Px(S1-yOy) (“x” satisfies 0<x<1 and “y” satisfies 0<y≦0.25). The reason therefor is to allow the sulfide solid electrolyte material with high ion conductivity. Incidentally, as described above, a composition of Li(4-x)Ge(1-x)PxS4 not having O element corresponds to a composition of a solid solution of Li3PS4 and Li4GeS4. Here, in consideration of the case where the raw material composition contains Li2S, P2S5 and GeS2, the ratio of Li2S and P2S5 such as to allow Li3PS4 is Li2S:P2S5=75:25 on a molar basis. On the other hand, the ratio of Li2S and GeS2 such as to allow Li4GeS4 is Li2S:GeS2=66.7:33.3 on a molar basis. Thus, the used amount of Li2S, P2S5 and GeS2 is preferably determined in consideration of these ratios. Also, a preferable range of “x” and “y” is the same as the contents described in the above-mentioned ‘A. Sulfide solid electrolyte material’.
In addition, the raw material composition preferably has a composition of Li(4-x)Si(1-x)Px(S1-yOy)4 (“x” satisfies 0<x<1 and “y” satisfies 0<y≦0.25). The reason therefor is to allow the sulfide solid electrolyte material with high ion conductivity. Incidentally, as described above, a composition of Li(4-x)Si(1-x)PxS4 not having O element corresponds to a composition of a solid solution of Li3PS4 and Li4SiS4. Here, in consideration of the case where the raw material composition contains Li2S, P2S5 and SiS2, the ratio of Li2S and P2S5 such as to allow Li3PS4 is Li2S:P2S5=75:25 on a molar basis. On the other hand, the ratio of Li2S and SiS2 such as to allow Li4SiS4 is Li2S:SiS2=66.7:33.3 on a molar basis. Thus, the used amount of Li2S, P2S5 and SiS2 is preferably determined in consideration of these ratios. Also, a preferable range of “x” and “y” is the same as the contents described in the above-mentioned ‘A. Sulfide solid electrolyte material’.
Mechanical milling is a method for grinding a test sample while allowing mechanical energy thereto. In the first embodiment, an amorphized ion conductive material is synthesized by allowing mechanical energy to the raw material composition. Examples of such mechanical milling include vibrating mill, ball mill, turbo mill, mechano-fusion and disk mill; and among them, preferably vibrating mill and ball mill.
The conditions of vibrating mill are not particularly limited if the conditions are such as to allow an amorphized ion conductive material. The vibration amplitude of vibrating mill is preferably, for example, within a range of 5 mm to 15 mm, and above all, within a range of 6 mm to 10 mm. The vibration frequency of vibrating mill is preferably, for example, within a range of 500 rpm to 2000 rpm, and above all, within a range of 1000 rpm to 1800 rpm. The filling factor of a test sample of vibrating mill is preferably, for example, within a range of 1% by volume to 80% by volume, and above all, within a range of 5% by volume to 60% by volume, and particularly, within a range of 10% by volume to 50% by volume. Also, a vibrator (such as a vibrator made of alumina) is preferably used for vibrating mill.
The conditions of ball mill are not particularly limited if the conditions are such as to allow an amorphized ion conductive material. Generally, larger number of revolutions brings higher production rate of the ion conductive material, and longer treating time brings higher conversion ratio of the raw material composition into the ion conductive material. The number of weighing table revolutions in performing planetary ball mill is preferably within a range of 200 rpm to 500 rpm, for example, and within a range of 250 rpm to 400 rpm, above all. Also, the treating time in performing planetary ball mill is preferably within a range of 1 hour to 100 hours, for example, and within a range of 1 hour to 70 hours, above all.
Incidentally, in the first embodiment, the amorphized ion conductive material is preferably synthesized so as to bring an environment such that the crystal phase having a peak in the vicinity of 2θ=29.58° is easily precipitated.
(2) Heating Step
A heating step in the first embodiment is a step of obtaining the above-mentioned sulfide solid electrolyte material by heating the above-mentioned amorphized ion conductive material.
In the first embodiment, the improvement of crystallinity is intended by heating the amorphized ion conductive material. This heating allows the crystal phase A with high ion conductivity (the crystal phase having a peak in the vicinity of 2θ=29.58° to be precipitated so positively as to allow a value of IB/IA to become less than 0.50, which has been conventionally impossible.
The heating temperature in the first embodiment is not particularly limited if the heating temperature is a temperature such as to allow a desired sulfide solid electrolyte material, but is preferably a temperature of crystallization temperature or more of the crystal phase A (the crystal phase having a peak in the vicinity of 2θ=29.58°). Specifically, the above-mentioned heating temperature is preferably 300° C. or more, more preferably 350° C. or more, far more preferably 400° C. or more, and particularly preferably 450° C. or more. On the other hand, the above-mentioned heating temperature is preferably 1000° C. or less, more preferably 700° C. or less, far more preferably 650° C. or less, and particularly preferably 600° C. or less. Also, the heating time is preferably adjusted properly so as to allow a desired sulfide solid electrolyte material. Also, heating in the first embodiment is preferably performed under an inert gas atmosphere or in a vacuum from the viewpoint of preventing oxidation. Also, the sulfide solid electrolyte material obtained by the first embodiment is the same as the contents described in the above-mentioned ‘A. Sulfide solid electrolyte material 1. First embodiment’; therefore, the description here is omitted.
2. Second Embodiment
The producing method for the sulfide solid electrolyte material of the second embodiment is a producing method for the sulfide solid electrolyte material described in ‘A. Sulfide solid electrolyte material 2. Second embodiment’, comprising steps of: an ion conductive material synthesizing step of synthesizing an amorphized ion conductive material by mechanical milling while using a raw material composition containing the above-mentioned M1 element, the above-mentioned M2a element, the above-mentioned M2b element, the above-mentioned S element and the above-mentioned O element, and a heating step of obtaining the above-mentioned sulfide solid electrolyte material by heating the above-mentioned amorphized ion conductive material.
According to the second embodiment, amorphization is performed in the ion conductive material synthesizing step to thereafter perform the heating step, so as to allow the sulfide solid electrolyte material such that the octahedron O, the tetrahedron T1 and the tetrahedron T2 have a predetermined crystal structure (a three-dimensional structure). Thus, the sulfide solid electrolyte material with favorable ion conductivity may be obtained. In addition, the inclusion of the O element in the raw material composition allows the sulfide solid electrolyte material with ion conductivity further improved.
The ion conductive material synthesizing step and the heating step in the second embodiment are basically the same as the contents described in the above-mentioned ‘C. Producing method for sulfide solid electrolyte material 1. First embodiment’; therefore, the description here is omitted. Various kinds of conditions are preferably determined so as to allow a desired sulfide solid electrolyte material.
Incidentally, the present invention is not limited to the above-mentioned embodiments. The above-mentioned embodiments are exemplification, and any is included in the technical scope of the present invention if it has substantially the same constitution as the technical idea described in the claim of the present invention and offers similar operation and effect thereto.
EXAMPLES
The present invention is described more specifically while showing examples hereinafter.
Example 1
Lithium sulfide (Li2S), lithium oxide (Li2O), phosphorus pentasulfide (P2S5) and germanium sulfide (GeS2) were used as a starting material. These powders were mixed in a glove box under an argon atmosphere at a ratio of 0.3495 g of Li2S, 0.03082 g of Li2O, 0.372641 g of P2S5 and 0.2469 g of GeS2 to obtain a raw material composition. The obtained raw material composition was ground by using vibrating mill. TI-100TM manufactured by Cosmic Mechanical Technology Co., Ltd. was used for vibrating mill. Specifically, 1 g of the raw material composition and a vibrator made of alumina (φ36.3 mm, height 48.9 mm) were put in a 10-mL pot and treated at the number of revolutions of 1440 rpm for 30 minutes. Thus, an amorphized ion conductive material having a composition of Li3.35Ge0.35P0.65(S0.95O0.05)4 was obtained.
Next, the obtained ion conductive material was molded into pellets, and the obtained pellets were put in a carbon-coated quartz tube and vacuum-sealed. The pressure of the quartz tube for vacuum-sealing was approximately 30 Pa. Next, the quartz tube was placed in a burning furnace, heated from room temperature to 550° C. over 6 hours, maintained at 550° C. for 8 hours, and thereafter slowly cooled up to room temperature. Thus, a crystalline sulfide solid electrolyte material having a composition of Li3.35Ge0.35P0.65(S0.95O0.05)4 was obtained. Incidentally, the above-mentioned composition corresponds to a composition of x=0.65 and y=0.05 in Li(4-x)Ge(1-x)Px(S1-yOy)4. The oxygen amount substituted is 5%.
Example 2
A crystalline sulfide solid electrolyte material was obtained in the same manner as Example 1 except for using a mixture at a ratio of 0.30728 g of Li2S, 0.06269 g of Li2O, 0.378922 g of P2S5 and 0.251096 g of GeS2 as a raw material composition. The obtained sulfide solid electrolyte material has a composition of Li3.35Ge0.35P0.65(S0.9O0.1)4, which corresponds to a composition of x=0.65 and y=0.1 in Li(4-x)Ge(1-x)Px(S1-yOy)4. The oxygen amount substituted is 10%.
Example 3
A crystalline sulfide solid electrolyte material was obtained in the same manner as Example 1 except for using a mixture at a ratio of 0.190304 g of Li2S, 0.150803 g of Li2O, 0.3962890 g of P2S5 and 0.262604 g of GeS2 as a raw material composition. The obtained sulfide solid electrolyte material has a composition of Li3.35Ge0.35P0.65 (S0.77O0.23)4, which corresponds to a composition of x=0.65 and y=0.23 in Li(4-x)Ge(1-x)Px(S1-yOy)4. The oxygen amount substituted is 23%.
Comparative Example 1
A crystalline sulfide solid electrolyte material was obtained in the same manner as Example 1 except for using a mixture at a ratio of 0.390529 g of Li2S, 0.366564 g of P2S5 and 0.242907 g of GeS2 as a raw material composition. The obtained sulfide solid electrolyte material has a composition of Li3.35Ge0.35P0.65S4, which corresponds to a composition of x=0.65 and y=0 in Li(4-x)Ge(1-x)Px(S1-yOy)4. The oxygen amount substituted is 0%.
[Evaluations 1]
(X-Ray Diffraction Measurement)
X-ray diffraction (XRD) measurement was performed while using the sulfide solid electrolyte material obtained in Examples 1 to 3 and Comparative Example 1. XRD measurement was performed for a powder sample under an inert atmosphere on the conditions of using a CuKα ray. The results are shown in FIGS. 6 to 9. As shown in FIG. 9, the single-phase sulfide solid electrolyte material was obtained in Comparative Example 1. The position of a peak was 2θ=17.38°, 20.18°, 20.44°, 23.56°, 23.96°, 24.93°, 26.96°, 29.07°, 29.58°, 31.71°, 32.66° and 33.39°. That is to say, these peaks are conceived to be the peaks of the crystal phase A with high ion conductivity. Incidentally, the peak of 2θ=27.33°±0.50° as the peak of the crystal phase B with low ion conductivity was not confirmed. Also, as shown in FIGS. 6 to 8, it was confirmed that Examples 1 to 3 had the same diffraction pattern as Comparative Example 1.
(X-Ray Structural Analysis)
The crystal structure of the sulfide solid electrolyte material obtained in Comparative Example 1 was identified by X-ray structural analysis. The crystal system and crystallographic group were determined by a direct method on the basis of a diffraction pattern obtained in XRD to thereafter identify the crystal structure by a real space method. As a result, it was confirmed that the sulfide solid electrolyte material had the above-mentioned crystal structure as shown in FIGS. 2 and 3. That is to say, the crystal structure was such that the tetrahedron T1 (GeS4 tetrahedron and PS4 tetrahedron) and the octahedron O (LiS6 octahedron) shared an edge, and the tetrahedron T2 (PS4 tetrahedron) and the octahedron O (LiS6 octahedron) shared a corner. Also, as described above, Examples 1 to 3 had the same diffraction pattern as Comparative Example 1, so that it was confirmed that the same crystal structure was formed in Examples 1 to 3.
(Measurement of Li Ion Conductance)
Li ion conductance at a temperature of 25° C. was measured while using the sulfide solid electrolyte material obtained in Examples 1 to 3 and Comparative Example 1. First, a test sample was weighed by a suitable amount in a glove box of an argon atmosphere, put in a polyethylene terephthalate tube (a PET tube, an inside diameter of 10 mm, an outside diameter of 30 mm, a height of 20 mm), and held between powder molding jigs made of carbon tool steel S45C anvil from the top and bottom. Next, the test sample was pressed at an indicating pressure of 6 MPa (a molding pressure of approximately 110 MPa) by using a uniaxial pressing machine (P-6TM manufactured by Rikenseiki Co., Ltd.), and molded into pellets with a diameter of 10 mm and an optional thickness. Next, gold powder (manufactured by The Nilaco Corporation, treelike, a particle diameter of approximately 10 μm) was mounted by 13 mg to 15 mg on both sides of the pellets, and dispersed uniformly on the surface of the pellets, which were molded at an indicating pressure of 30 MPa (a molding pressure of approximately 560 MPa). Thereafter, the obtained pellets were put in a closed electrochemical cell which may maintain an argon atmosphere.
An impedance gain-phase analyzer manufactured by Solartron Inc. (solartron 1260TM) was used for the measurement as FRA (Frequency Response Analyzer), and a small-sized environmental tester (Espec corp, SU-241TM, −40° C. to 150° C.) was used as a constant temperature unit. The measurement was started from a high-frequency range on the conditions of an alternating voltage of 10 mV to 1000 mV, a frequency range of 1 Hz to 10 MHz, an integration time of 0.2 second, and a temperature of 23° C. ZplotTM was used for measurement software and ZviewTM was used for analysis software. The obtained results are shown in FIG. 10.
As shown in FIG. 10, it was confirmed that Li ion conductance was high in Examples 1 to 3 such that sulfur was substituted with oxygen as compared with Comparative Example 1 such that sulfur was not substituted with oxygen. The reason why Li ion conductance of the sulfide solid electrolyte material obtained in Examples 1 to 3 is high is conceived to be that the introduction of the O element causes the size of a tunnel through which an Li ion passes (a tunnel existing in a crystal) to change into a size for allowing easier conduction.
Example 4
Lithium sulfide (Li2S, manufactured by Nippon Chemical Industrial Co., Ltd.), lithium oxide (Li2O, manufactured by Kojundo Chemical Lab. Co., Ltd.), phosphorus pentasulfide (P2S5, manufactured by Sigma-Aldrich Co. LLC.) and silicon sulfide (SiS2, manufactured by Kojundo Chemical Lab. Co., Ltd.) were used as a starting material. These powders were mixed in a glove box under an argon atmosphere at a ratio of 0.34083 g of Li2S, 0.06819 g of Li2O, 0.38049 g of P2S5 and 0.21047 g of SiS2 to obtain a raw material composition. Next, 1 g of the raw material composition was put in a pot made of zirconia (45 ml) together with zirconia ball (10 mmφ, 10 pieces) to hermetically seal the pot completely (an argon atmosphere). This pot was mounted on a planetary ball milling machine (P7TM manufactured by Fritsch Japan Co., Ltd.) to perform mechanical milling for 40 hours at the number of weighing table revolutions of 370 rpm. Thus, an amorphized ion conductive material was obtained.
Next, powder of the obtained ion conductive material was put in a carbon-coated quartz tube and vacuum-sealed. The pressure of the quartz tube for vacuum-sealing was approximately 30 Pa. Next, the quartz tube was placed in a burning furnace, heated from room temperature to 550° C. over 6 hours, maintained at 550° C. for 8 hours, and thereafter slowly cooled up to room temperature. Thus, a crystalline sulfide solid electrolyte material having a composition of Li3.4Si0.4P0.6(S0.9O0.1)4 was obtained. Incidentally, the above-mentioned composition corresponds to a composition of x=0.6 and y=0.1 in Li(4-x)Si(1-x)Px(S1-yO4. The oxygen amount substituted is 10%.
Example 5
A crystalline sulfide solid electrolyte material was obtained in the same manner as Example 4 except for using a mixture at a ratio of 0.386186 g of Li2S, 0.03348565 g of Li2O, 0.373641747 g of P2S5 and 0.2066865 g of SiS2 as a raw material composition. The obtained sulfide solid electrolyte material has a composition of Li3.4Si0.4P0.6 (S0.95O0.05)4, which corresponds to a composition of x=0.6 and y=0.05 in Li(4-x)Si(1-x)Px (S1-yOy)4. The oxygen amount substituted is 5%.
Example 6
A crystalline sulfide solid electrolyte material was obtained in the same manner as Example 4 except for using a mixture at a ratio of 0.2449428 g of Li2S, 0.141591 g of Li2O, 0.3949774 g of P2S5 and 0.21848871 g of SiS2 as a raw material composition. The obtained sulfide solid electrolyte material has a composition of Li3.4Si0.4P0.6(S3.8O0.2)4, which corresponds to a composition of x=0.6 and y=0.2 in Li(4-x)Si(1-x)Px(S1-yOy)4. The oxygen amount substituted is 20%.
Comparative Example 2
A crystalline sulfide solid electrolyte material was obtained in the same manner as Example 4 except for using a mixture at a ratio of 0.429936 g of Li2S, 0.367033 g of P2S5 and 0.203030 g of SiS2 as a raw material composition. The obtained sulfide solid electrolyte material has a composition of Li3.4Si0.4P0.6S4, which corresponds to a composition of x=0.6 and y=0 in Li(4-x)Si(1-x)Px(S1-yOy)4. The oxygen amount substituted is 0%.
[Evaluations 2]
(X-Ray Diffraction Measurement)
X-ray diffraction (XRD) measurement was performed while using the sulfide solid electrolyte material obtained in Examples 4 to 6 and Comparative Example 2. XRD measurement was performed for a powder sample under an inert atmosphere on the conditions of using a CuKα ray. The results are shown in FIGS. 11 to 14. As shown in FIGS. 11 to 14, it was confirmed that Examples 4 to 6 and Comparative Example 2 had the same diffraction pattern as the above-mentioned Comparative Example 1.
(Measurement of Li Ion Conductance)
Li ion conductance at a temperature of 25° C. was measured while using the sulfide solid electrolyte material obtained in Examples 4 to 6 and Comparative Example 2. The measuring method is the same as the method described in Evaluations 1. The obtained results are shown in FIG. 15. As shown in FIG. 15, it was confirmed that Li ion conductance was equal or high in Examples 4 to 6 such that sulfur was substituted with oxygen as compared with Comparative Example 2 such that sulfur was not substituted with oxygen. The reason why Li ion conductance of the sulfide solid electrolyte material obtained in Examples 1 to 3 is high is conceived to be that the introduction of the O element causes the size of a tunnel through which an Li ion passes (a tunnel existing in a crystal) to change into a size for allowing easier conduction.
REFERENCE SIGNS LIST


    
    
        1 . . . cathode active material layer
        2 . . . anode active material layer
        3 . . . electrolyte layer
        4 . . . cathode current collector
        5 . . . anode current collector
        6 . . . battery case
        10 . . . battery

## Claims

1. A sulfide solid electrolyte material comprising an M1 element, an M2 element, a S element and an O element, wherein
the M1 contains at least Li;
the M2 is at least one kind selected from the group consisting of P, Sb, Si, Ge, Sn, B, Al, Ga, In, Ti, Zr, V and Nb; and
having a peak at a position of 2θ=20.18°±0.50°, 2θ=20.44°±0.50°, 2θ=26.96°±0.50° and 2θ=29.58°±0.50° in an X-ray diffraction measurement using a CuKα ray; and
wherein when a diffraction intensity at the peak of 2θ=29.58°±0.50° is regarded as IA and a diffraction intensity at a peak of 2θ=27.33°±0.50° is regarded as IB, a value of IB/IA is less than 0.50.

2. A sulfide solid electrolyte material comprising an M1 element, an M2 element, a S element and an O element, wherein
the M1 contains at least Li; the M2 is at least one kind selected from the group consisting of P, Sb, Si, Ge, Sn, B, Al, Ga, In, Ti, Zr, V and Nb; and
having a peak at a position of 2θ=20.18°±0.50°, 2θ=20.44°±0.50°, 2θ=26.96°±0.50° and 2θ=29.58°±0.50° in an X-ray diffraction measurement using a CuKα ray; and
wherein the sulfide solid electrolyte material does not have a peak at a position of 2θ=27.33°±0.50° in the X-ray diffraction measurement using the CuKα ray, or wherein when a diffraction intensity at the peak of 2θ=29.58°±0.50° is regarded as IA and a diffraction intensity at the peak of 2θ=27.33°±0.50° is regarded as IB in a case the sulfide solid electrolyte material has a peak at the position of 2θ=27.33°±0.50°, a value of IB/IA is less than 0.50.

3. A sulfide solid electrolyte material having an octahedron O composed of an M1 element and a S element, a tetrahedron T1 composed of an M2a element and a S element, and a tetrahedron T2 composed of an M2b element and a S element,
wherein the tetrahedron T1 and the octahedron O share an edge, the tetrahedron T2 and the octahedron O contain a crystal structure sharing a corner as a main body;
the M1 contains at least Li;
the M2a and the M2b are each independently at least one kind selected from the group consisting of P, Sb, Si, Ge, Sn, B, Al, Ga, In, Ti, Zr, V and Nb; and
at least one of the octahedron O, the tetrahedron T1 and the tetrahedron T2 is such that a part of the S element is substituted with an O element.

4. The sulfide solid electrolyte material according to claim 1, comprising at least a Li element, a Ge element, a P element, the S element and the O element, wherein a ratio of the O element to a total of the S element and the O element is 25% or less.

5. The sulfide solid electrolyte material according to claim 1, comprising at least a Li element, a Si element, a P element, the S element and the O element, wherein a ratio of the O element to a total of the S element and the O element is 10% or less.

6. A battery comprising a cathode active material layer containing a cathode active material, an anode active material layer containing an anode active material, and an electrolyte layer formed between the cathode active material layer and the anode active material layer, wherein at least one of the cathode active material layer, the anode active material layer and the electrolyte layer contains the sulfide solid electrolyte material according to claim 1.

7. A producing method for a sulfide solid electrolyte material, the sulfide solid electrolyte material being the sulfide solid electrolyte material according to claim 1, comprising steps of:
an ion conductive material synthesizing step of synthesizing an amorphized ion conductive material by mechanical milling while using a raw material composition containing the M1 element, the M2 element, the S element and the O element, and
a heating step of obtaining the sulfide solid electrolyte material by heating the amorphized ion conductive material.

8. A producing method for a sulfide solid electrolyte material, the sulfide solid electrolyte material being the sulfide solid electrolyte material according to claim 3, comprising steps of:
an ion conductive material synthesizing step of synthesizing an amorphized ion conductive material by mechanical milling while using a raw material composition containing the M1 element, the M2a element, the M2b element, the S element and the O element, and
a heating step of obtaining the sulfide solid electrolyte material by heating the amorphized ion conductive material.