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    • 专利摘要:
    A solid electrolyte sulphide material contains vitreous ceramic containing Li, A, X, and S, and has peaks at 2Teta = 20.2 ° and 23.6 ° in X-ray diffraction measurement with the CuKo line. A is at least one type of P. Si, Ge, Al, and B and X is a halogen. A method for producing a solid electrolyte material of sulfide includes amortizing the composition of a raw material containing Li2S, an A sulfide, and LiX to synthesize sulfide glass, and heating the sulfide glass to a treatment temperature thermal, equal to or greater than the crystallization temperature of the same in order to synthesize the vitreous ceramic with peaks in 2Teta = 20.2 ° and 23.6 ° in the measurement by X-ray diffraction with the CuKα line, in which the proportion between the LiX contained in the composition of the raw material and the temperature of the heat treatment is controlled to obtain the vitreous ceramics.
    公开号:BR112014000252B1
    申请号:R112014000252-5
    申请日:2012-06-19
    公开日:2020-06-30
    发明作者:Takamasa Ohtomo；Koji Kawamoto；Shigenori Hama；Yuki KATO
    申请人:Toyota Jidosha Kabushiki Kaisha；
    IPC主号:
    专利说明:

    [0001] [001] The present invention relates to a solid electrolyte material of sulfide that has high conductivity of lithium ions. Background of the Invention
    [0002] [002] In recent years, since devices related to information and communication devices, such as personal computers, video cameras and portable phones are spreading rapidly, the development of batteries used as their power source has been considered as important. In addition, also in automobile industries and so on, batteries for electric cars or hybrid cars, which have high performance and high capacity, are under development. At the present time, among the various types of batteries, lithium batteries are under attention from the point of view of high energy density.
    [0003] [003] The lithium batteries that are commercially available at the present time use an electrolyte solution containing flammable organic solvent and, therefore, a safety device that can prevent the temperature from rising at the time of the short circuit has to be provided, as well as an improvement in structure and material is needed to prevent short circuits. On the other hand, all lithium batteries in solid state, in which a layer of solid electrolyte is used in place of the electrolyte solution, do not contain flammable organic solvent inside, and consequently, the safety device can be simplified. Solid-state lithium batteries are therefore considered to be superior in production costs and productivity. In addition, like solid electrolyte materials useful for the solid electrolyte layer like this, solid electrolyte sulfide materials are known.
    [0004] [004] The solid electrolyte materials of sulfide have high conductivity of Li ions and are advantageous in achieving a high battery performance and, consequently, several studies have been carried out on them. For example, in Tomei et al., "Preparation of Amorphous Materials in the system Lil-Li 2 SP 2 S 5 by Mechanical Milling and Their Lithium Ion Conducting Properties", Proceedings of The Symposium On Solid State Ionics, Vol. 23, p . 26 - 27 (2003) (Non-Patent Document 1), the amorphous materials of the Lil-Li 2 SP 2 S 5 system obtained by mechanical grinding are disclosed. In addition, in F. Stader et al., "Crystalline halide substituted Li-argyrodites as solid electrolyte for lithium ion batteries", 216th ECS (The Electrochemical Society) Meeting with EuroCVD 17 and SOFC XI - 11 th International Symposium On Solid Oxide Fuel Cells, 2009, http://www.electrochem.org/meetings/scheduler/abstracts / 216 / 0590.pdf (Non-Patent Document 2), the crystalline materials represented by Li 6 PS 5 X (X = Cl , Br, I) are disclosed. Summary of the Invention
    [0005] [005] There is a demand for solid electrolyte materials of sulfide with high conductivity of Li ions. The present invention provides the solid electrolyte materials of sulfide with high conductivity of Li ions.
    [0006] [006] After controlled studies have been carried out, the present inventors have found that, during the synthesis of vitreous ceramics by heat treatment of doped LiX sulfide glass, in a limited range of each amount of LiX addition and heat treatment temperature , a glassy ceramic with extremely high conductivity of Li ions can be obtained. In addition, the present inventors have also found that the high conductivity of Li ions is due to a new crystalline phase that was not known until then. The present invention is achieved on the basis of these findings.
    [0007] [007] That is, a first aspect of the present invention relates to a solid electrolyte material of sulfide. The sulfide solid electrolyte material contains a glassy ceramic with Li, A, X and S. A is at least one element of P, Si, Ge, Al and B. X is a halogen. The sulfide solid electrolyte material has peaks at 2θ = 20.2 ° and 23.6 ° when measuring by X-ray diffraction with the CuKα line.
    [0008] [008] According to the first aspect of the present invention, due to the peaks indicated in the measurement by X-ray diffraction, the solid electrolyte material of sulfide can have high conductivity of Li ions.
    [0009] [009] In the solid electrolyte sulphide material, the vitreous ceramic may include an ion conductor containing Li, A and S, and LiX.
    [0010] [010] In the solid electrolyte sulphide material, a proportion of LiX can be 14% per mol or greater and less than 30% per mol.
    [0011] [011] In the solid electrolyte sulphide material, the proportion of LiX can be greater than 14% per mole and less than 30% per mole.
    [0012] [012] In the solid electrolyte material of sulfide, the proportion of LiX can be 25% per mol or less.
    [0013] [013] In the solid electrolyte sulphide material, the ion conductor may have an ortho composition. This is because the sulphide solid electrolyte material can have high chemical stability.
    [0014] [014] The sulfide solid electrolyte material may include 50% per mol or more of a crystalline phase corresponding to 2θ = 20.2 ° and 23.6 ° in relation to a solid total crystalline phase of the sulfide solid electrolyte material.
    [0015] [015] A second aspect of the present invention concerns a solid state lithium battery. The solid-state lithium battery includes a layer of positive electrode active material that contains a positive electrode active material, a layer of negative electrode active material containing a negative electrode active material, and a solid electrolyte layer formed between the positive electrode active material layer and negative electrode active material layer. At least one layer of positive electrode active material, the layer of negative electrode active material, and the solid electrolyte layer includes the sulfide solid electrolyte material described above.
    [0016] [016] According to the second aspect of the present invention, by using the solid electrolyte material of sulfide, a solid state lithium battery with high conductivity of Li ions can be obtained. As a result, the output power of the solid-state lithium battery can be increased.
    [0017] [017] A third aspect of the present invention concerns a solid state lithium battery. The solid-state lithium battery includes a layer of positive electrode active material containing a positive electrode active material, a layer of negative electrode active material containing a negative electrode active material, and a layer of solid electrolyte formed between a layer of positive electrode active material and one layer of negative electrode active material. At least one layer of positive electrode active material, the layer of negative electrode active material and the solid electrolyte layer includes the sulfide solid electrolyte material described above. LiX being Lil. The positive electrode active material has a potential of 2.8 V or more compared to Li.
    [0018] [018] In addition, a fourth aspect of the present invention relates to a method for the production of a solid electrolyte material of sulfide. The method for producing a solid electrolyte material of sulfide includes: amorphizing the composition of a raw material containing Li 2 S, an A sulfide, and LiX to synthesize the sulphide glass, and heat the sulphide glass to a temperature heat treatment, equal to or greater than the crystallization temperature of the sulphide glass in order to synthesize the vitreous ceramic with peaks at 2θ = 20.2 ° and 23.6 ° in X-ray diffraction measurement with the CuKα line . A is at least one element of P, Si, Ge, Al and B. X is a halogen. The proportion between the LiX contained in the raw material composition and the heat treatment temperature is controlled to obtain the vitreous ceramic.
    [0019] [019] According to the fourth aspect of the present invention, by controlling the proportion of LiX contained in the raw material composition and the temperature of the heat treatment in the heating step, the solid electrolyte materials of sulfide with high conductivity of ions of Li can be obtained.
    [0020] [020] In the method for the production of a solid electrolyte material of sulfide, the proportion between the LiX contained in the composition of raw material can be in a first range of 14% per mol or greater or less than 30% per mol or , in a second band close to the first band and allows the synthesis of vitreous ceramics, and an upper limit of the heat treatment temperature is a temperature that allows the synthesis of vitreous ceramics close to 200 ° C.
    [0021] [021] In the method for the production of a solid electrolyte material of sulfide, the ratio between the LiX contained in the composition of raw material can be 14% per mol or greater and less than 30% per mol, and the temperature of heat treatment can be less than 200 ° C.
    [0022] [022] In the method for producing a solid sulfide electrolyte material, the heat treatment temperature can be 170 ° C or more. In the method for producing a solid sulfide electrolyte material, the heat treatment temperature can be 190 ° C or less.
    [0023] [023] The present invention achieves the effect of obtaining solid electrolyte material of sulfide with high conductivity of Li ions. Brief Description of the Figures
    [0024] [024] The characteristics, advantages and technical and industrial significance of the exemplary embodiments of the invention will be described below with reference to the accompanying drawings, in which the same numbers denote the same elements, where: Figure 1 is a schematic sectional view showing an example of a solid-state lithium battery of the present invention; Figure 2 is a flow chart showing an example of a method for producing a solid electrolyte sulfide material of the present invention; Figure 3 shows the results of the X-ray diffraction measurements of the glass ceramics obtained in Examples 1 to 5; Figure 4 shows the results of the X-ray diffraction measurements of the vitreous ceramics obtained in Comparative Examples 2 to 4; Figure 5 shows the results of the Li ion conductivity measurements of the samples obtained in Examples 1 to 5 and Comparative Examples 1 to 9; Figure 6 shows the results of measurements by X - ray diffraction of the vitreous ceramics obtained in Examples 6 to 8 and Comparative Example 11; and Figure 7 shows the results of the conductivity measurements of Li ions in the samples obtained in Examples 6 to 8 and Comparative Examples 10 to 11. Detailed Description of the Invention
    [0025] [025] A solid sulphide electrolyte material, a solid state lithium battery, and a method for producing the solid sulphide electrolyte material will be described in more detail below. A. Sulfide Solid Electrolyte Material
    [0026] [026] First, a solid electrolyte sulfide material will be described according to an embodiment of the invention. The sulfide solid electrolyte material of the embodiment of the invention is a glassy ceramic containing Li, A (A is at least one type of P, Si, Ge, Al and B), X (X is a halogen atom) and S, and has peaks at 2θ = 20.2 ° and 23.6 ° when measuring by X-ray diffraction with the CuKα line.
    [0027] [027] According to the invention, due to the peaks indicated in the measurement by X-ray diffraction, solid materials of sulfide electrolyte with high conductivity of Li ions can be obtained. These peaks are peaks of a new crystalline phase that is unknown until now. Since the Li-ion conductivity of the new crystalline phase is high, the Li-ion conductivity of the solid sulfide electrolyte material can be improved.
    [0028] [028] Furthermore, since the solid electrolyte material of sulphide according to the embodiment of the invention is vitreous ceramic, it has an advantage that its heat resistance is greater than that of sulphide glass . For example, when Lil is doped in the sulphide glass of the Li 2 SP 2 S 5 system , the conductivity of Li ions can be improved. However, when Lil is doped, in some cases, the crystallization temperature of the sulfide glass can be reduced. In the case where the low temperature of crystallization of the sulphide glass is used, for example, in a battery, when the temperature of the battery reaches the crystallization temperature of the glass and sulphide or more, the heat generation caused by the crystallization of the glass occurs sulfide. As a result, the respective materials that make up the battery can be altered (deteriorated) or a battery case and so on can be damaged. On the other hand, according to the present invention, through the preparation of crystallized glass ceramics in advance, the solid electrolyte material of sulfide, in which the adverse effect of heat generation due to crystallization is inhibited, can be obtained. In addition, there are also advantages regarding the simplification of the cooling mechanism and the safety mechanism for the battery.
    [0029] [029] In addition, in Tomei et al ., Preparation of Amorphous Materials in the system Lil-Li 2 SP 2 S 5 by Mechanical Milling and Their Lithium Ion Conducting Properties ", Proceedings of The Symposium On Solid State Ionics, Vol. 23 , p. 26 - 27 (2003) (Non-Patent Document 1), the amorphous materials of the Lil-Li 2 SP 2 S 5 system obtained by mechanical grinding are disclosed, however, in Non-Patent Document 1, the heat treatment of glass of sulphide of the Lil-Li 2 SP 2 S 5 system is not disclosed or indicated, and even when the sulphide glass of the Lil-Li 2 S-P 2 S 5 system is heat treated in order to precipitate the crystalline phase new, it is necessary to adjust the proportion between Lil and the heat treatment temperature, however, there is no indication of it in Non-Patent Document 1. Furthermore, in F. Stader et al ., "Crystalline halide substituted Li-argyrodites as solid electrolyte for lithium ion batteries ", 216th ECS (The Electrochemical Society) Meeting with EuroCVD 17 and SOFC XI - 11 th International Symposium On Solid Oxide Fuel Cells, 2009, http://www.electrochem.org/meetings/scheduler/abstracts/216/0590.pdf (Non-Patent Document 2), materials crystalline crystals represented by Li 6 PS 5 X (X = Cl, Br, I) are disclosed. However, it is also reported that when I is added, the conductivity of Li ions in the crystalline material is rendered useless. That is, it is shown that the conductivity of Li ions cannot be improved in the crystal (vitreous ceramics) merely by the addition of halogen.
    [0030] [030] The sulphide solid electrolyte material of the embodiment of the invention may be glassy ceramic. The vitreous ceramic of the invention refers to a material obtained by crystallizing the sulfide glass. If the glassy ceramic can be confirmed by X-ray diffraction, for example. In addition, sulfide glass refers to a material that is synthesized by amorphizing the compositions of the raw materials, including not only an exact "glass", in which the periodicity as a crystal is not observed in measurements by diffraction of X-rays. X, but also materials, in general, that are synthesized by amortization through mechanical crushing, which will be described below. Therefore, even when measuring by X-ray diffraction and so on, the peaks derived, for example, from raw materials (Li and others) are observed, as long as the material is synthesized by amorphization, they correspond to the glass sulfide.
    [0031] [031] The sulfide solid electrolyte material, according to the embodiment of the invention, has peaks at 2θ = 20.2 ° and 23.6 ° in the measurement by X-ray diffraction with the CuKα line. These peaks are peaks of a new crystalline phase that is unknown at the moment and have high Li ion conductivity. In some cases, then, the crystalline phase is referred to as a crystalline phase that has high Li ion conductivity. Here , a peak at 2θ = 20.2 ° refers not only to a peak exactly at 2θ = 20.2 °, but also to a peak in the range of 2θ = 20.2 ° ± 0.5 °. Depending on the state of the crystal, a peak position may vary slightly and, consequently, the definition, as mentioned above, is adopted. Likewise, a peak at 2θ = 23.6 ° refers not only to a peak exactly at 2θ = 23.6 °, but also to a peak in the range of 2θ = 23.6 ° ± 0.5 °. The solid electrolyte material of sulfide, according to the embodiment of the invention, preferably has mainly the crystalline phase with high conductivity of Li ions. Specifically, a proportion of crystalline phase with high conductivity of Li ions is preferably 50% by mol or more of an entire crystalline phase.
    [0032] [032] On the other hand, the solid electrolyte material of sulfide, according to the embodiment of the invention, has in some cases peaks at 2θ = 21.0 ° and 28.0 ° in the measurement by X-ray diffraction with CuKα line. These peaks were found by our studies and are peaks of a new crystalline phase which is hitherto unknown, as described above, and which has a lower Li ion conductivity than the high conductive Li ion crystalline phase. In some cases, the crystalline phase is referred to as a crystalline phase having a low Li ion conductivity. Here, a peak at 2θ = 21.0 ° refers not only to a peak exactly at 2θ = 21.0 °, but also at a peak in the range of 2θ = 21.0 0 ± 0.5 °. Depending on the state of the crystal, a peak position may vary slightly and, consequently, the definition, as mentioned above, is adopted. Likewise, a peak at 2θ = 28.0 ° refers not only to a peak exactly at 2θ = 28.0 °, but also to a peak in the range of 2θ = 28.0 ° ± 0.5 °. The solid electrolyte material of sulfide according to the embodiment of the invention preferably contains a crystalline phase with low conductivity of Li ions in a smaller proportion.
    [0033] [033] Furthermore, it can be determined from the results of measurement by X-ray diffraction that the solid electrolyte material of sulfide, according to the embodiment of the invention, has specified peaks. On the other hand, for example, when a proportion of crystalline phase that has high Li ion conductivity is low and a proportion of crystalline phase that has low Li ion conductivity is high, peaks at 2θ = 20.2 ° and 23.6 ° appear smaller, and peaks at 2θ = 21.0 ° and 28.0 ° appear larger. Now, a ratio of a peak intensity at 2θ = 20.2 ° to a peak intensity at 2θ = 21.0 ° is expressed as I 20.2 / I 21.0 and a proportion of a peak intensity at 2θ = 23.6 ° by a peak intensity at 2θ = 21.0 ° is expressed as I 23.6 / I 21.0 . The solid electrolyte material of sulfide, of the embodiment of the invention, is determined to have peaks at 2θ = 20.2 ° and 23.6 ° for each of the I 20.2 / I 21.0 and I 23.6 / I 21.0 of 0.1 or more (preferably 0.2 or more). In the embodiment of the invention, I 20.2 / I 21.0 is preferably 1 or more. This is because a solid electrolyte material of sulfide with a high proportion of the crystalline phase that has high conductivity of Li ions can be obtained.
    [0034] [034] The solid electrolyte sulfide material of the embodiment of the invention includes Li, A (A is at least one type of P, Si, Ge, Al and B), X (X is a halogen atom), and S On the other hand, as described above, the solid electrolyte material of sulfide, in an embodiment of the invention, provided the peaks in the measurement by X-ray diffraction. Here, X-ray diffraction measurement is a method in which, by analyzing the results of X-ray diffraction from a crystal lattice, an atomic arrangement in a crystal is specified. Therefore, based on this principle, a peak pattern in X-ray diffraction measurement depends on a crystalline structure, but it does not depend much on the types of atoms that configure the crystal structure. Therefore, regardless of the type of A and X, when the same crystal structure is formed, a similar pattern can be obtained. That is, regardless of the type of A and X, when a crystalline phase that has high conductivity of Li ions is formed, a similar pattern can be obtained. The position of the pattern may vary slightly. Also from this point of view, peaks at 2θ = 20.2 ° and 23.6 ° are preferably defined in a range of 2θ = 20.2 ° ± 0.5 ° and 23.6 ° ± 0.5 °, respectively.
    [0035] [035] Furthermore, the solid electrolyte sulphide material of the embodiment of the invention is preferably configured by an ion conductor comprising Li, A (A is at least one type of P, Si, Ge, Al and B ), and S, and LiX (X is a halogen atom). At least a part of LiX is generally present embedded in an ion conductor structure as a LiX component.
    [0036] [036] The ion conductor, in the embodiment of the invention, includes Li, A (A is at least one type of P, Si, Ge, Al and B), and S. The ion conductor is not particularly limited since that it includes Li, A, and S., however, among these, it is preferred that the ion conductor has an ortho composition. This is because a solid electrolyte sulphide material with high chemical stability can be obtained. Here, ortho, generally refers to an oxo acid with the highest degree of hydration among the oxo acids obtained by hydration of the same oxide. In the embodiment of the invention, a sulphide crystal composition to which Li 2 S is added most is referred to as an ortho composition. For example, in a Li 2 SP 2 S 5 system , Li 3 PS 4 corresponds to the ortho composition, in a Li 2 S-AI 2 S 3 system , Li 3 AIS 3 corresponds to the ortho composition, in a Li 2 SB system 2 S 3 , Li 3 BS 3 corresponds to the ortho composition, in a Li 2 S- SiS 2 system , Li 4 SiS 4 corresponds to the ortho composition, and in a Li 2 S-GeS 2 system , Li 4 GeS 4 corresponds to the composition ortho.
    [0037] [037] Furthermore, in the embodiment of the present invention, "it has an ortho composition" includes not only an exact ortho composition, but also a composition in its proximity. Specifically, "has an ortho composition" means that an anionic structure of the ortho composition (the PS 4 -3 structure, SiS 4 -4 structure, GeS 4 -4 structure, AIS 3 -3 structure, and BS 3 -3 structure) is mostly contained. A ratio of the anionic structure of the ortho composition to a total anion structure of an ion conductor is preferably 60% per mol or more, more preferably 70% per mol or more, even more preferably 80% per mol or more, and primarily 90% per mol or more. The proportion of the anionic structure of the ortho composition can be determined using Raman spectrometry, NMR, XPS and so on.
    [0038] [038] Furthermore, the solid sulfide electrolyte material, of the embodiment of the invention, is preferably obtained in such a way that the composition of a raw material containing Li 2 S, A sulfide (A is at least one type of P, Si, Ge, Al and B), and LiX (X is a halogen atom) is amorphized and heat treated further on.
    [0039] [039] The Li 2 S contained in the raw material composition preferably contain less impurities. This is because a secondary reaction can be suppressed. As a method for synthesizing Li 2 S, a method described, for example, in Japanese Patent Application Publication No. 07 - 330312 (JP 07-330312 A), among others, can be cited. In addition, Li 2 S is preferably purified using a method described in WO 2005 / 040039. On the other hand, as the A sulfide contained in the raw material composition, P 2 S 3 , P 2 S 5 , SiS 2 , GeS 2 , AI 2 S 3 , B 2 S 3 , others can be mentioned.
    [0040] [040] Furthermore, the solid sulfide electrolyte material does not preferably contain Li 2 S. This is because a solid sulfide electrolyte material that generates a small amount of hydrogen sulfide can be obtained. When Li 2 S reacts with water, hydrogen sulfide is generated. For example, when a proportion of Li 2 S contained in the raw material composition is high, Li 2 S tends to remain, if the solid electrolyte material of sulfide "does not substantially contain Li 2 S" can be confirmed by ray diffraction -X. Specifically, when Li 2 S peaks (2θ = 27.0 °, 31.2 °, 44.8 ° and 53.1 °) are not contained, the solid sulphide electrolyte material is determined not to contain substantially Li 2 S .
    [0041] [041] Furthermore, the solid sulfide electrolyte material does not preferably contain cross-linked sulfur. This is because a solid sulfide electrolyte material that generates a small amount of hydrogen sulfide can be obtained. "Cross-linked sulfur" refers to cross-linked sulfur in a compound formed by a reaction between Li 2 S and A. sulfide. For example, cross-linked sulfur with an S 3 structure PS-PS 3 that is formed by a reaction between Li 2 S and P 2 S 5 corresponds to this. This cross-linked sulfur tends to react with water and tends to generate hydrogen sulfide. In addition, whether the solid electrolyte material of sulfide "does not substantially contain cross-linked sulfur" can be confirmed by measuring the Raman spectrum. For example, in the case of solid sulphide electrolyte material from the Li 2 SP 2 S 5 system , a peak of the S 3 PS-PS 3 structure generally appears at 402 cm -1 . Therefore, it is preferable that the peak is not detected. In addition, a peak of a PS 4 -3 structure usually appears at 417 cm -1 . In the embodiment of the present invention, an intensity I 402 at 402 cm -1 is preferably less than an intensity I 417 at 417 cm -1 . More specifically, in relation to the intensity of I 417 , the intensity I 402 is preferably, for example, 70% or less, more preferably 50% or less, and even more preferably 35% or less. In addition, a solid sulphide electrolyte material, other than the solid sulphide electrolyte material of the Li 2 SP 2 S 5 system , does not substantially contain cross-linked sulfur can be determined by specifying a unit containing sulfur of cross-linking and by measuring a unit peak.
    [0042] [042] In addition, in the case of the solid sulphide electrolyte material of the Li 2 SP 2 S 5 system , the proportion of Li 2 S and P 2 S 5 to obtain the ortho composition is, per mol, Li 2 S: P 2 S 5 = 75: 25. The same proportion applies also in the case of the solid electrolyte material of the Li 2 S-AI 2 S 3 system and in the case of the solid electrolyte material of the Li 2 SB 2 system. S 3 . On the other hand, in the case of solid sulphide electrolyte material of the Li 2 S-SiS 2 system , the proportion of Li 2 S and SiS 2 to obtain the ortho composition is, per mol, Li 2 S: SiS 2 = 66, 7: 33.3. The same proportion also applies to the case of the solid electrolyte material of the Li 2 S-GeS 2 system .
    [0043] [043] In the case where the raw material composition contains Li 2 S and P 2 S 5 , a ratio between Li 2 S and a total sum of Li 2 S and P 2 S 5 is preferably defined in the range of 70% per mol to 80% per mol, more preferably in the range of 72% per mol to 78% per mol, and even more preferably, in the range of 74% per mol to 76% per mol. The proportion defined in the same range is also applied both in the case where the raw material composition contains Li 2 S and AI 2 S 3 and the case where the raw material composition contains Li 2 S and B 2 S 3 . On the other hand, in the case where the raw material composition contains Li 2 S and SiS 2 , the ratio between Li 2 S and a total sum of Li 2 S and SiS 2 is defined, preferably in the range of 62.5% per mol to 70.9% per mol, more preferably, in the range of 63% per mol to 70% per mol, and even more preferably, in the range of 64% per mol to 68% per mol. The proportion defined in the same range is also applied in the case where the raw material composition contains Li 2 S and GeS 2 .
    [0044] [044] Now, X in LiX is a halogen that is specifically F, Cl, Br and I. Among these, Cl, Br and I are preferable. This is because a solid electrolyte material of sulfide with high ion conductivity can be obtained. In addition, a proportion of LiX in the sulphide solid electrolyte material of the embodiment of the invention is not particularly limited as long as it allows the desired vitreous ceramic to be synthesized. However, for example, the proportion of LiX is preferably in the range of 14% per mol or more and 30% per mol or less, and preferably in the range of 15% per mol or more and 25% per mol or less.
    [0045] [045] The solid sulfide electrolyte material of the embodiment of the invention is in the form of particles, for example. An average particle size (D50) of the solid electrolyte material in the form of particles is preferably in the range, for example, 0.1 μm to 50 μm. In addition, the solid sulphide electrolyte material preferably has a high conductivity of Li ions. The conductivity of Li ions therein at room temperature is preferably, for example, 1 x 10 -4 S / cm or more, and more preferably 1 x 10 -3 S / cm or more.
    [0046] [046] The sulphide solid electrolyte material of the embodiment of the invention can be used in all applications requiring Li ion conductivity. Among these, the sulphide solid electrolyte material is preferably used in batteries. B. Solid State Lithium Battery
    [0047] [047] Next, a solid state lithium battery of an embodiment of the invention will be described. A solid-state lithium battery of an embodiment of the invention includes a layer of positive electrode active material that contains a positive electrode active material, a layer of negative electrode active material that contains a negative electrode active material, and a solid electrolyte layer formed between the positive electrode active material layer and the negative electrode active material layer, and at least one positive electrode active material layer, the negative electrode active material layer and the electrolyte layer solid contains the sulfide solid electrolyte material.
    [0048] [048] According to the embodiment of the present invention, by using the solid electrolyte material of sulfide, the lithium battery in solid state with high conductivity of Li ions can be obtained. As a result, the output power of the lithium battery can be higher.
    [0049] [049] Figure 1 is a schematic sectional view showing an example of the solid-state lithium battery of the embodiment of the invention. A solid-state lithium battery 10 shown in Figure 1 includes a layer of positive electrode active material 1 containing a positive electrode active material, a layer of negative electrode active material 2 containing a negative electrode active material, a layer of solid electrolyte 3 formed between a layer of active material of electrode 1 and a layer of active material of negative electrode 2, a collector of positive electrode 4 that captures the current from the layer of active material of electrode 1, and a collector of negative electrode 5 that captures the current from the electrode active material layer 2. In the embodiment of the invention, at least one of the positive electrode active material layers 1, a negative electrode active material layer 2 and the solid electrolyte layer 3 includes the solid sulfide electrolyte material described in " A. Solid Sulfide Electrolyte Material ". The respective constituents of the solid-state lithium battery of the embodiment of the invention will be described below. 1. Positive Electrode Active Material Layer
    [0050] [050] First, a layer of positive electrode active material, in an embodiment of the invention will be described. The layer of positive electrode active material in the embodiment of the invention is a layer that contains at least one positive electrode active material, and can also contain at least one of a solid electrolyte material, a conductive material and a binder, as necessary.
    [0051] [051] In the embodiment of the invention, a solid electrolyte material contained in the positive electrode active material layer is preferably the solid sulfide electrolyte material described in " A. Solid Sulphide Electrolyte Material ". The content of the sulphide solid electrolyte material in the positive electrode active material layer is preferably, for example, in the range of 0.1% by volume to 80% by volume, more preferably in the range of 1% by volume at 60 % by volume, and particularly in the range of 10% by volume to 50% by volume.
    [0052] [052] Examples of positive electrode active materials include, but are not particularly limited to, a layer of rock salt, such as active materials, such as LiC0O 2 , LiMnO 2 , LiNiO 2 , LiVO 2 and LiNi 1/3 Co 1/3 Mn 1/3 O 2 , active spinel -type materials ( spynel-type ), such as LiMn 2 O 4 and Li (Ni 0.5 Mn 1.5 ) O 4 , and active materials of the olivine type ( olivine-type) such as LiFePO 4, LiMnPO 4, 4 and LiNiPO LiCuPO 4. In addition, silicon-containing oxides, such as Li 2 FeSiO 4 Li 2 MnSiO 4 , can also be used as positive electrode active material.
    [0053] [053] In particular, when the sulfide solid electrolyte material has an ion conductor with an ortho composition and is formed with Lil, the positive electrode active material preferably has a potential of 2.8 V (vs. Li) or more and, more preferably, it has a potential of 3.0 V (vs. Li) or more. This is because Lil can be efficiently inhibited from oxidative decomposition. Since the decomposition of Lil is considered to occur in the vicinity of 2.8 V, a solid electrolyte material of sulfide with Lil has not been used in a layer of positive electrode active material. In contrast, the sulphide solid electrolyte material has an ion conductor that has the ortho composition and, as a consequence, Lil is considered to be stabilized through an interaction with the ion conductor, thereby inhibiting oxidative decomposition of the Lil.
    [0054] [054] The positive electrode active material is in the form of particles, for example, and preferably in the form of a real sphere or an oval sphere. In addition, when the positive electrode active material is in the form of particles, their average particle size is preferably in the range, for example, 0.1 μm to 50 μm. In addition, a positive electrode active material content in the positive electrode active material layer is preferably in the range, for example, 10% by volume to 99% by volume, and more preferably in the range of 20% by volume. volume to 99% by volume.
    [0055] [055] The layer of positive electrode active material in the embodiment of the invention may also contain, in addition to the positive electrode active material and the solid electrolyte material, at least one of a conductive material and a binder. Examples of conductive materials include acetylene black , Ketjen black , carbon fibers and so on. Examples of binders include fluorine-containing binders, such as PTFE and PVDF. The thickness of the positive electrode active material layer is preferably in the range, for example, 0.1 μm to 1000 μm. 2. Negative Electrode active material layer
    [0056] [056] Next, a layer of active material of negative electrode in the embodiment of the invention will be described. The layer of active negative electrode material of the embodiment of the invention is a layer that contains at least one active negative electrode material and can also contain at least one of a solid electrolyte material, a conductive material and a binder, as required.
    [0057] [057] In the embodiment of the invention, a solid electrolyte material contained in the negative electrode active material layer is preferably the solid sulfide electrolyte material described in " A. Solid Sulphide Electrolyte Material ". The content of the sulfide solid electrolyte material in the negative electrode active material layer is preferably, for example, in the range of 0.1% by volume to 80% by volume, more preferably, in the range of 1% by volume at 60% by volume, and particularly in the range of 10% by volume to 50% by volume.
    [0058] [058] Examples of active negative electrode material include active metallic materials and active carbon materials. Examples of metallic active material include In, Al, Si and Sn. On the other hand, examples of active carbon materials include meso - carbon microspheres (MCMB), highly oriented pyrolytic graphite (HOPG), hard carbon, soft carbon and so on. The content of the negative electrode active material in the negative electrode active material layer is preferably in the range of 10% by volume to 99% by volume, for example, and more preferably in the range of 20% by volume to 99% by volume. Both the conductive material and the binder are the same as those used in the positive electrode active material layer. The thickness of the negative electrode active material layer is preferably in the range of 0.1 μm to 1000 μm, for example. 3. Solid Electrolyte Layer
    [0059] [059] Next, the solid electrolyte layer of the embodiment of the invention will be described. The solid electrolyte layer of the embodiment of the invention is formed by a solid electrolyte material disposed between a layer of positive electrode active material and the layer of active electrode negative material. The solid electrolyte material contained in the solid electrolyte layer is not particularly limited, as long as it has the conductivity of Li ions.
    [0060] [060] In the present invention, the solid electrolyte material contained in the solid electrolyte layer is preferably the solid sulfide electrolyte material described in " A. Solid Sulphide Electrolyte Material ". The content of the sulphide solid electrolyte material in the solid electrolyte layer is not particularly limited, as long as the desired insulating properties are obtained. The content of the sulfide solid electrolyte material is preferably in the range of 10% by volume to 100% by volume, for example, and more particularly, in the range of 50% by volume to 100% by volume. In particular, in the present invention, the solid electrolyte layer is preferably configured only by the solid sulfide electrolyte material.
    [0061] [061] In addition, the solid electrolyte layer may contain a binder. This is because, when the binder is contained, the layer of flexible solid electrolyte can be obtained. Examples of binders include fluorine-containing binders, such as PTFE and PVDF. The thickness of the solid electrolyte layer is preferably in the range of 0.1 μm to 1000 μm, and, more preferably, in the range of 0.1 μm to 300 μm. 4. Another Configuration
    [0062] [062] The solid-state lithium battery of the embodiment of the invention includes at least the positive electrode active material layer, the negative electrode active material layer, and the solid electrolyte layer. In addition, the solid-state lithium battery typically includes a positive electrode collector that picks up current from the positive electrode active material layer, and a negative electrode collector that picks up current from the negative electrode active material layer. Examples of positive electrode collector material include SUS, aluminum, nickel, iron, titanium, carbon and so on. Among these, SUS is preferable. On the other hand, examples of negative electrode collector material include SUS, copper, nickel, carbon and so on. Among them, SUS is preferable. In addition, the thickness, shape, among others, of the positive electrode collector and negative electrode collector are preferably selected appropriately, in accordance with the uses and so on of the solid state lithium battery. In addition, as well as a battery case used in the invention, a battery case can be used for general solid-state lithium batteries. An example of a battery box includes a SUS battery box. 5. Solid State Lithium Battery
    [0063] [063] The solid-state lithium battery of the embodiment of the invention can be a primary battery or a secondary battery. However, the secondary battery is preferable. This is because the secondary battery can be charged and discharged repeatedly and is useful as a car battery. Examples of a solid-state lithium battery form of the embodiment of the invention include the coin form, a laminated form, a cylindrical form, and a rectangular form.
    [0064] [064] Furthermore, the method for producing a solid-state lithium battery of the embodiment of the invention is not particularly limited, as long as the solid-state lithium battery described above can be produced. That is, a general method for producing a solid-state lithium battery can also be used. Examples of the method for producing a solid-state lithium battery include a method in which a material that sets up a layer of positive electrode active material, a material that sets up a layer of solid electrolyte, and a material that sets up a layer of active negative electrode material are sequentially pressed to prepare an electricity generating element, the electricity generating element is housed within a battery box, and the battery box is caulked, and so on. C. Method for Producing Solid Sulfide Electrolyte Material
    [0065] [065] Next, a method for producing the sulfide solid electrolyte material of the embodiment of the invention will be described. The method for producing the sulfide solid electrolyte material of the embodiment of the invention includes the steps of: amortizing the composition of a raw material containing Li 2 S, an A sulfide (A is at least one type of P, Si, Ge, Al, and B), and LiX (X is a halogen) to synthesize the sulfide glass; and heat the sulphide glass to a temperature equal to or greater than a crystallization temperature of the same in order to synthesize the glass ceramic with peaks at 2θ = 20.2 ° and 23.6 ° in X-ray diffraction measurement with the CuKα line, in which the proportion between the LiX contained in the raw material composition and the temperature of the heat treatment in the heating step is controlled to obtain the vitreous ceramic.
    [0066] [066] Figure 2 is a flow chart showing an example of the production method of a solid electrolyte material of sulfide of the embodiment of the invention. In Figure 2, first, the composition of a raw material containing Lil, Li 2 S and P 2 S 5 is prepared. Then, the raw material composition is mechanically ground to synthesize sulfide glass containing an ion conductor (for example, Li 3 PS 4 ) containing Li, P, and S, and Lil. Then, the sulphide glass is heated to a temperature equal to or greater than its crystallization temperature to obtain the glass ceramics (solid electrolyte material of sulfide) with peaks at 2θ = 20.2 ° and 23.6 ° in X - ray diffraction measurement with CuKα line.
    [0067] [067] According to the invention, when the ratio between the LiX contained in the raw material composition and the heat treatment temperature in the heating stage of the sulfide glass is adjusted, a solid electrolyte material of sulfide with high ion conductivity Li can be obtained. The method for producing the sulfide solid electrolyte material of the embodiment of the invention will be described below, for each step. 1. Amortization Stage
    [0068] [068] The amortization step in the embodiment of the invention is the step of amortizing a composition of a raw material containing Li 2 S, an A sulfide (A is at least one type of P, Si, Ge, Al and B), and LiX (X is a halogen) to synthesize the sulfide glass.
    [0069] [069] Now Li 2 S, an A sulfide (A is at least one type of P, Si, Ge, Al, and B), and LiX (X is a halogen atom) in the raw material composition are the same as those described in " A. Solid Sulfide Electrolyte Material ", and, consequently, its description will be omitted. The proportion of LiX in the raw material composition is not particularly limited, as long as it allows the synthesis of the desired glassy ceramics, and varies slightly, depending on the condition of synthesis. The proportion of LiX in the raw material composition is preferably in the range of 14% per mole to 30% per mole or in the range close to them, which allows the synthesis of the vitreous ceramic. According to the conditions of the examples described below, when the proportion of LiX is greater than 14% per mole and less than 30% per mole, the desired glassy ceramic can be obtained.
    [0070] [070] Examples of a method for amortizing the raw material composition include a mechanical grinding method and a melt quenching method . Among these, the preferred method is mechanical grinding. This is because the mechanical grinding method allows processing at room temperature to simplify the production process. In addition, although the tempering fusion method is limited by the reaction atmosphere and the reaction vessel, the mechanical grinding method is advantageous in that sulfide glass, which has a target composition, can be conveniently synthesized. The mechanical shredding method can be a dry mechanical shredding method or a wet mechanical shredding method. However, the preferred method is wet mechanical grinding. This is because the raw material composition can be inhibited by adhering to a surface of the container wall in order to allow obtaining the sulphide glass with superior amorphous properties.
    [0071] [071] The method of mechanical crushing is not particularly limited as long as it can mix the composition of raw material during the transmission of mechanical energy. Examples of the method include a ball mill, a vibration mill, a turbo mill, a mechanical melting mill, and a disc mill. Among these, the ball mill is preferable, and a satellite ball mill is particularly preferable. This is because the desired sulfide glass can be efficiently obtained.
    [0072] [072] Various types of mechanical crushing conditions are defined in order to obtain the desired sulfide glass. For example, when a satellite ball mill is used, a raw material composition and spray spheres are loaded into a container and treated at a predetermined speed of rotation for a predetermined time. In general, the higher the speed of rotation, the greater the speed of production of the sulfide glass, and the longer the processing time, the greater the conversion rate of the composition of the raw material into the sulfide glass. The rotation speed of a base when a satellite ball mill is used is, for example, in the range of 200 rpm to 500 rpm, and preferably in the range of 250 rpm to 400 rpm. In addition, a processing time is defined when the satellite ball mill is used, for example, in the range of one hour to 100 hours, and preferably in the range of one hour to 50 hours. Examples of materials for the container and the spray balls for the ball mill include ZrO 2 and AI 2 O 3 . In addition, the diameter of the spray balls is, for example, in the range of 1 mm to 20 mm.
    [0073] [073] A liquid used for wet mechanical crushing that preferably has a property that does not generate hydrogen sulphide during the reaction with the raw material composition is preferred. Hydrogen sulfide is generated when protons dissociated from molecules in the liquid react with the raw material composition of the sulfide glass. Therefore, the liquid preferably has non-protonic properties to the point that it does not generate hydrogen sulfide. In addition, the non-protonic liquid can generally be divided into polar non-protonic liquids and non-protonic supporting liquids.
    [0074] [074] Examples of polar non-protonic liquids include, but are not particularly limited to, ketones, such as acetone, nitriles, such as acetonitrile, amides such as N, N - dimethyl formamide (DMF), and sulfoxides, such as dimethyl sulfoxide (DMSO).
    [0075] [075] Examples of non-protonic non-proton liquids include an alkane that has a liquid form at room temperature (25 ° C). The alkane can be a chain alkane or a cyclic alkane. The chain alkane preferably has 5 or more carbon atoms. On the other hand, the upper limit on the number of carbon atoms in the chain alkane is not particularly limited, as long as it is in liquid form at room temperature. Specific examples of chain alkane include pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, and paraffin. The chain alkane can have a branched chain. On the other hand, specific examples of cyclic alkane include cyclopentane, cyclohexane, cycloheptane, cyclooctane, and cycloparaffin.
    [0076] [076] In addition, other examples of non-protonic apolar liquids include aromatic hydrocarbons, such as benzene, toluene, and xylene, chain ethers, such as diethyl ether and dimethyl ether, cyclic ethers such as tetrahydrofuran, alkyl halogenates, such as chloroform, methyl chloride, and methylene chloride; esters, such as ethyl acetate, and fluorocarbons, such as benzene fluoride, heptane fluoride, 2,3 - dihydroperfluoropentane, and 1,1,2,2,3,3,4 - heptafluorocyclopentane. An amount of liquid addition is not particularly limited, as long as it is an amount that allows obtaining a desired solid electrolyte material of sulfide. 2. Heating Step
    [0077] [077] Next, the heating step in the embodiment of the invention will be described. The heating step in the embodiment of the invention is the step of heating the sulphide glass to a temperature equal to or greater than the crystallization temperature of the same to synthesize vitreous ceramic having peaks at 2θ = 20.2 ° and 23.6 ° in X-ray diffraction measurement with the CuKα line.
    [0078] [078] The heat treatment temperature is generally a temperature equal to or greater than the crystallization temperature of the sulfide glass. The crystallization temperature of the sulfide glass can be determined by differential thermal analysis (DTA). The heat treatment temperature is not particularly limited, as long as it is a temperature equal to or greater than the crystallization temperature. However, it is preferably, for example, 160 ° C or more. On the other hand, the upper limit of the heat treatment temperature is not particularly limited, as long as it is a temperature that allows the synthesis of the desired glass ceramic and varies slightly depending on a sulphide glass composition. The upper limit of the heat treatment temperature is generally a temperature that is in the vicinity of 200 ° C and allows the synthesis of glass ceramics. According to the conditions of the examples described below, when the heat treatment temperature is less than 200 ° C, the desired glass ceramic can be obtained.
    [0079] [079] The heat treatment time is not particularly limited, as long as the heat treatment time allows to obtain the desired glassy ceramics, and preferably in the range, for example, one minute to 24 hours. In addition, heat treatment is preferably conducted in an inert gas atmosphere (for example, Ar gas atmosphere). This is because inhibition of the deterioration of vitreous ceramics (eg oxidation) can occur. A method of heat treatment is not particularly limited. For example, a method that uses a firing oven can be used.
    [0080] [080] The above embodiments are for illustrative purposes only, and anything that has substantially the same constitution and produces the same effect, such as the technical idea that is described in the claims of the present invention, is included in the technical scope of the present invention. Examples
    [0081] [081] The present invention will be described more specifically below, with reference to the examples. Unless clearly stated otherwise, the respective weighing, synthesis, drying operations, and so on, were conducted under an atmosphere of Ar. Example 1
    [0082] [082] As starting raw materials, lithium sulfide (Li 2 S, manufactured by Nippon Chemical Industrial Co., Ltd.), phosphorus pentasulfide (P 2 S 5 , manufactured by Aldrich Corporation) and iodide Lithium (Lil, manufactured by Aldrich Corporation) were used. Then, Li 2 S and P 2 S 5 were measured to be 75 Li 2 S. 25 P 2 S 5 by molar ratio (Li 3 PS 4 , ortho composition). Then, Lil was measured so that the proportion of Lil can be 14% per mole. The measured starting raw materials were mixed in an agate mortar for 5 minutes, 2 g of the mixture was loaded into a container (45 cc, ZrO 2 ) of a satellite ball mill, the dehydrated heptane (water content: 30 ppm or less, 4 g) was loaded into this location, as were the balls of ZrO 2 (Φ = 5 mm, 53 g), then the container was completely and hermetically sealed. The container was installed in a satellite ball mill machine (trade name: P7, manufactured by Fritsch GmbH), and the mechanical grinding was carried out at 500 rpm of base for 40 hours. After that, the mixture was dried at 100 ° C to remove the heptane to obtain the sulfide glass.
    [0083] [083] Then, 0.5 g of the resulting sulfide glass was loaded into a glass tube, and the glass tube was loaded into a hermetically sealed SUS container. The hermetically sealed container was heated to 190 ° C for 10 hours and the vitreous ceramics were obtained. The molar composition of the resulting glass ceramics corresponds to x = 14 in xLil. (100 - x) (0.75 Li 2 S. 0.25 P 2 S 5 ). Examples 2 to 5
    [0084] [084] Glass ceramics were obtained in a similar manner to Example 1, except that the ratio of Lil to xLil. (100 - x) (0.75 Li 2 S. 0.25 P 2 S 5 ) was changed to x = 15, 20, 24, and 25, respectively, and the heat treatment temperature was changed to the temperatures described in Table 1, respectively. Comparative Examples 1 to 4
    [0085] [085] The sulfide glasses were obtained in a similar manner to that of Example 1, except that the ratio of Lil to xLil. (100 - x) (0.75 Li 2 S. 0.25 P 2 S 5 ) was changed to x = 0, 10, 13, and 30, respectively, and the heat treatment temperature was changed to the temperatures described in Table 1, respectively. Comparative Examples 5 to 9
    [0086] [086] The sulfide glasses were obtained in a similar manner to that of Example 1, except that the ratio of Lil to xLil. (100 - x) (0.75 Li 2 S. 0.25 P 2 S 5 ) was changed to x = 0.10, 20, 30, and 40, respectively. After that, without the thermal treatment, the sulfide glasses were prepared as reference samples.
    [0087] [087] Measurements by X-ray diffraction (XRD), with CuKα line, were carried out on the glass ceramics obtained in Examples 1 to 5 and in Comparative Examples 2 to 4. In the measurement of XRD, RJNT Ultima III (name commercially manufactured by Rigaku Corporation) was used. The results are shown in Figure 3 and Figure 4. As illustrated in Figure 3, it was confirmed that each of the glass ceramics obtained in Examples 1 to 5, has peaks in a crystalline phase with high conductivity of Li ions in 2θ = 20.2 ° and 23.6 °. On the other hand, as illustrated in Figure 4, in the vitreous ceramics obtained in Comparative Examples 2 to 4, the peaks of the crystalline phase with high conductivity of Li ions were not confirmed, and only the peaks of a crystalline phase with low conductivity of ions Li at 2θ = 21.0 ° and 28.0 ° were confirmed. In addition, from each of the graphs obtained from XRD, a ratio of a peak intensity at 2θ = 20.2 ° to a peak intensity at 2θ = 21.0 ° (I 20.2 / I 21.0 ) and a peak ratio of 2θ = 23.6 ° to a peak intensity of 2θ = 21.0 ° (I 23.6 / l 21.0 ) were obtained. The results are shown in Table 2. In Example 1, the peaks at 2θ = 21.0 ° and 28.0 ° have not been confirmed and, consequently, the proportion of peak intensities has not been obtained.
    [0088] [088] The conductivity of Li ions (at room temperature) was measured in each of the samples obtained in Examples 1 to 5 and Comparative Examples 1 to 9, by the AC impedance method. The conductivity of Li ions was measured as described below. First, a powder sample was cold pressed under pressure of 4 tonnes / cm 2 and a pellet that had a diameter of 11.29 mm and a thickness of about 500 μm was prepared. Then, the sediment was installed in a container with an inert gas atmosphere, which was filled with Ar gas, to perform the measurement. In the measurement, SOLARTRON (trade name: SI 1260, manufactured by Toyo Corporation) was used. The temperature measurement was controlled at 25 ° C using a thermostat. The results are shown in Table 3 and Figure 5.
    [0089] [089] As shown in Table 3 and Figure 5, all glass ceramics obtained in Examples 1 to 5 had high Li ion conductivity. This is considered because the glass ceramics obtained in Examples 1 to 5 have a crystalline phase with high conductivity of Li ions, which have peaks at 2θ = 20.2 ° and 23.6 °. In addition, the content of Lil x is the same between Comparative Example 1 and Comparative Example 5, between Comparative Example 2 and Comparative Example 6, and between Comparative Example 4 and Comparative Example 8, respectively. As described above, when the Lil doped sulfide glass is heat treated, the conductivity of Li ions is generally lost. On the other hand, in the glass ceramics obtained in Examples 1 to 5, a characteristic behavior was revealed: when the sulphide glass is heat treated, the conductivity of Li ions is improved, and, in addition, the conductivity of Li ions was improved. extremely high when compared to glass ceramics. Examples 6 to 8
    [0090] [090] Glassy ceramics were obtained in a similar manner to Example 1, except that the ratio of Lil to xLil. (100 - x) (0.75 Li 2 S. 0.25 P 2 S 5 ) was changed to x = 15, and the heat treatment temperature was changed to 170 ° C, 180 ° C and 190 ° C, respectively . Comparative Example 10
    [0091] [091] The sulfide glass was obtained in a similar manner to that of Example 1, except that the ratio of Lil to xLil. (100 - x) (0.75 Li 2 S. 0.25 P 2 S 5 ) was changed to x = 15. Subsequently, without conducting a heat treatment, for example, the sulphide glass (as a reference sample ) It was obtained. Comparative Example 11
    [0092] [092] The glassy ceramic was obtained in a similar manner to that of Example 1, except that the ratio of Lil to xLil. (100 - x) (0.75 Li 2 S. 0.2 5P 2 S 5 ) was changed to x = 15, and the heat treatment temperature was changed to 200 ° C. Rating 2 X-ray Diffraction Measurement
    [0093] [093] An X-ray diffraction (XRD) measurement with the CuKα line was performed on each of the vitreous ceramics obtained in Examples 6 to 8 and Comparative Example 11.0 The measurement method was the same as that described in Evaluation 1. The results are shown in Figure 6. As illustrated in Figure 6, it was confirmed that each of the glass ceramics obtained in Examples 6 to 8 has peaks of a crystalline phase with high conductivity of Li ions at 2θ = 20.2 ° and 23.6 °. On the other hand, in the vitreous ceramics obtained in Comparative Example 11, while the peaks of the crystalline phase with high conductivity of Li ions were not confirmed, only the peaks of a crystalline phase with low conductivity of Li ions at 2θ = 21, 0 ° and 28.0 ° were confirmed Measurement of Li ion conductivity
    [0094] [094] The conductivity of Li ions (at room temperature) was measured in each of the samples obtained in Examples 6 to 8 and Comparative Examples 10 and 11 by the AC impedance method. The measurement method was the same as that described in Evaluation 1. The results are shown in the Figure. 7. As shown in Figure 7, all glass ceramics obtained in Examples 6 to 8 exhibited a higher Li ion conductivity than Comparative Example 10, where heat treatment was not carried out. On the other hand, in the sample obtained in Comparative Example 11, it is considered that the heat treatment temperature was too high to obtain the crystalline phase with high conductivity of Li ions
    权利要求:
    Claims (17)
    [0001]
    Solid electrolyte sulphide material CHARACTERIZED by understanding: a glassy ceramic containing Li, A, X and S, where A is at least one element among P, Si, Ge, Al, and B, X is a halogen, and the sulphide solid electrolyte material has peaks at 2θ = 20.2 ° and 23.6 ° when measuring by X-ray diffraction using the CuKα line.
    [0002]
    Solid electrolyte sulphide material according to claim 1, CHARACTERIZED by the fact that a ratio between a peak intensity at 2θ = 20.2 ° and a peak intensity at 2θ = 21.0 ° is 1 or more.
    [0003]
    Sulfide solid electrolyte material according to claim 1 or 2, CHARACTERIZED by the fact that the sulphide solid electrolyte material does not contain cross-linked sulfur.
    [0004]
    Solid electrolyte sulphide material according to any one of claims 1 to 3, CHARACTERIZED by the fact that the vitreous ceramic includes an ion conductor containing Li, A and S, and LiX.
    [0005]
    Solid electrolyte sulphide material, according to claim 4, CHARACTERIZED by the fact that a proportion of LiX is 14% per mol or greater and less than 30% per mol.
    [0006]
    Solid electrolyte sulphide material, according to claim 5, CHARACTERIZED by the fact that the proportion of LiX is greater than 14% per mole and less than 30% per mole.
    [0007]
    Solid electrolyte sulphide material, according to claim 5 or 6, CHARACTERIZED by the fact that the proportion of LiX is 25% per mol or less.
    [0008]
    Solid electrolyte sulphide material according to any one of claims 4 to 7, CHARACTERIZED by the fact that the ion conductor has an ortho composition.
    [0009]
    Solid electrolyte sulphide material according to any one of claims 1 to 8, CHARACTERIZED by the fact that the solid electrolyte sulphide material includes 50% per mol or more of a crystalline phase corresponding to 2θ = 20.2 ° and 23, 6 ° with respect to a total crystalline phase of the sulphide solid electrolyte material.
    [0010]
    Solid-state lithium battery FEATURED for understanding: a layer of positive electrode active material (1) containing a positive electrode active material; a layer of active negative electrode material (2) containing an active negative electrode material, and a solid electrolyte layer (3) disposed between the positive electrode active material layer (1) and the negative electrode active material layer (2), wherein at least one of the positive electrode active material layer (1), the negative electrode active material layer (2), and the solid electrolyte layer (3) includes the sulfide solid electrolyte material as defined in any one of claims 1 to 9.
    [0011]
    Solid-state lithium battery FEATURED for understanding: a layer of positive electrode active material (1) containing a positive electrode active material; a layer of active negative electrode material (2) containing an active negative electrode material, and a solid electrolyte layer (3) disposed between the positive electrode active material layer (1) and the negative electrode active material layer (2), wherein at least one of the positive electrode active material layer (1), the negative electrode active material layer (2), and the solid electrolyte layer (3) includes the sulfide solid electrolyte material as defined in the claim 8, the glassy ceramic includes an ion conductor containing, Li, A, and S, and LiX where LiX is Lil, where the ion conductor has an ortho composition, and the positive electrode active material has a potential of 2.8 V or more compared to Li.
    [0012]
    Method to produce a solid electrolyte material of sulfide including glassy ceramic, the method being CHARACTERIZED by understanding: amorphize a raw material composition containing Li2S, an A sulfide, and LiX to synthesize sulfide glass, and heat the sulphide glass to a heat treatment temperature equal to or greater than a crystallization temperature of the sulphide glass to synthesize the glass ceramic having peaks at 2θ = 20.2 ° and 23.6 ° in the measurement by diffraction of X with CuKα line, where A is at least one element among P, Si, Ge, Al and B, X is a halogen, and a proportion between the LiX contained in the raw material composition and the heat treatment temperature is controlled to obtain the glassy ceramic.
    [0013]
    Method according to claim 12, CHARACTERIZED by the fact that a ratio between a peak intensity at 2θ = 20.2 ° and a peak intensity at 2θ = 21.0 o is 1 or more.
    [0014]
    Method according to claim 12 or 13, CHARACTERIZED by the fact that the solid sulfide electrolyte material does not contain cross-linked sulfur.
    [0015]
    Method according to any one of claims 12 to 14, CHARACTERIZED by the fact that the proportion of LiX contained in the raw material composition is 14% per mol or greater and less than 30% per mol, and the temperature of heat treatment is less than 200 ° C.
    [0016]
    Method according to any one of claims 12 to 15, CHARACTERIZED by the fact that the heat treatment temperature is 170 ° C or higher.
    [0017]
    Method according to any one of claims 12 to 16, CHARACTERIZED by the fact that the heat treatment temperature is 190 ° C or less.
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    同族专利:
    公开号 | 公开日
    JP5443445B2|2014-03-19|
    EP2712468A1|2014-04-02|
    JP2013016423A|2013-01-24|
    US9172113B2|2015-10-27|
    CN103650231A|2014-03-19|
    US9484597B2|2016-11-01|
    CN103650231B|2015-11-25|
    CA2840671C|2016-08-02|
    EP2712468B1|2016-07-27|
    AU2012280008A1|2014-01-23|
    KR101506109B1|2015-03-25|
    KR20140025542A|2014-03-04|
    WO2013005085A1|2013-01-10|
    US20140141341A1|2014-05-22|
    BR112014000252A8|2019-02-12|
    CA2840671A1|2013-01-10|
    AU2012280008B2|2015-10-29|
    BR112014000252A2|2017-02-14|
    US20150357675A1|2015-12-10|
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    法律状态:
    2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-08-06| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-04-28| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-06-30| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 19/06/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    JP2011-150002|2011-07-06|
    JP2011150002A|JP5443445B2|2011-07-06|2011-07-06|Sulfide solid electrolyte material, lithium solid battery, and method for producing sulfide solid electrolyte material|
    PCT/IB2012/001203|WO2013005085A1|2011-07-06|2012-06-19|Sulfide solid electrolyte material, lithium solid-state battery, and method for producing sulfide solid electrolyte material|
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