WO2013094757A1 - 硫化物固体電解質材料、電池および硫化物固体電解質材料の製造方法 - Google Patents
硫化物固体電解質材料、電池および硫化物固体電解質材料の製造方法 Download PDFInfo
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- C01B17/00—Sulfur; Compounds thereof
- C01B17/20—Methods for preparing sulfides or polysulfides, in general
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- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/10—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances sulfides
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/77—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by unit-cell parameters, atom positions or structure diagrams
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Definitions
- the present invention relates to a sulfide solid electrolyte material having good ion conductivity.
- lithium batteries currently on the market use an electrolyte containing a flammable organic solvent, it is possible to install safety devices that suppress the temperature rise during short circuits and to improve the structure and materials to prevent short circuits. Necessary.
- a lithium battery in which the electrolyte is changed to a solid electrolyte layer to make the battery completely solid does not use a flammable organic solvent in the battery, so the safety device can be simplified, and manufacturing costs and productivity can be reduced. It is considered excellent.
- Non-Patent Document 1 discloses a Li ion conductor (sulfide solid electrolyte material) having a composition of Li (4-x) Ge (1-x) P x S 4 .
- Patent Document 1 discloses a LiGePS-based sulfide solid electrolyte material having a specific peak in X-ray diffraction measurement.
- Non-Patent Document 2 discloses a LiGePS-based sulfide solid electrolyte material.
- the present invention has been made in view of the above circumstances, and a main object thereof is to provide a sulfide solid electrolyte material having good ion conductivity.
- a sulfide solid electrolyte material having good ion conductivity can be obtained. Furthermore, by introducing an O element into a sulfide solid electrolyte material having M 1 element, M 2 element, and S element, a sulfide solid electrolyte material with further improved ion conductivity can be obtained.
- a sulfide solid electrolyte material having good ion conductivity can be obtained. Furthermore, by introducing an O element into a sulfide solid electrolyte material having M 1 element, M 2 element, and S element, a sulfide solid electrolyte material with further improved ion conductivity can be obtained.
- the octahedron O composed of the M 1 element and the S element
- the tetrahedron T 1 composed of the M 2a element and the S element
- the tetrahedron T 1 and the octahedron O share a crest above tetrahedron T 2 and the octahedron O contains mainly a crystalline structure that share vertices
- the M 1 is , At least Li
- each of the M 2a and the M 2b is independently selected from the group consisting of P, Sb, Si, Ge, Sn, B, Al, Ga, In, Ti, Zr, V, and Nb.
- At least one of the octahedron O, the tetrahedron T 1 and the tetrahedron T 2 is a sulfide in which a part of the S element is substituted with an O element.
- a solid electrolyte material is provided.
- a sulfide solid electrolyte material having good ion conductivity can be obtained.
- At least one of the octahedron O, tetrahedron T 1 and tetrahedron T 2 is a sulfide solid electrolyte material in which ion conductivity is further improved because a part of the S element is replaced with the O element. be able to.
- the sulfide solid electrolyte material contains at least Li element, Ge element, P element, S element and O element, and the ratio of the O element to the total of the S element and the O element is 25%.
- the following is preferable. This is because a sulfide solid electrolyte material having higher ionic conductivity can be obtained.
- the sulfide solid electrolyte material contains at least Li element, Si element, P element, S element and O element, and the ratio of the O element to the total of the S element and the O element is 10%.
- the following is preferable. This is because a sulfide solid electrolyte material having higher ionic conductivity can be obtained.
- at least one of the positive electrode active material layer, the negative electrode active material layer, and the electrolyte layer contains the sulfide solid electrolyte material described above.
- a high output battery can be obtained by using the above-described sulfide solid electrolyte material.
- a method for producing a sulfide solid electrolyte material having the above-described peak intensity ratio wherein a raw material composition containing the M 1 element, the M 2 element, the S element, and the O element is used. And using an ion conductive material synthesis step of synthesizing an amorphous ion conductive material by mechanical milling, and heating the amorphous ion conductive material to form the sulfide solid electrolyte material. And a heating step for obtaining a sulfide solid electrolyte material.
- the present invention also provides a method for producing a sulfide solid electrolyte material having the above-described crystal structure, which contains the M 1 element, the M 2a element, the M 2b element, the S element, and the O element.
- a method for producing a sulfide solid electrolyte material is provided.
- the octahedron O, the tetrahedron T 1 and the tetrahedron T 2 have a predetermined crystal structure (three-dimensional) by performing amorphization in an ion conductive material synthesis step and then performing a heating step.
- a sulfide solid electrolyte material having a structure can be obtained. Therefore, a sulfide solid electrolyte material having good ion conductivity can be obtained.
- the raw material composition contains the O element, a sulfide solid electrolyte material with improved ion conductivity can be obtained.
- FIG. 3 is an X-ray diffraction spectrum of a sulfide solid electrolyte material obtained in Example 2.
- FIG. 3 is an X-ray diffraction spectrum of a sulfide solid electrolyte material obtained in Example 3.
- FIG. 2 is an X-ray diffraction spectrum of a sulfide solid electrolyte material obtained in Comparative Example 1.
- 3 is a measurement result of Li ion conductivity of sulfide solid electrolyte materials obtained in Examples 1 to 3 and Comparative Example 1.
- FIG. 3 is an X-ray diffraction spectrum of a sulfide solid electrolyte material obtained in Example 4.
- FIG. 6 is an X-ray diffraction spectrum of the sulfide solid electrolyte material obtained in Example 5.
- FIG. 7 is an X-ray diffraction spectrum of the sulfide solid electrolyte material obtained in Example 6.
- 3 is an X-ray diffraction spectrum of a sulfide solid electrolyte material obtained in Comparative Example 2.
- 3 is a measurement result of Li ion conductivity of the sulfide solid electrolyte material obtained in Examples 4 to 6 and Comparative Example 2.
- the sulfide solid electrolyte material of the present invention will be described.
- the sulfide solid electrolyte material of the present invention can be roughly divided into two embodiments. Therefore, the sulfide solid electrolyte material of the present invention will be described separately for the first embodiment and the second embodiment.
- the reason why the ion conductivity is improved is considered to be that the size of the tunnel through which Li ions pass (tunnel existing in the crystal) is changed to a size that facilitates conduction by the introduction of the O element.
- FIG. 1 is an X-ray diffraction spectrum for explaining a difference between a sulfide solid electrolyte material having high ion conductivity and a sulfide solid electrolyte material having low ion conductivity.
- the two sulfide solid electrolyte materials in FIG. 1 both have a composition of Li 3.25 Ge 0.25 P 0.75 S 4 .
- FIG. 1 is an X-ray diffraction spectrum for explaining a difference between a sulfide solid electrolyte material having high ion conductivity and a sulfide solid electrolyte material having low ion conductivity.
- the two sulfide solid electrolyte materials in FIG. 1 both have a composition of Li
- the sulfide solid electrolyte material with low ion conductivity also has the same peak.
- This sulfide solid electrolyte material having high ion conductivity has a crystal structure similar to that of the sulfide solid electrolyte material of the first embodiment, as will be described later.
- Crystal phases A and B are both crystalline phases exhibiting ionic conductivity, but there are differences in ionic conductivity.
- the crystal phase A is considered to have significantly higher ionic conductivity than the crystal phase B.
- the proportion of the crystal phase B having low ion conductivity cannot be reduced, and the ion conductivity cannot be sufficiently increased.
- the crystal phase A having high ion conductivity can be positively precipitated, a sulfide solid electrolyte material having high ion conductivity can be obtained.
- the sulfide solid electrolyte material in the first embodiment preferably has a high proportion of the crystal phase A having high ion conductivity.
- the sulfide solid electrolyte material of the first embodiment contains M 1 element, M 2 element, S element and O element.
- the M 1 is not particularly limited as long as it contains at least Li, and may be Li alone or a combination of Li and another element.
- the other element is preferably, for example, a monovalent or divalent element, and specifically, at least one selected from the group consisting of Na, K, Mg, Ca, and Zn is preferable.
- the M 1 is a monovalent element (for example, Li, Na, K), and a part thereof may be substituted with a divalent or higher element (for example, Mg, Ca, Zn). Thereby, a monovalent element becomes easy to move and ion conductivity improves.
- M 2 is preferably a trivalent, tetravalent or pentavalent element.
- M 2 include one selected from the group consisting of P, Sb, Si, Ge, Sn, B, Al, Ga, In, Ti, Zr, V, and Nb.
- the M 2 preferably includes at least one selected from the group consisting of P, Si, Ge, Al, Zr, Sn, and B, and preferably includes at least P and Ge. Or it is more preferable that P and Si are included at least.
- the sulfide solid electrolyte material of the first embodiment contains an S element and an O element.
- the ratio of the O element contained in the sulfide solid electrolyte material is the same as that of the same sulfide solid electrolyte material (sulfide solid electrolyte material for comparison) except that the valence was adjusted with S without containing the O element. It is preferable that the ratio is such that ion conductivity higher than conductivity is obtained.
- the sulfide solid electrolyte material as a comparison object is, for example, when the sulfide solid electrolyte material of the first embodiment is Li 3.35 Ge 0.35 P 0.65 (S 1-y O y ) 4 Li 3.35 Ge 0.35 P 0.65 S 4 is applicable.
- 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 further preferably 1% or more.
- the ratio of the O element is preferably 25% or less, for example. This is because a sulfide solid electrolyte material having higher ionic conductivity can be obtained.
- the proportion of the O element can be determined by XPS or EDX, for example.
- the sulfide solid electrolyte material LiGePSO system in the above general formula, the M 1 element corresponds to the Li element, and the M 2 element corresponds to the Ge element and the P element.
- the sulfide solid electrolyte material of the first embodiment usually has a specific crystal structure described in the second embodiment described later.
- the M 1 element and the M 2 element can take a similar crystal structure in the LiGePSO-based sulfide solid electrolyte material in any combination thereof. Therefore, it is considered that a sulfide solid electrolyte material having good ion conductivity can be obtained in any combination of M 1 element and M 2 element.
- a sulfide solid electrolyte material having good ion conductivity can be obtained in any combination of M 1 element and M 2 element.
- the position of the peak of X-ray diffraction depends on the crystal structure, it is similar if the sulfide solid electrolyte material has the above crystal structure, regardless of the types of the M 1 element and M 2 element. It is considered that an XRD pattern is obtained.
- the sulfide solid electrolyte material of the first embodiment preferably contains at least a Li element, a Ge element, a P element, an S element, and an O element.
- 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 1% or more. More preferably it is.
- the ratio of the O element is preferably 25% or less, for example.
- composition of the sulfide solid electrolyte material LiGePSO system is not particularly limited as long as the composition can be obtained the value of a given I B / I A, Li ( 4-x) Ge (1-x ) P x (S 1-y O y ) 4 (x satisfies 0 ⁇ x ⁇ 1 and y satisfies 0 ⁇ y ⁇ 0.25). This is because a sulfide solid electrolyte material having high ion conductivity can be obtained.
- the composition of Li (4-x) Ge (1-x) P x S 4 having no O element corresponds to the composition of the solid solution of Li 3 PS 4 and Li 4 GeS 4 .
- this composition corresponds to the composition on the tie line of Li 3 PS 4 and Li 4 GeS 4 .
- both Li 3 PS 4 and Li 4 GeS 4 correspond to the ortho composition and have an advantage of high chemical stability.
- the sulfide solid electrolyte material having such a composition of Li (4-x) Ge (1-x) P x S 4 has been conventionally known as thiolysicon, and the sulfide solid electrolyte material of the first embodiment is The composition may be the same as that of conventional thiolysicon.
- the ratio of the crystal phase contained in the sulfide solid electrolyte material of the first embodiment is completely different from the ratio of the conventional crystal phase.
- the sulfide solid electrolyte material of the first embodiment contains an O element, there is an advantage that ion conductivity is further high.
- x in Li (4-x) Ge ( 1-x) P x (S 1-y O y) 4 is particularly limited as long as the value can be obtained the value of a given I B / I A
- it preferably satisfies 0.4 ⁇ x, and more preferably satisfies 0.5 ⁇ x.
- the x preferably satisfies x ⁇ 0.8, and more preferably satisfies x ⁇ 0.75. This is because the value of I B / I A can be further reduced by setting the range of such x.
- the y preferably satisfies 0.001 ⁇ y, more preferably satisfies 0.005 ⁇ y, and still more preferably satisfies 0.01 ⁇ y.
- y preferably satisfies y ⁇ 0.25.
- the sulfide solid electrolyte material of the first embodiment is made of at least Li 2 S, P 2 S 5 and GeS 2 .
- the sulfide solid electrolyte material of the first embodiment preferably contains at least Li element, Si element, P element, S element and O element.
- the ratio of the O element to the sum of the S element and the O element is preferably 0.1% or more, more preferably 0.5% or more, and further preferably 1% or more.
- the proportion of the O element is, for example, preferably 20% or less, more preferably 15% or less, and further preferably 10% or less.
- the composition of the sulfide solid electrolyte material LiSiPSO system is not particularly limited as long as the composition can be obtained the value of a given I B / I A, Li ( 4-x) Si (1 -X) P x (S 1-y O y ) 4 (x preferably satisfies 0 ⁇ x ⁇ 1 and y satisfies 0 ⁇ y ⁇ 0.25).
- a sulfide solid electrolyte material having high ion conductivity can be obtained.
- the composition of Li (4-x) Si (1-x) P x S 4 having no O element corresponds to the composition of the solid solution of Li 3 PS 4 and Li 4 SiS 4 . That is, this composition corresponds to the composition on the tie line of Li 3 PS 4 and Li 4 SiS 4 .
- both Li 3 PS 4 and Li 4 SiS 4 correspond to the ortho composition and have an advantage of high chemical stability.
- x in Li (4-x) Si ( 1-x) P x (S 1-y O y) 4 is particularly limited as long as the value can be obtained the value of a given I B / I A
- it preferably satisfies 0.4 ⁇ x, and more preferably satisfies 0.5 ⁇ x.
- the x preferably satisfies x ⁇ 0.8, and more preferably satisfies x ⁇ 0.75. This is because the value of I B / I A can be further reduced by setting the range of such x.
- the y preferably satisfies 0.001 ⁇ y, more preferably satisfies 0.005 ⁇ y, and still more preferably satisfies 0.01 ⁇ y.
- y preferably satisfies y ⁇ 0.2, more preferably satisfies y ⁇ 0.15, and further preferably satisfies y ⁇ 0.1.
- the sulfide solid electrolyte material of the first embodiment is preferably formed using at least Li 2 S, P 2 S 5 and SiS 2 .
- the sulfide solid electrolyte material of the first embodiment is usually a crystalline sulfide solid electrolyte material.
- the sulfide solid electrolyte material of the first embodiment preferably has high ionic conductivity, and the ionic conductivity of the sulfide solid electrolyte material at 25 ° C. is 1.0 ⁇ 10 ⁇ 3 S / cm or more. It is preferably 2.3 ⁇ 10 ⁇ 3 S / cm or more.
- the shape of the sulfide solid electrolyte material of the first embodiment is not particularly limited, and examples thereof include powder. Further, the average particle diameter of the powdered sulfide solid electrolyte material is preferably in the range of 0.1 ⁇ m to 50 ⁇ m, for example.
- the sulfide solid electrolyte material of the first embodiment has high ionic conductivity, it can be used for any application that requires ionic conductivity. Especially, it is preferable that the sulfide solid electrolyte material of a 1st embodiment is what is used for a battery. This is because it can greatly contribute to the high output of the battery.
- the method for producing the sulfide solid electrolyte material of the first embodiment will be described in detail in “C. Method for producing sulfide solid electrolyte material” described later. Further, the sulfide solid electrolyte material of the first embodiment may have the characteristics of the second embodiment described later.
- the sulfide solid electrolyte material of the second embodiment is composed of octahedron O composed of M 1 element and S element, tetrahedron T 1 composed of M 2a element and S element, M 2b element and S element.
- M 1 includes at least Li
- M 2a and M 2b are each independently P, Sb, Si, Ge, Sn, B, Al, Ga, In, Ti, Zr, V, and Nb.
- at least one of the octahedron O, the tetrahedron T 1 and the tetrahedron T 2 is one in which a part of the S element is substituted with an O element. It is characterized by.
- a sulfide solid electrolyte material having good ion conductivity is obtained.
- At least one of the octahedron O, tetrahedron T 1 and tetrahedron T 2 is a sulfide solid electrolyte material in which ion conductivity is further improved because a part of the S element is replaced with the O element. be able to. Therefore, a high output battery can be obtained by using the sulfide solid electrolyte material of the second embodiment.
- FIG. 2 is a perspective view for explaining an example of the crystal structure of the sulfide solid electrolyte material of the second embodiment.
- the octahedron O has M 1 as a central element, and has six S at the apex of the octahedron (note that a part of S may be substituted with O).
- it is a LiS 6-x O x (0 ⁇ x ⁇ 6) octahedron.
- the tetrahedron T 1 has M 2a as a central element, and has four Ss (note that a part of S may be substituted with O) at the apex of the tetrahedron, Are both GeS 4 ⁇ x O x (0 ⁇ x ⁇ 4) tetrahedron and PS 4 ⁇ x O x (0 ⁇ x ⁇ 4) tetrahedron.
- the tetrahedron T 2 has M 2b as a central element, and has four Ss (note that a part of S may be replaced with O) at the apex of the tetrahedron, Is a PS 4 ⁇ x O x (0 ⁇ x ⁇ 4) tetrahedron.
- At least one of octahedron O, tetrahedron T 1 and tetrahedron T 2 is one in which a part of S element is substituted with O element.
- the fact that part of the S element is replaced with the O element can be confirmed by, for example, analysis of an XRD pattern by the Rietveld method, neutron diffraction, or the like.
- the tetrahedron T 1 and the octahedron O share a ridge
- the tetrahedron T 2 and the octahedron O share a vertex.
- FIG. 3 is a plan view for explaining ion conduction in the second embodiment.
- Li ions are conducted in the c-axis direction (perpendicular to the paper surface) inside the crystal structure (tunnel T) composed of octahedron O, tetrahedron T 1 and tetrahedron T 2 .
- the Li ions are slightly arranged in a zigzag manner.
- the size of the tunnel T is determined by the size of the vertex element and the central element of each polyhedron.
- the sulfide solid electrolyte material of the second embodiment is characterized mainly by containing the above crystal structure as a main component.
- the ratio of the crystal structure in the entire crystal structure of the sulfide solid electrolyte material is not particularly limited, but is preferably higher. This is because a sulfide solid electrolyte material having high ion conductivity can be obtained.
- the ratio of the crystal structure is preferably 70 wt% or more, and more preferably 90 wt% or more.
- the ratio of the said crystal structure can be measured by synchrotron radiation XRD, for example.
- the sulfide solid electrolyte material of the second embodiment is preferably a single-phase material having the above crystal structure. This is because the ion conductivity can be made extremely high.
- M 1 element, M 2 element (M 2a element, M 2b element) and other matters in the second embodiment are the same as those in the first embodiment described above, description thereof is omitted here.
- the battery of the present invention includes a positive electrode active material layer containing a positive electrode active material, a negative electrode active material layer containing a negative electrode active material, an electrolyte layer formed between the positive electrode active material layer and the negative electrode active material layer, In which at least one of the positive electrode active material layer, the negative electrode active material layer, and the electrolyte layer contains the sulfide solid electrolyte material described above.
- a high output battery can be obtained by using the above-described sulfide solid electrolyte material.
- FIG. 4 is a schematic cross-sectional view showing an example of the battery of the present invention.
- the battery 10 in FIG. 4 was formed between the positive electrode active material layer 1 containing the positive electrode active material, the negative electrode active material layer 2 containing the negative electrode active material, and the positive electrode active material layer 1 and the negative electrode active material layer 2.
- At least one of the positive electrode active material layer 1, the negative electrode active material layer 2, and the electrolyte layer 3 contains the sulfide solid electrolyte material described in the above-mentioned “A. Sulfide solid electrolyte material”. And hereinafter, the battery of this invention is demonstrated for every structure.
- Electrolyte layer The electrolyte layer in this invention is a layer formed between a positive electrode active material layer and a negative electrode active material layer.
- the electrolyte layer is not particularly limited as long as it is a layer capable of conducting ions, but is preferably a solid electrolyte layer made of a solid electrolyte material. This is because a battery with higher safety can be obtained as compared with a battery using an electrolytic solution.
- a solid electrolyte layer contains the sulfide solid electrolyte material mentioned above.
- the ratio of the sulfide solid electrolyte material contained in the solid electrolyte layer is, for example, preferably in the range of 10% to 100% by volume, and more preferably in the range of 50% to 100% by volume.
- the solid electrolyte layer is composed only of the sulfide solid electrolyte material. This is because a high output battery can be obtained.
- the thickness of the solid electrolyte layer is, for example, preferably in the range of 0.1 ⁇ m to 1000 ⁇ m, and more preferably in the range of 0.1 ⁇ m to 300 ⁇ m.
- the method of compression-molding a solid electrolyte material etc. can be mentioned, for example.
- the electrolyte layer in the present invention may be a layer composed of an electrolytic solution.
- the electrolytic solution it is necessary to further consider safety compared to the case where the solid electrolyte layer is used, but a battery with higher output can be obtained.
- at least one of the positive electrode active material layer and the negative electrode active material layer contains the above-described sulfide solid electrolyte material.
- the electrolytic solution usually contains a lithium salt and an organic solvent (nonaqueous solvent).
- lithium salt examples include inorganic lithium salts such as LiPF 6 , LiBF 4 , LiClO 4 , LiAsF 6 , and LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 2 , LiN (C 2 F 5 SO 2 ) 2 , LiC An organic lithium salt such as (CF 3 SO 2 ) 3 can be used.
- organic solvent examples include ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), butylene carbonate (BC), and the like.
- the positive electrode active material layer in the present invention is a layer containing at least a positive electrode active material, and may contain at least one of a solid electrolyte material, a conductive material and a binder, if necessary. good.
- the positive electrode active material layer preferably contains a solid electrolyte material, and the solid electrolyte material is preferably the sulfide solid electrolyte material described above. This is because a positive electrode active material layer having high ion conductivity can be obtained.
- the ratio of the sulfide solid electrolyte material contained in the positive electrode active material layer varies depending on the type of battery.
- the positive electrode active material include LiCoO 2 , LiMnO 2 , Li 2 NiMn 3 O 8 , LiVO 2 , LiCrO 2 , LiFePO 4 , LiCoPO 4 , LiNiO 2 , LiNi 1/3 Co 1/3 Mn 1/3 O. 2 etc. can be mentioned.
- the positive electrode active material layer in the present invention may further contain a conductive material.
- a conductive material By adding a conductive material, the conductivity of the positive electrode active material layer can be improved.
- the conductive material include acetylene black, ketjen black, and carbon fiber.
- the positive electrode active material layer may contain a binder. Examples of the type of binder include fluorine-containing binders such as polytetrafluoroethylene (PTFE).
- the thickness of the positive electrode active material layer is preferably in the range of 0.1 ⁇ m to 1000 ⁇ m, for example.
- the negative electrode active material layer in the present invention is a layer containing at least a negative electrode active material, and may contain at least one of a solid electrolyte material, a conductive material and a binder as necessary.
- the negative electrode active material layer preferably contains a solid electrolyte material, and the solid electrolyte material is the sulfide solid electrolyte material described above. This is because a negative electrode active material layer having high ion conductivity can be obtained.
- the ratio of the sulfide solid electrolyte material contained in the negative electrode active material layer varies depending on the type of battery.
- the negative electrode active material examples include a metal active material and a carbon active material.
- the metal active material examples include In, Al, Si, and Sn.
- examples of the carbon active material include mesocarbon microbeads (MCMB), highly oriented graphite (HOPG), hard carbon, and soft carbon.
- MCMB mesocarbon microbeads
- HOPG highly oriented graphite
- hard carbon examples of the conductive material and the binder used in the negative electrode active material layer are the same as those in the positive electrode active material layer described above.
- the thickness of the negative electrode active material layer is preferably in the range of 0.1 ⁇ m to 1000 ⁇ m, for example.
- the battery of the present invention has at least the electrolyte layer, the positive electrode active material layer, and the negative electrode active material layer described above. Furthermore, it usually has a positive electrode current collector for collecting current of the positive electrode active material layer and a negative electrode current collector for collecting current of the negative electrode active material layer.
- the material for the positive electrode current collector include SUS, aluminum, nickel, iron, titanium, and carbon. Among them, SUS is preferable.
- examples of the material for the negative electrode current collector include SUS, copper, nickel, and carbon. Of these, SUS is preferable.
- the thickness and shape of the positive electrode current collector and the negative electrode current collector are preferably appropriately selected according to the use of the battery.
- the battery case of a general battery can be used for the battery case used for this invention. Examples of the battery case include a SUS battery case.
- Battery The battery of the present invention may be a primary battery or a secondary battery, but among them, a secondary battery is preferable. This is because it can be repeatedly charged and discharged and is useful, for example, as an in-vehicle battery.
- Examples of the shape of the battery of the present invention include a coin type, a laminate type, a cylindrical type, and a square type.
- the manufacturing method of the battery of this invention will not be specifically limited if it is a method which can obtain the battery mentioned above, The method similar to the manufacturing method of a general battery can be used.
- the battery of the present invention is an all-solid battery
- a material constituting the positive electrode active material layer, a material constituting the solid electrolyte layer, and a material constituting the negative electrode active material layer are sequentially provided.
- Examples of the method include producing a power generation element by pressing, housing the power generation element inside the battery case, and caulking the battery case.
- the method for producing a sulfide solid electrolyte material of the present invention can be roughly divided into two embodiments. Then, the manufacturing method of the sulfide solid electrolyte material of this invention is divided and demonstrated to a 1st embodiment and a 2nd embodiment.
- the manufacturing method of the sulfide solid electrolyte material of 1st embodiment is a manufacturing method of the sulfide solid electrolyte material described in "A. Sulfide solid electrolyte material 1. 1st embodiment", Comprising: An ion conductive material synthesis step for synthesizing an amorphous ion conductive material by mechanical milling using a raw material composition containing M 1 element, M 2 element, S element and O element; A heating step of obtaining the sulfide solid electrolyte material by heating the amorphous ion conductive material.
- a solid electrolyte material can be obtained. Therefore, a sulfide solid electrolyte material having good ion conductivity can be obtained.
- the raw material composition contains the O element, a sulfide solid electrolyte material with improved ion conductivity can be obtained.
- FIG. 5 is an explanatory view showing an example of a method for producing a sulfide solid electrolyte material of the first embodiment.
- a raw material composition is prepared by mixing Li 2 S, Li 2 O, P 2 S 5 and GeS 2 .
- the raw material composition is ball milled to obtain an amorphous ion conductive material.
- the amorphous ion conductive material is heated to improve the crystallinity, thereby obtaining a sulfide solid electrolyte material.
- an ion conductive material that has been made amorphous once is synthesized.
- the ion conductive material synthesis step in the first embodiment will be described.
- the ion conductive material synthesis step is performed by using a raw material composition containing the M 1 element, the M 2 element, the S element, and the O element to make amorphous ions by mechanical milling. This is a step of synthesizing a conductive material.
- the raw material composition in the first embodiment is not particularly limited as long as it contains M 1 element, M 2 element, S element and O element.
- the M 1 element and the M 2 element in the raw material composition are the same as those described in “A. Sulfide solid electrolyte material”.
- Compounds containing M 1 element although not particularly limited, for example, a sulfide of a single and M 1 of M 1.
- Examples of the sulfide of M 1 include Li 2 S, Na 2 S, K 2 S, MgS, CaS, and ZnS.
- Compounds containing M 2 element but are not particularly limited, for example, a sulfide of a single and M 2 of M 2.
- Examples of the sulfide of M 2 include Me 2 S 3 (Me is a trivalent element, for example, Al, B, Ga, In, and Sb), MeS 2 (Me is a tetravalent element, for example, Ge , Si, Sn, Zr, Ti, and Nb), Me 2 S 5 (Me is a pentavalent element such as P and V), and the like.
- the compound containing S element is not particularly limited, and may be a simple substance or a sulfide.
- the sulfide can include sulfides containing the above M 1 element or M 2 element.
- the compound containing O element is usually an oxide.
- Type oxide is not particularly limited, but is preferably an oxide containing the above M 1 element or M 2 element. This is because unnecessary side reactions do not occur.
- the oxide include Me 2 O 3 (Me is a trivalent element, such as Al, B, Ga, In, and Sb), MeO 2 (Me is a tetravalent element, such as Ge, Si, and the like).
- Me 2 O 5 is a pentavalent element such as P or V
- Li 5 MeO 4 is a trivalent element such as Al , B, Ga, In, and Sb
- Li 4 MeO 4 is a tetravalent element, for example, Ge, Si, Sn, Zr, Ti, and Nb
- Li 3 MeO 4 is five
- Valent elements such as P and V).
- the raw material composition is Li (4-x) Ge (1-x) P x (S 1-y O y ) 4 (x satisfies 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 0.25 It is preferable to have a composition of This is because a sulfide solid electrolyte material having high ion conductivity can be obtained. Note that, as described above, the composition of Li (4-x) Ge (1-x) P x S 4 having no O element corresponds to the composition of the solid solution of Li 3 PS 4 and Li 4 GeS 4 .
- the raw material composition is Li (4-x) Si (1-x) P x (S 1-y O y ) 4 (x satisfies 0 ⁇ x ⁇ 1 and 0 ⁇ y ⁇ 0.25 It is preferable to have a composition of This is because a sulfide solid electrolyte material having high ion conductivity can be obtained.
- the composition of Li (4-x) Si (1-x) P x S 4 having no O element corresponds to the composition of the solid solution of Li 3 PS 4 and Li 4 SiS 4 .
- Mechanical milling is a method of crushing a sample while applying mechanical energy.
- an amorphous ion conductive material is synthesized by applying mechanical energy to the raw material composition.
- Examples of such mechanical milling include a vibration mill, a ball mill, a turbo mill, a mechanofusion, a disk mill, and the like, and among them, a vibration mill and a ball mill are preferable.
- the conditions of the vibration mill are not particularly limited as long as an amorphous ion conductive material can be obtained.
- the vibration amplitude of the vibration mill is, for example, preferably in the range of 5 mm to 15 mm, and more preferably in the range of 6 mm to 10 mm.
- the vibration frequency of the vibration mill is, for example, preferably in the range of 500 rpm to 2000 rpm, and more preferably in the range of 1000 rpm to 1800 rpm.
- the filling rate of the sample of the vibration mill is, for example, preferably in the range of 1 to 80% by volume, more preferably in the range of 5 to 60% by volume, and particularly in the range of 10 to 50% by volume.
- a vibrator for example, an alumina vibrator
- the conditions of the ball mill are not particularly limited as long as an amorphous ion conductive material can be obtained.
- the rotation speed of the platform when performing the planetary ball mill is preferably in the range of 200 rpm to 500 rpm, and more preferably in the range of 250 rpm to 400 rpm.
- the treatment time when performing the planetary ball mill is preferably in the range of, for example, 1 hour to 100 hours, and more preferably in the range of 1 hour to 70 hours.
- Heating step in the first embodiment is a step of obtaining the sulfide solid electrolyte material by heating the amorphous ion conductive material.
- the crystallinity is improved by heating the amorphized ion conductive material.
- the temperature is preferably equal to or higher than the crystallization temperature of the phase.
- the heating temperature is preferably 300 ° C. or higher, more preferably 350 ° C. or higher, further preferably 400 ° C. or higher, and particularly preferably 450 ° C. or higher.
- the heating temperature is preferably 1000 ° C. or less, more preferably 700 ° C. or less, further preferably 650 ° C. or less, and particularly preferably 600 ° C. or less.
- the heating in the first embodiment is preferably performed in an inert gas atmosphere or in vacuum from the viewpoint of preventing oxidation.
- 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”. .
- a method for producing a sulfide solid electrolyte material according to a second embodiment is the method for producing a sulfide solid electrolyte material described in “A. Sulfide solid electrolyte material 2. Second embodiment”. Ion conductivity for synthesizing an amorphous ion conductive material by mechanical milling using a raw material composition containing M 1 element, M 2a element, M 2b element, S element and O element. The method includes a material synthesis step and a heating step of obtaining the sulfide solid electrolyte material by heating the amorphous ion conductive material.
- the octahedron O, the tetrahedron T 1, and the tetrahedron T 2 are made to have a predetermined crystal structure (amorphization is performed in the ion conductive material synthesis step and then the heating step is performed).
- a sulfide solid electrolyte material having a three-dimensional structure can be obtained. Therefore, a sulfide solid electrolyte material having good ion conductivity can be obtained.
- the raw material composition contains the O element, a sulfide solid electrolyte material with improved ion conductivity can be obtained.
- 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. Method for producing sulfide solid electrolyte material 1. First embodiment”. The description here is omitted. It is preferable to set various conditions so that a desired sulfide solid electrolyte material can be obtained.
- the present invention is not limited to the above embodiment.
- the above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.
- Example 1 As starting materials, lithium sulfide (Li 2 S), lithium oxide (Li 2 O), diphosphorus pentasulfide (P 2 S 5 ), and germanium sulfide (GeS 2 ) were used. These powders were mixed in a glove box under an argon atmosphere at a ratio of 0.3495 g of Li 2 S, 0.03082 g of Li 2 O, 0.372641 g of P 2 S 5 and 0.2469 g of GeS 2 ; A raw material composition was obtained. The obtained raw material composition was pulverized using a vibration mill. TI-100 manufactured by CM Science Co., Ltd. was used for the vibration mill.
- the obtained ion conductive material was molded into pellets, and the obtained pellets were placed in a carbon-coated quartz tube and vacuum-sealed.
- the pressure of the vacuum sealed quartz tube was about 30 Pa.
- the quartz tube was placed in a firing furnace, heated from room temperature to 550 ° C. over 6 hours, maintained at 550 ° C. for 8 hours, and then gradually cooled to room temperature.
- the amount of oxygen substitution is 5%.
- Example 2 Implementation was performed except that the raw material composition used was a mixture of Li 2 S at 0.30728 g, Li 2 O at 0.06269 g, P 2 S 5 at 0.378922 g, and GeS 2 at a ratio of 0.251096 g.
- a crystalline sulfide solid electrolyte material was obtained.
- the amount of oxygen substitution is 10%.
- Example 3 Implementation was carried out except that 0.190304 g of Li 2 S, 0.150803 g of Li 2 O, 0.3962890 g of P 2 S 5 and 0.262604 g of GeS 2 were used as the raw material composition.
- a crystalline sulfide solid electrolyte material was obtained.
- the amount of oxygen substitution is 23%.
- Example 1 The crystalline material was the same as in Example 1 except that the raw material composition used was a mixture of Li 2 S 0.390529 g, P 2 S 5 0.366564 g, and GeS 2 0.242907 g.
- the sulfide solid electrolyte material was obtained.
- the oxygen substitution amount is 0%.
- tetrahedron T 1 (GeS 4 tetrahedron and PS 4 tetrahedron) and octahedron O (LiS 6 octahedron) share a ridge
- tetrahedron T 2 (PS 4 tetrahedron) and octahedron O (LiS 6 octahedron) was a crystal structure sharing a vertex.
- Examples 1 to 3 have the same diffraction pattern as Comparative Example 1, and thus it was confirmed that the same crystal structure was formed in Examples 1 to 3.
- Li ion conductivity at 25 ° C. was measured. First, an appropriate amount of sample is weighed in a glove box in an argon atmosphere and placed in a polyethylene terephthalate tube (PET tube, inner diameter 10 mm, outer diameter 30 mm, height 20 mm), and powder molding made of carbon tool steel S45C anvil from above and below. I pinched it with a jig.
- PET tube polyethylene terephthalate tube
- a frequency response analyzer FRA Frequency Response Analyzer
- Solartron impedance / gain phase analyzer solartron 1260
- Espec corp, SU-241, -40 ° C ⁇ 150 ° C was used.
- the measurement was started from the high frequency region under the conditions of an AC voltage of 10 mV to 1000 mV, a frequency range of 1 Hz to 10 MHz, an integration time of 0.2 seconds, and a temperature of 23 ° C.
- Zplot was used as measurement software, and Zview was used as analysis software. The obtained result is shown in FIG.
- Example 4 As starting materials, lithium sulfide (Li 2 S, manufactured by Nippon Chemical Industry Co., Ltd.), lithium oxide (Li 2 O, manufactured by High Purity Chemical Co., Ltd.), diphosphorus pentasulfide (P 2 S 5 , manufactured by Aldrich), Silicon sulfide (SiS 2 , manufactured by Kojundo Chemical Co., Ltd.) was used. These powders were mixed in a glove box under an argon atmosphere at a ratio of 0.34083 g of Li 2 S, 0.06819 g of Li 2 O, 0.38049 g of P 2 S 5 and 0.21047 g of SiS 2 , A raw material composition was obtained.
- the obtained ion conductive material powder was placed in a carbon-coated quartz tube and vacuum-sealed.
- the pressure of the vacuum sealed quartz tube was about 30 Pa.
- the quartz tube was placed in a firing furnace, heated from room temperature to 550 ° C. over 6 hours, maintained at 550 ° C. for 8 hours, and then gradually cooled to room temperature.
- a crystalline sulfide solid electrolyte material having a composition of Li 3.4 Si 0.4 P 0.6 (S 0.9 O 0.1 ) 4 was obtained.
- the amount of oxygen substitution is 10%.
- Example 5 Implementation was carried out except that the raw material composition used was a mixture of Li 2 S at 0.386186 g, Li 2 O at 0.03348565 g, P 2 S 5 at 0.373364747 g, and SiS 2 at a ratio of 0.20668665 g.
- a crystalline sulfide solid electrolyte material was obtained.
- the amount of oxygen substitution is 5%.
- Example 6 Except for using a raw material composition in which Li 2 S was mixed at a rate of 0.24449428 g, Li 2 O was 0.141591 g, P 2 S 5 was mixed at a rate of 0.3949774 g, and SiS 2 was mixed at a rate of 0.21848871 g. In the same manner as in Example 4, a crystalline sulfide solid electrolyte material was obtained.
- the amount of oxygen substitution is 20%.
- Example 2 The crystalline material was the same as in Example 4 except that the raw material composition used was a mixture of Li 2 S at a rate of 0.429936 g, P 2 S 5 at a rate of 0.367033 g, and SiS 2 at a rate of 0.203030 g.
- the sulfide solid electrolyte material was obtained.
- the oxygen substitution amount is 0%.
Abstract
Description
まず、本発明の硫化物固体電解質材料について説明する。本発明の硫化物固体電解質材料は、2つの実施態様に大別することができる。そこで、本発明の硫化物固体電解質材料について、第一実施態様および第二実施態様に分けて説明する。
第一実施態様の硫化物固体電解質材料は、M1元素、M2元素、S元素およびO元素を含有し、上記M1は、少なくともLiを含み、上記M2は、P、Sb、Si、Ge、Sn、B、Al、Ga、In、Ti、Zr、V、Nbからなる群から選択される少なくとも一種であり、CuKα線を用いたX線回折測定における2θ=29.58°±0.50°の位置にピークを有し、上記2θ=29.58°±0.50°のピークの回折強度をIAとし、2θ=27.33°±0.50°のピークの回折強度をIBとした場合に、IB/IAの値が0.50未満であることを特徴とするものである。
次に、本発明の硫化物固体電解質材料の第二実施態様について説明する。第二実施態様の硫化物固体電解質材料は、M1元素およびS元素から構成される八面体Oと、M2a元素およびS元素から構成される四面体T1と、M2b元素およびS元素から構成される四面体T2とを有し、上記四面体T1および上記八面体Oは稜を共有し、上記四面体T2および上記八面体Oは頂点を共有する結晶構造を主体として含有し、上記M1は、少なくともLiを含み、上記M2aおよび上記M2bは、それぞれ独立に、P、Sb、Si、Ge、Sn、B、Al、Ga、In、Ti、Zr、V、Nbからなる群から選択される少なくとも一種であり、上記八面体O、上記四面体T1および上記四面体T2の少なくとも一つは、上記S元素の一部がO元素に置換されたものであることを特徴とするものである。
次に、本発明の電池について説明する。本発明の電池は、正極活物質を含有する正極活物質層と、負極活物質を含有する負極活物質層と、上記正極活物質層および上記負極活物質層の間に形成された電解質層とを含有する電池であって、上記正極活物質層、上記負極活物質層および上記電解質層の少なくとも一つが、上述した硫化物固体電解質材料を含有することを特徴とするものである。
以下、本発明の電池について、構成ごとに説明する。
本発明における電解質層は、正極活物質層および負極活物質層の間に形成される層である。電解質層は、イオンの伝導を行うことができる層であれば特に限定されるものではないが、固体電解質材料から構成される固体電解質層であることが好ましい。電解液を用いる電池に比べて、安全性の高い電池を得ることができるからである。さらに、本発明においては、固体電解質層が、上述した硫化物固体電解質材料を含有することが好ましい。固体電解質層に含まれる上記硫化物固体電解質材料の割合は、例えば10体積%~100体積%の範囲内、中でも50体積%~100体積%の範囲内であることが好ましい。特に、本発明においては、固体電解質層が上記硫化物固体電解質材料のみから構成されていることが好ましい。高出力な電池を得ることができるからである。固体電解質層の厚さは、例えば0.1μm~1000μmの範囲内、中でも0.1μm~300μmの範囲内であることが好ましい。また、固体電解質層の形成方法としては、例えば、固体電解質材料を圧縮成形する方法等を挙げることができる。
本発明における正極活物質層は、少なくとも正極活物質を含有する層であり、必要に応じて、固体電解質材料、導電化材および結着材の少なくとも一つを含有していても良い。特に、本発明においては、正極活物質層が固体電解質材料を含有し、その固体電解質材料が、上述した硫化物固体電解質材料であることが好ましい。イオン伝導性の高い正極活物質層を得ることができるからである。正極活物質層に含まれる上記硫化物固体電解質材料の割合は、電池の種類によって異なるものであるが、例えば0.1体積%~80体積%の範囲内、中でも1体積%~60体積%の範囲内、特に10体積%~50体積%の範囲内であることが好ましい。また、正極活物質としては、例えばLiCoO2、LiMnO2、Li2NiMn3O8、LiVO2、LiCrO2、LiFePO4、LiCoPO4、LiNiO2、LiNi1/3Co1/3Mn1/3O2等を挙げることができる。
次に、本発明における負極活物質層について説明する。本発明における負極活物質層は、少なくとも負極活物質を含有する層であり、必要に応じて、固体電解質材料、導電化材および結着材の少なくとも一つを含有していても良い。特に、本発明においては、負極活物質層が固体電解質材料を含有し、その固体電解質材料が、上述した硫化物固体電解質材料であることが好ましい。イオン伝導性の高い負極活物質層を得ることができるからである。負極活物質層に含まれる上記硫化物固体電解質材料の割合は、電池の種類によって異なるものであるが、例えば0.1体積%~80体積%の範囲内、中でも1体積%~60体積%の範囲内、特に10体積%~50体積%の範囲内であることが好ましい。また、負極活物質としては、例えば金属活物質およびカーボン活物質を挙げることができる。金属活物質としては、例えばIn、Al、SiおよびSn等を挙げることができる。一方、カーボン活物質としては、例えばメソカーボンマイクロビーズ(MCMB)、高配向性グラファイト(HOPG)、ハードカーボン、ソフトカーボン等を挙げることができる。なお、負極活物質層に用いられる導電化材および結着材については、上述した正極活物質層における場合と同様である。また、負極活物質層の厚さは、例えば0.1μm~1000μmの範囲内であることが好ましい。
本発明の電池は、上述した電解質層、正極活物質層および負極活物質層を少なくとも有するものである。さらに通常は、正極活物質層の集電を行う正極集電体、および負極活物質層の集電を行う負極集電体を有する。正極集電体の材料としては、例えばSUS、アルミニウム、ニッケル、鉄、チタンおよびカーボン等を挙げることができ、中でもSUSが好ましい。一方、負極集電体の材料としては、例えばSUS、銅、ニッケルおよびカーボン等を挙げることができ、中でもSUSが好ましい。また、正極集電体および負極集電体の厚さや形状等については、電池の用途等に応じて適宜選択することが好ましい。また、本発明に用いられる電池ケースには、一般的な電池の電池ケースを用いることができる。電池ケースとしては、例えばSUS製電池ケース等を挙げることができる。
本発明の電池は、一次電池であっても良く、二次電池であっても良いが、中でも二次電池であることが好ましい。繰り返し充放電でき、例えば車載用電池として有用だからである。本発明の電池の形状としては、例えば、コイン型、ラミネート型、円筒型および角型等を挙げることができる。また、本発明の電池の製造方法は、上述した電池を得ることができる方法であれば特に限定されるものではなく、一般的な電池の製造方法と同様の方法を用いることができる。例えば、本発明の電池が全固体電池である場合、その製造方法の一例としては、正極活物質層を構成する材料、固体電解質層を構成する材料、および負極活物質層を構成する材料を順次プレスすることにより、発電要素を作製し、この発電要素を電池ケースの内部に収納し、電池ケースをかしめる方法等を挙げることができる。
次に、本発明の硫化物固体電解質材料の製造方法について説明する。本発明の硫化物固体電解質材料の製造方法は、2つの実施態様に大別することができる。そこで、本発明の硫化物固体電解質材料の製造方法について、第一実施態様および第二実施態様に分けて説明する。
第一実施態様の硫化物固体電解質材料の製造方法は、「A.硫化物固体電解質材料 1.第一実施態様」に記載した硫化物固体電解質材料の製造方法であって、上記M1元素、上記M2元素、上記S元素および上記O元素を含有する原料組成物を用いて、メカニカルミリングにより、非晶質化したイオン伝導性材料を合成するイオン伝導性材料合成工程と、上記非晶質化したイオン伝導性材料を加熱することにより、上記硫化物固体電解質材料を得る加熱工程と、を有することを特徴とするものである。
以下、第一実施態様の硫化物固体電解質材料の製造方法について、工程ごとに説明する。
まず、第一実施態様におけるイオン伝導性材料合成工程について説明する。第一実施態様におけるイオン伝導性材料合成工程は、上記M1元素、上記M2元素、上記S元素および上記O元素を含有する原料組成物を用いて、メカニカルミリングにより、非晶質化したイオン伝導性材料を合成する工程である。
第一実施態様における加熱工程は、上記非晶質化したイオン伝導性材料を加熱することにより、上記硫化物固体電解質材料を得る工程である。
第二実施態様の硫化物固体電解質材料の製造方法は、「A.硫化物固体電解質材料 2.第二実施態様」に記載した硫化物固体電解質材料の製造方法であって、上記M1元素、上記M2a元素、上記M2b元素、上記S元素および上記O元素を含有する原料組成物を用いて、メカニカルミリングにより、非晶質化したイオン伝導性材料を合成するイオン伝導性材料合成工程と、上記非晶質化したイオン伝導性材料を加熱することにより、上記硫化物固体電解質材料を得る加熱工程と、を有することを特徴とするものである。
出発原料として、硫化リチウム(Li2S)と、酸化リチウム(Li2O)と、五硫化二リン(P2S5)と、硫化ゲルマニウム(GeS2)とを用いた。これらの粉末をアルゴン雰囲気下のグローブボックス内で、Li2Sを0.3495g、Li2Oを0.03082g、P2S5を0.372641g、GeS2を0.2469gの割合で混合し、原料組成物を得た。得られた原料組成物を、振動ミルを用いて粉砕した。振動ミルにはシーエムティー科学社製TI-100を使用した。具体的には、10mLのポットに、原料組成物1gと、アルミナ製振動子(φ36.3mm、高さ48.9mm)とを入れ、回転数1440rpmで30分間処理を行った。これにより、Li3.35Ge0.35P0.65(S0.95O0.05)4の組成を有する、非晶質化したイオン伝導性材料を得た。
原料組成物として、Li2Sを0.30728g、Li2Oを0.06269g、P2S5を0.378922g、GeS2を0.251096gの割合で混合したものを用いたこと以外は、実施例1と同様にして結晶質の硫化物固体電解質材料を得た。得られた硫化物固体電解質材料は、Li3.35Ge0.35P0.65(S0.9O0.1)4の組成を有し、この組成はLi(4-x)Ge(1-x)Px(S1-yOy)4におけるx=0.65、y=0.1の組成に該当するものである。酸素置換量は10%である。
原料組成物として、Li2Sを0.190304g、Li2Oを0.150803g、P2S5を0.3962890g、GeS2を0.262604gの割合で混合したものを用いたこと以外は、実施例1と同様にして結晶質の硫化物固体電解質材料を得た。得られた硫化物固体電解質材料は、Li3.35Ge0.35P0.65(S0.77O0.23)4の組成を有し、この組成はLi(4-x)Ge(1-x)Px(S1-yOy)4におけるx=0.65、y=0.23の組成に該当するものである。酸素置換量は23%である。
原料組成物として、Li2Sを0.390529g、P2S5を0.366564g、GeS2を0.242907gの割合で混合したものを用いたこと以外は、実施例1と同様にして結晶質の硫化物固体電解質材料を得た。得られた硫化物固体電解質材料は、Li3.35Ge0.35P0.65S4の組成を有し、この組成はLi(4-x)Ge(1-x)Px(S1-yOy)4におけるx=0.65、y=0の組成に該当するものである。酸素置換量は0%である。
(X線回折測定)
実施例1~3および比較例1で得られた硫化物固体電解質材料を用いて、X線回折(XRD)測定を行った。XRD測定は、粉末試料に対して、不活性雰囲気下、CuKα線使用の条件で行った。その結果を図6~図9に示す。図9に示すように、比較例1では単相の硫化物固体電解質材料が得られた。ピークの位置は、2θ=17.38°、20.18°、20.44°、23.56°、23.96°、24.93°、26.96°、29.07°、29.58°、31.71°、32.66°、33.39°であった。すなわち、これらのピークが、イオン伝導性の高い結晶相Aのピークであると考えられる。なお、イオン伝導性の低い結晶相Bのピークである2θ=27.33°±0.50°のピークは確認されなかった。また、図6~図8に示すように、実施例1~3は、比較例1と同様の回折パターンを有することが確認された。
比較例1で得られた硫化物固体電解質材料の結晶構造をX線構造解析により同定した。XRDで得られた回折図形を基に直接法で晶系・結晶群を決定し、その後、実空間法により結晶構造を同定した。その結果、上述した図2、図3のような結晶構造を有することが確認された。すなわち、四面体T1(GeS4四面体およびPS4四面体)と、八面体O(LiS6八面体)とは稜を共有し、四面体T2(PS4四面体)と、八面体O(LiS6八面体)とは頂点を共有している結晶構造であった。また、上述したように実施例1~3は比較例1と同様の回折パターンを有することから、実施例1~3においても同様の結晶構造が形成されていることが確認された。
実施例1~3および比較例1で得られた硫化物固体電解質材料を用いて、25℃でのLiイオン伝導度を測定した。まず、アルゴン雰囲気のグローブボックス内で、試料を適量秤量し、ポリエチレンテレフタラート管(PET管、内径10mm、外径30mm、高さ20mm)に入れ、上下から、炭素工具鋼S45Cアンビルからなる粉末成型治具で挟んだ。次に、一軸プレス機(理研精機社製P-6)を用いて、表示圧力6MPa(成型圧力約110MPa)でプレスし、直径10mm、任意の厚さのペレットを成型した。次に、ペレットの両面に、金粉末(ニラコ社製、樹状、粒径約10μm)を13mg~15mgずつ乗せて、均一にペレット表面上に分散させ、表示圧力30MPa(成型圧力約560MPa)で成型した。その後、得られたペレットを、アルゴン雰囲気を維持できる密閉式電気化学セルに入れた。
出発原料として、硫化リチウム(Li2S、日本化学工業社製)と、酸化リチウム(Li2O、高純度化学社製)と、五硫化二リン(P2S5、アルドリッチ社製)と、硫化珪素(SiS2、高純度化学社製)を用いた。これらの粉末をアルゴン雰囲気下のグローブボックス内で、Li2Sを0.34083g、Li2Oを0.06819g、P2S5を0.38049g、SiS2を0.21047gの割合で混合し、原料組成物を得た。次に、原料組成物1gを、ジルコニアボール(10mmφ、10個)とともに、ジルコニア製のポット(45ml)に入れ、ポットを完全に密閉した(アルゴン雰囲気)。このポットを遊星型ボールミル機(フリッチュ製P7)に取り付け、台盤回転数370rpmで、40時間メカニカルミリングを行った。これにより、非晶質化したイオン伝導性材料を得た。
原料組成物として、Li2Sを0.386186g、Li2Oを0.03348565g、P2S5を0.373641747g、SiS2を0.2066865gの割合で混合したものを用いたこと以外は、実施例4と同様にして結晶質の硫化物固体電解質材料を得た。得られた硫化物固体電解質材料は、Li3.4Si0.4P0.6(S0.95O0.05)4の組成を有し、この組成はLi(4-x)Si(1-x)Px(S1-yOy)4におけるx=0.6、y=0.05の組成に該当するものである。酸素置換量は5%である。
原料組成物として、Li2Sを0.2449428g、Li2Oを0.141591g、P2S5を0.3949774g、SiS2を0.21848871gの割合で混合したものを用いたこと以外は、実施例4と同様にして結晶質の硫化物固体電解質材料を得た。得られた硫化物固体電解質材料は、Li3.4Si0.4P0.6(S0.8O0.2)4の組成を有し、この組成はLi(4-x)Si(1-x)Px(S1-yOy)4におけるx=0.6、y=0.2の組成に該当するものである。酸素置換量は20%である。
原料組成物として、Li2Sを0.429936g、P2S5を0.367033g、SiS2を0.203030gの割合で混合したものを用いたこと以外は、実施例4と同様にして結晶質の硫化物固体電解質材料を得た。得られた硫化物固体電解質材料は、Li3.4Si0.4P0.6S4の組成を有し、この組成はLi(4-x)Si(1-x)Px(S1-yOy)4におけるx=0.6、y=0の組成に該当するものである。酸素置換量は0%である。
(X線回折測定)
実施例4~6および比較例2で得られた硫化物固体電解質材料を用いて、X線回折(XRD)測定を行った。XRD測定は、粉末試料に対して、不活性雰囲気下、CuKα線使用の条件で行った。その結果を図11~図14に示す。図11~図14に示すように、実施例4~6および比較例2は、上述した比較例1と同様の回折パターンを有することが確認された。
実施例4~6および比較例2で得られた硫化物固体電解質材料を用いて、25℃でのLiイオン伝導度を測定した。測定方法は、評価1に記載した方法と同様である。得られた結果を図15に示す。図15に示されるように、硫黄を酸素で置換した実施例4~6は、硫黄を酸素で置換していない比較例2に比べて、Liイオン伝導度が同等か高いことが確認された。実施例1~3で得られた硫化物固体電解質材料のLiイオン伝導度が高い理由は、Liイオンが通過するトンネル(結晶中に存在するトンネル)のサイズが、O元素の導入により、より伝導しやすいサイズに変化したためであると考えられる。
2 … 負極活物質層
3 … 電解質層
4 … 正極集電体
5 … 負極集電体
6 … 電池ケース
10 … 電池
Claims (8)
- M1元素、M2元素、S元素およびO元素を含有し、
前記M1は、少なくともLiを含み、
前記M2は、P、Sb、Si、Ge、Sn、B、Al、Ga、In、Ti、Zr、V、Nbからなる群から選択される少なくとも一種であり、
CuKα線を用いたX線回折測定における2θ=29.58°±0.50°の位置にピークを有し、
前記2θ=29.58°±0.50°のピークの回折強度をIAとし、2θ=27.33°±0.50°のピークの回折強度をIBとした場合に、IB/IAの値が0.50未満であることを特徴とする硫化物固体電解質材料。 - M1元素、M2元素、S元素およびO元素を含有し、
前記M1は、少なくともLiを含み、
前記M2は、P、Sb、Si、Ge、Sn、B、Al、Ga、In、Ti、Zr、V、Nbからなる群から選択される少なくとも一種であり、
CuKα線を用いたX線回折測定における2θ=29.58°±0.50°の位置にピークを有し、
CuKα線を用いたX線回折測定における2θ=27.33°±0.50°の位置にピークを有しないか、
前記2θ=27.33°±0.50°の位置にピークを有する場合、前記2θ=29.58°±0.50°のピークの回折強度をIAとし、前記2θ=27.33°±0.50°のピークの回折強度をIBとした際に、IB/IAの値が0.50未満であることを特徴とする硫化物固体電解質材料。 - M1元素およびS元素から構成される八面体Oと、M2a元素およびS元素から構成される四面体T1と、M2b元素およびS元素から構成される四面体T2とを有し、前記四面体T1および前記八面体Oは稜を共有し、前記四面体T2および前記八面体Oは頂点を共有する結晶構造を主体として含有し、
前記M1は、少なくともLiを含み、
前記M2aおよび前記M2bは、それぞれ独立に、P、Sb、Si、Ge、Sn、B、Al、Ga、In、Ti、Zr、V、Nbからなる群から選択される少なくとも一種であり、
前記八面体O、前記四面体T1および前記四面体T2の少なくとも一つは、前記S元素の一部がO元素に置換されたものであることを特徴とする硫化物固体電解質材料。 - Li元素、Ge元素、P元素、S元素およびO元素を少なくとも含有し、
前記S元素および前記O元素の合計に対する前記O元素の割合が、25%以下であることを特徴とする請求項1から請求項3までのいずれかの請求項に記載の硫化物固体電解質材料。 - Li元素、Si元素、P元素、S元素およびO元素を少なくとも含有し、
前記S元素および前記O元素の合計に対する前記O元素の割合が、10%以下であることを特徴とする請求項1から請求項3までのいずれかの請求項に記載の硫化物固体電解質材料。 - 正極活物質を含有する正極活物質層と、負極活物質を含有する負極活物質層と、前記正極活物質層および前記負極活物質層の間に形成された電解質層とを含有する電池であって、
前記正極活物質層、前記負極活物質層および前記電解質層の少なくとも一つが、請求項1から請求項5までのいずれかの請求項に記載の硫化物固体電解質材料を含有することを特徴とする電池。 - 請求項1または請求項2に記載の硫化物固体電解質材料の製造方法であって、
前記M1元素、前記M2元素、前記S元素および前記O元素を含有する原料組成物を用いて、メカニカルミリングにより、非晶質化したイオン伝導性材料を合成するイオン伝導性材料合成工程と、
前記非晶質化したイオン伝導性材料を加熱することにより、前記硫化物固体電解質材料を得る加熱工程と、
を有することを特徴とする硫化物固体電解質材料の製造方法。 - 請求項3に記載の硫化物固体電解質材料の製造方法であって、
前記M1元素、前記M2a元素、前記M2b元素、前記S元素および前記O元素を含有する原料組成物を用いて、メカニカルミリングにより、非晶質化したイオン伝導性材料を合成するイオン伝導性材料合成工程と、
前記非晶質化したイオン伝導性材料を加熱することにより、前記硫化物固体電解質材料を得る加熱工程と、
を有することを特徴とする硫化物固体電解質材料の製造方法。
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Cited By (7)
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---|---|---|---|---|
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WO2017022464A1 (ja) * | 2015-07-31 | 2017-02-09 | 国立大学法人東京工業大学 | α-リチウム固体電解質 |
US9748602B2 (en) | 2013-04-16 | 2017-08-29 | Toyota Jidosha Kabushiki Kaisha | Sulfide solid electrolyte material, battery, and producing method for sulfide solid electrolyte material |
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US11127974B2 (en) | 2018-05-14 | 2021-09-21 | Samsung Electronics Co., Ltd. | Method of preparing sulfide-based solid electrolyte, sulfide-based solid electrolyte prepared therefrom, and solid secondary battery including the sulfide electrolyte |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR102443148B1 (ko) | 2013-05-15 | 2022-09-13 | 퀀텀스케이프 배터리, 인코포레이티드 | 배터리용 고상 캐소라이트 또는 전해질 |
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US10116001B2 (en) | 2015-12-04 | 2018-10-30 | Quantumscape Corporation | Lithium, phosphorus, sulfur, and iodine including electrolyte and catholyte compositions, electrolyte membranes for electrochemical devices, and annealing methods of making these electrolytes and catholytes |
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US10403933B2 (en) | 2017-03-31 | 2019-09-03 | Tokyo Institute Of Technology | Solid electrolyte material and method for producing the same |
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Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007012324A (ja) * | 2005-06-28 | 2007-01-18 | Sumitomo Electric Ind Ltd | リチウム二次電池負極部材およびその製造方法 |
JP2007273217A (ja) * | 2006-03-31 | 2007-10-18 | Idemitsu Kosan Co Ltd | 固体電解質、その製造方法及び全固体二次電池 |
JP2007273214A (ja) * | 2006-03-31 | 2007-10-18 | Idemitsu Kosan Co Ltd | 固体電解質、その製造方法及び全固体二次電池 |
JP2007305552A (ja) * | 2006-05-15 | 2007-11-22 | Sumitomo Electric Ind Ltd | 固体電解質とその形成方法 |
WO2010038313A1 (ja) * | 2008-10-03 | 2010-04-08 | トヨタ自動車株式会社 | 全固体型リチウム電池の製造方法 |
JP2011057500A (ja) * | 2009-09-09 | 2011-03-24 | Osaka Prefecture Univ | 硫化物固体電解質 |
WO2011118801A1 (ja) | 2010-03-26 | 2011-09-29 | 国立大学法人東京工業大学 | 硫化物固体電解質材料、電池および硫化物固体電解質材料の製造方法 |
JP2012089424A (ja) * | 2010-10-21 | 2012-05-10 | Sumitomo Electric Ind Ltd | 固体電解質および非水電解質電池 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4498688B2 (ja) | 2003-04-24 | 2010-07-07 | 出光興産株式会社 | リチウムイオン伝導性硫化物ガラス及びガラスセラミックスの製造方法 |
JP4813767B2 (ja) | 2004-02-12 | 2011-11-09 | 出光興産株式会社 | リチウムイオン伝導性硫化物系結晶化ガラス及びその製造方法 |
JP4754209B2 (ja) * | 2004-12-16 | 2011-08-24 | 日本化学工業株式会社 | リチウムコバルト系複合酸化物粉末の製造方法 |
US20110171398A1 (en) * | 2010-01-12 | 2011-07-14 | Oladeji Isaiah O | Apparatus and method for depositing alkali metals |
-
2012
- 2012-10-23 JP JP2012234153A patent/JP5888610B2/ja active Active
- 2012-12-21 US US14/365,950 patent/US9263763B2/en active Active
- 2012-12-21 CN CN201280061858.8A patent/CN103999279B/zh active Active
- 2012-12-21 EP EP12860207.5A patent/EP2797152B1/en active Active
- 2012-12-21 KR KR1020147016378A patent/KR101667468B1/ko active IP Right Grant
- 2012-12-21 WO PCT/JP2012/083350 patent/WO2013094757A1/ja active Application Filing
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007012324A (ja) * | 2005-06-28 | 2007-01-18 | Sumitomo Electric Ind Ltd | リチウム二次電池負極部材およびその製造方法 |
JP2007273217A (ja) * | 2006-03-31 | 2007-10-18 | Idemitsu Kosan Co Ltd | 固体電解質、その製造方法及び全固体二次電池 |
JP2007273214A (ja) * | 2006-03-31 | 2007-10-18 | Idemitsu Kosan Co Ltd | 固体電解質、その製造方法及び全固体二次電池 |
JP2007305552A (ja) * | 2006-05-15 | 2007-11-22 | Sumitomo Electric Ind Ltd | 固体電解質とその形成方法 |
WO2010038313A1 (ja) * | 2008-10-03 | 2010-04-08 | トヨタ自動車株式会社 | 全固体型リチウム電池の製造方法 |
JP2011057500A (ja) * | 2009-09-09 | 2011-03-24 | Osaka Prefecture Univ | 硫化物固体電解質 |
WO2011118801A1 (ja) | 2010-03-26 | 2011-09-29 | 国立大学法人東京工業大学 | 硫化物固体電解質材料、電池および硫化物固体電解質材料の製造方法 |
JP2012089424A (ja) * | 2010-10-21 | 2012-05-10 | Sumitomo Electric Ind Ltd | 固体電解質および非水電解質電池 |
Non-Patent Citations (2)
Title |
---|
NORIAKI KAMAYA ET AL.: "A lithium superionic conductor", NATURE MATERIALS, ADVANCED ONLINE PUBLICATION, 31 July 2011 (2011-07-31) |
RYOJI KANNO ET AL.: "Lithium Ionic Conductor Thio-LISICON The Li S-GeS -P S System", JOURNAL OF THE ELECTROCHEMICAL SOCIETY, vol. 148, no. 7, 2001, pages A742 - A746, XP055175241, DOI: doi:10.1149/1.1379028 |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9748602B2 (en) | 2013-04-16 | 2017-08-29 | Toyota Jidosha Kabushiki Kaisha | Sulfide solid electrolyte material, battery, and producing method for sulfide solid electrolyte material |
CN105210154A (zh) * | 2013-07-04 | 2015-12-30 | 三井金属矿业株式会社 | 结晶性固体电解质及其制造方法 |
EP3018660A4 (en) * | 2013-07-04 | 2016-11-30 | Mitsui Mining & Smelting Co | CRYSTALLINE FIXED ELECTROLYTE AND MANUFACTURING METHOD THEREFOR |
CN105210154B (zh) * | 2013-07-04 | 2017-07-14 | 三井金属矿业株式会社 | 结晶性固体电解质及其制造方法 |
US10644348B2 (en) | 2013-07-04 | 2020-05-05 | Mitsui Mining & Smelting Co., Ltd. | Crystalline solid electrolyte and production method therefor |
US10461363B2 (en) | 2014-06-25 | 2019-10-29 | Tokyo Institute Of Technology | Sulfide solid electrolyte material, battery, and producing method for sulfide solid electrolyte material |
WO2017022464A1 (ja) * | 2015-07-31 | 2017-02-09 | 国立大学法人東京工業大学 | α-リチウム固体電解質 |
JP2017033770A (ja) * | 2015-07-31 | 2017-02-09 | 国立大学法人東京工業大学 | α−リチウム固体電解質 |
US10741299B2 (en) | 2015-07-31 | 2020-08-11 | Tokyo Insititute of Technology | Solid α-lithium electrolyte |
US11127974B2 (en) | 2018-05-14 | 2021-09-21 | Samsung Electronics Co., Ltd. | Method of preparing sulfide-based solid electrolyte, sulfide-based solid electrolyte prepared therefrom, and solid secondary battery including the sulfide electrolyte |
US11799126B2 (en) | 2019-05-31 | 2023-10-24 | Samsung Electronics Co., Ltd. | Method of preparing solid electrolyte and all-solid battery including solid electrolyte prepared by the method |
JP2020123581A (ja) * | 2020-04-07 | 2020-08-13 | 国立大学法人東京工業大学 | α−リチウム固体電解質 |
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CN103999279B (zh) | 2017-05-31 |
KR20140103957A (ko) | 2014-08-27 |
CN103999279A (zh) | 2014-08-20 |
EP2797152B1 (en) | 2019-01-23 |
US20140363745A1 (en) | 2014-12-11 |
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