Modified sulfide solid electrolyte, manufacturing method thereof, electrode composite material and lithium ion battery

Abstract

Provided is a modified sulfide solid electrolyte which is capable of effectively exhibiting excellent battery performance even when applied as a paste even if the sulfide solid electrolyte has a large specific surface area, the modified sulfide solid electrolyte comprising: a sulfide solid electrolyte which has a BET specific surface area of 10 m2 / g or more and contains lithium atoms, sulfur atoms, phosphorus atoms, and halogen atoms; the present invention provides at least two compounds selected from specific compounds (A)-(I), a method for producing the modified sulfide solid electrolyte, and an electrode composite material and a lithium ion battery using the modified sulfide solid electrolyte.

Description

Technical Field

[0001] The invention relates to a modified sulfide solid electrolyte and a preparation method thereof, an electrode composite material and a lithium ion battery. Background Art

[0002] In recent years, with the rapid spread of information-related devices and communication devices such as personal computers, video cameras and mobile phones, the development of batteries used as their power sources has also attracted attention. Among them, lithium-ion batteries have attracted attention due to their high energy density.

[0003] In the past, an electrolyte containing a flammable organic solvent was used in a battery for such a purpose, and therefore, a safety device for suppressing the temperature rise during a short circuit, a structure for preventing a short circuit, and improvements in materials were required. In contrast, by changing the electrolyte to a solid electrolyte and making the battery fully solid, a flammable organic solvent is not used in the battery, and the safety device is simplified, and the manufacturing cost and productivity are excellent, so a battery in which the electrolyte is replaced by a solid electrolyte layer is developed.

[0004] As a solid electrolyte used in the solid electrolyte layer, sulfide solid electrolytes are known in the past. For sulfide solid electrolytes, it is first desired to improve the ion conductivity, and further, it is also required to improve the battery performance when used in lithium ion batteries. As methods for improving these performances, for example, a technique for coating the surface of a solid electrolyte, a technique for preparing a composition containing a solid electrolyte and an organic compound, etc. have been studied.

[0005] For example, in Patent Document 1, in order to improve ion conductivity, a method for manufacturing a composite solid electrolyte in which a specified halogenated hydrocarbon compound is used as a coating material to coat the surface of a sulfide solid electrolyte is proposed. Patent Document 2 discloses a solid electrolyte composition in which a compound having a C=O bond and a compound having an S=O bond are used to form a coating on the surface of the solid electrolyte in order to improve the affinity between the active material used in the negative electrode, positive electrode, etc. when manufacturing a lithium-ion battery and the sulfide solid electrolyte, thereby improving the cycle characteristics. In Patent Document 3, as a solid electrolyte composition capable of manufacturing an all-solid secondary battery showing excellent battery capacity, a solid electrolyte composition containing a dispersion medium such as a ketone compound and an alcohol compound is disclosed.

[0006] In addition, for example, in Patent Document 4, in order to achieve good cycle characteristics, a solid electrolyte composition containing a fluorine-containing compound is disclosed, the fluorine-containing compound containing fluorine atoms and P=O or C=O. Patent Document 5 discloses the following technology: as an all-solid secondary battery that suppresses the growth of lithium dendrites, is not prone to short circuits, and can suppress the reduction of battery voltage at a high level, a solid electrolyte composition containing an inorganic solid electrolyte and an organic compound having a non-ionic monovalent halogen atom other than fluorine is used as a solid electrolyte layer.

[0007] Furthermore, for example, Patent Document 6 discloses that in a sulfide solid electrolyte containing lithium, phosphorus, and sulfur and also containing an ester compound of carboxylic acid and alcohol, the ester compound is bonded to or adsorbed on the surface of the conductive sulfide to improve the cycle characteristics of the solid battery, and the sulfide solid electrolyte is obtained by a production method having a step of wet-grinding a slurry containing lithium ion conductive sulfide, an organic solvent, and the ester compound. Patent Document 7 discloses a technology for improving ion conductivity by coating a sulfide solid electrolyte with a predetermined organic compound having a halogen element as a functional group as a coating agent, and Patent Document 8 discloses a technology for improving ion conductivity and formability by containing a phosphorus compound such as a phosphate ester. In addition, Patent Document 9 discloses: a method for producing a solid electrolyte in which an anionic surfactant such as a sulfosuccinate salt or a benzenesulfonate salt as a monomer or oligomer, a solvent, and a sulfide solid electrolyte are mixed, and then the solvent is removed; and a solid electrolyte containing a predetermined amount of the surfactant in terms of specific surface area. Furthermore, it is disclosed that the use of a surfactant can provide a sulfide solid electrolyte in which generation of hydrogen sulfide and coarsening of particle size are suppressed.

[0008] As described above, in recent years, with the goal of practical application of lithium-ion batteries, there have been various requirements for improving not only the ion conductivity of the sulfide solid electrolyte itself, but also other performances, such as the performance when the solid electrolyte is applied to lithium-ion batteries. In order to meet such requirements, research is currently underway on technologies for coating the surface of the solid electrolyte and technologies for preparing a composition containing a solid electrolyte and an organic compound.

[0009] Prior art literature

[0010] Patent Literature

[0011] Patent Document 1: Japanese Patent Application Publication No. 2020-87633

[0012] Patent Document 2: Japanese Patent Application Publication No. 2017-147173

[0013] Patent Document 3: International Publication No. 2019 / 151373

[0014] Patent Document 4: Japanese Patent Application Publication No. 2017-157300

[0015] Patent Document 5: Japanese Patent Application Publication No. 2019-067523

[0016] Patent Document 6: International Publication No. 2020 / 203231

[0017] Patent Document 7: Japanese Patent Application Publication No. 2020-087633

[0018] Patent Document 8: Japanese Patent Application Publication No. 2020-166994

[0019] Patent Document 9: International Publication No. 2021 / 029315 Summary of the invention

[0020] Technical problem to be solved by the invention

[0021] The present invention has been made in view of such actual conditions, and its object is to provide a modified sulfide solid electrolyte having excellent coating adaptability when applied as a paste and capable of effectively exhibiting excellent battery performance, and a method for producing the same, as well as an electrode composite material and a lithium ion battery exhibiting excellent battery performance.

[0022] Solutions for solving the above technical problems

[0023] The modified sulfide solid electrolyte of the present invention is:

[0024] A modified sulfide solid electrolyte, comprising: a sulfide solid electrolyte having a BET specific surface area of ​​10 m 2 / g or more and containing a lithium atom, a sulfur atom, a phosphorus atom and a halogen atom; at least two compounds selected from the following compounds (A) to (I).

[0025] Compound (A) has a heterocyclic ring containing carbon atoms and oxygen atoms;

[0026] Compound (B) a compound having two or more heterocyclic rings containing carbon atoms and oxygen atoms;

[0027] Compound (C) an organic halide other than the following compound (F) 1;

[0028] Compound (D) a compound having a formyl group (CH(=O)-);

[0029] Compound (E) a compound having two or more acetyl groups (CH3C(=O)-);

[0030] Compound (F) has two or more -CH2X 1FAn organic halide 2 containing a halogen group and an organic group represented by 1F represents a fluorine atom or a bromine atom;

[0031] Compound (G) a thiol compound;

[0032] Compound (H) is a metal-free phosphorus compound, wherein the compound does not contain an oxygen atom singly bonded to a phosphorus atom;

[0033] Compound (I) contains no metal boron compound.

[0034] The method for preparing the modified sulfide solid electrolyte of the present invention is:

[0035] A method for manufacturing a modified sulfide solid electrolyte comprising: preparing a sulfide solid electrolyte having a BET specific surface area of ​​10 m 2 / g or more sulfide solid electrolyte containing lithium atoms, sulfur atoms, phosphorus atoms and halogen atoms, at least two compounds selected from the following compounds (A) to (I) and an organic solvent; and

[0036] The organic solvent is removed.

[0037] Compound (A) has a heterocyclic ring containing carbon atoms and oxygen atoms;

[0038] Compound (B) a compound having two or more heterocyclic rings containing carbon atoms and oxygen atoms;

[0039] Compound (C) an organic halide other than the following compound (F) 1;

[0040] Compound (D) a compound having a formyl group (CH(=O)-);

[0041] Compound (E) a compound having two or more acetyl groups (CH3C(=O)-);

[0042] Compound (F) has two or more -CH2X 1F An organic halide 2 containing a halogen group and an organic group represented by 1F represents a fluorine atom or a bromine atom;

[0043] Compound (G) a thiol compound;

[0044] Compound (H) is a metal-free phosphorus compound, wherein the compound does not contain an oxygen atom singly bonded to a phosphorus atom;

[0045] Compound (I) contains no metal boron compound.

[0046] The electrode composite material of the present invention is:

[0047] An electrode composite material comprises the modified sulfide solid electrolyte of the present invention and an electrode active material.

[0048] Furthermore, the lithium ion battery of the present invention is,

[0049] A lithium ion battery comprises at least one of the modified sulfide solid electrolyte of the present invention and the electrode composite material of the present invention.

[0050] Effects of the Invention

[0051] The present invention can provide a modified sulfide solid electrolyte having excellent coating suitability when applied as a paste and capable of effectively exhibiting excellent battery performance, and a method for producing the same, and can also provide an electrode composite material and a lithium ion battery exhibiting excellent battery performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0052] Figure 1 It is a graph showing the oil absorption amount (index) and the oxidation current (index) of Examples and Comparative Examples. DETAILED DESCRIPTION

[0053] Hereinafter, an embodiment of the present invention (hereinafter sometimes referred to as "the present embodiment") is described. In addition, in this specification, the upper and lower limits of the numerical ranges of "above", "below", and "to" are numerical values ​​that can be combined arbitrarily, and the numerical values ​​of the embodiments can also be used as the upper and lower limits.

[0054] (Discovery made by the inventors to complete the present invention)

[0055] The present inventors have conducted intensive studies to solve the above-mentioned technical problems and, as a result, have found the following matters and have completed the present invention.

[0056] Conventionally, there is a technique for coating or containing a certain compound on the surface of a sulfide solid electrolyte, as in Patent Documents 1 to 9. Patent Documents 1 to 9 set as a technical problem the improvement of battery performance such as improvement of ion conductivity, improvement of battery capacity and suppression of battery voltage drop when a lithium ion battery is manufactured, and maintenance of discharge capacity during repeated charge and discharge, etc. by using this technique.

[0057] However, in the manufacturing process of lithium-ion batteries (also called "all-solid batteries"), a paste mixed with a solid electrolyte, other specified components and a solvent is prepared and applied to form a diaphragm layer and an electrode composite material layer. In order to improve the performance of these layers, it is necessary to increase the density of the solid electrolyte constituting these layers. For the increase in this density, it is effective to use a solid electrolyte with a large specific surface area.

[0058] Thus, there is a requirement to use a solid electrolyte with a large specific surface area as the solid electrolyte, but if the specific surface area of ​​the solid electrolyte is large, there will be manufacturing problems such as increased viscosity of the paste and significantly reduced coating adaptability. On the other hand, although the coating adaptability of the paste can be improved by reducing the viscosity of the paste by using a large amount of solvent, there will be problems such as a longer drying time or a decrease in the density of the solid electrolyte constituting the layer, which leads to reduced battery performance. Therefore, the coating adaptability of the paste is in a contradictory relationship with obtaining higher battery performance. In this way, a solid electrolyte with a large specific surface area of ​​10m 2 As described above, when a sulfide solid electrolyte with a concentration of 100 μg or more is made into a paste, the viscosity becomes high, which not only significantly reduces the coating suitability, but also requires a large amount of solvent to reduce the viscosity of the paste, thereby prolonging the drying time and significantly reducing the battery performance due to the reduction in density.

[0059] Many methods have been studied to improve ion conductivity and battery performance as technical issues, such as Patent Documents 1 to 9. However, as the practical application of lithium-ion batteries is rapidly progressing, no research has been conducted on methods to improve performance in the manufacturing process, such as paste coating suitability, with an eye on mass production.

[0060] The present inventors have continued to conduct intensive research based on the techniques disclosed in Patent Documents 1 to 9 for coating a certain compound on the surface of a sulfide solid electrolyte and have found that even a sulfide solid electrolyte with a large specific surface area of ​​10 m 2 A sulfide solid electrolyte with a specific surface area of ​​10 m / s or more can be made into a sulfide solid electrolyte with excellent coating adaptability when applied as a paste and can effectively exhibit excellent battery performance by combining a plurality of predetermined compounds used in the present invention and attaching them to the surface. 2 / g or more, even a sulfide solid electrolyte can obtain an effect of excellent coating suitability when applied as a paste, which is a surprising phenomenon that has never been recognized so far.

[0061] In this specification, "solid electrolyte" refers to an electrolyte that remains solid at 25° C. in a nitrogen atmosphere. The "sulfide solid electrolyte" obtained by the production method of this embodiment is a solid electrolyte containing lithium atoms, sulfur atoms, phosphorus atoms, and halogen atoms, and having ion conductivity caused by lithium atoms.

[0062] The "sulfide solid electrolyte" includes both crystalline sulfide solid electrolytes and amorphous sulfide solid electrolytes having a crystal structure. In this specification, the crystalline sulfide solid electrolyte refers to a solid electrolyte in which a peak derived from a solid electrolyte is observed in an X-ray diffraction pattern in a powder X-ray diffraction (XRD) measurement, and is a material that is independent of whether or not there is a peak derived from a raw material of the solid electrolyte. That is, the crystalline sulfide solid electrolyte includes a crystal structure derived from a solid electrolyte, and a part of it may be a crystal structure derived from the solid electrolyte, or all of it may be a crystal structure derived from the solid electrolyte. In addition, as long as the crystalline sulfide solid electrolyte has the above-mentioned X-ray diffraction pattern, it may also include an amorphous sulfide solid electrolyte (also referred to as a "glass component") in a part thereof. Therefore, the crystalline sulfide solid electrolyte includes so-called glass ceramics obtained by heating an amorphous solid electrolyte (glass component) to a crystallization temperature or above.

[0063] In addition, in this specification, an amorphous sulfide solid electrolyte (glass component) means that in powder X-ray diffraction (XRD) measurement, the X-ray diffraction pattern is a halo pattern in which substantially no peaks other than peaks derived from the material are observed, regardless of the presence or absence of peaks derived from the raw materials of the solid electrolyte.

[0064] In the present embodiment, the above distinction between crystallinity and amorphousness is also applicable to both the sulfide solid electrolyte and the modified sulfide solid electrolyte.

[0065] (Various Aspects of the Present Embodiment)

[0066] The modified sulfide solid electrolyte of the first embodiment of the present invention is:

[0067] A modified sulfide solid electrolyte, comprising: a sulfide solid electrolyte having a BET specific surface area of ​​10 m 2 / g or more and containing a lithium atom, a sulfur atom, a phosphorus atom and a halogen atom; at least two compounds selected from the following compounds (A) to (I).

[0068] Compound (A) has a heterocyclic ring containing carbon atoms and oxygen atoms;

[0069] Compound (B) a compound having two or more heterocyclic rings containing carbon atoms and oxygen atoms;

[0070] Compound (C) an organic halide other than the following compound (F) 1;

[0071] Compound (D) a compound having a formyl group (CH(=O)-);

[0072] Compound (E) a compound having two or more acetyl groups (CH3C(=O)-);

[0073] Compound (F) has two or more -CH2X 1F An organic halide 2 containing a halogen group and an organic group represented by 1F represents a fluorine atom or a bromine atom;

[0074] Compound (G) a thiol compound;

[0075] Compound (H) is a metal-free phosphorus compound, wherein the compound does not contain an oxygen atom singly bonded to a phosphorus atom;

[0076] Compound (I) contains no metal boron compound.

[0077] As the sulfide solid electrolyte containing lithium atoms, sulfur atoms, phosphorus atoms and halogen atoms, a sulfide solid electrolyte obtained by a conventional method, for example, using lithium sulfide, phosphorus pentasulfide, lithium halide, monomeric halogen, etc. as raw materials can be typically exemplified. That is, the modified sulfide solid electrolyte of the present embodiment includes a sulfide solid electrolyte having a BET specific surface area of ​​10 m2 obtained by a conventional method. 2 / g or more, and a sulfide solid electrolyte having a large specific surface area and at least two compounds selected from the above compounds (A) to (I) (hereinafter also referred to as "plural specific compounds").

[0078] In the past, the BET specific surface area was relatively large, only 10m 2 In a sulfide solid electrolyte having a content of more than 100 g, the coating performance of the paste containing the required content to ensure the density of the solid electrolyte in the layer in order to exhibit the specified battery performance is significantly reduced, and it is extremely difficult to effectively form the positive electrode, negative electrode, and electrolyte layer. The sulfide solid electrolyte of this embodiment contains a conventional sulfide solid electrolyte and a plurality of specific compounds, and the coating adaptability is significantly improved, that is, it is "modified" and should be called a "modified sulfide solid electrolyte".

[0079] The above-mentioned multiple specific compounds used in the modified sulfide solid electrolyte of the present embodiment are common in that they are all compounds containing heteroatoms such as oxygen atoms, halogen atoms, sulfur atoms, phosphorus atoms, and boron atoms. As the modified sulfide solid electrolyte of the present embodiment, among the compounds containing heteroatoms, it is necessary to use a combination of multiple specific compounds such as the above-mentioned compounds (A) to (I). By using a combination of multiple such specific compounds, it is possible to achieve excellent coating adaptability when applied as a paste and effectively achieve excellent battery performance.

[0080] In the modified sulfide solid electrolyte of the present embodiment, it has not been determined how the above compounds (A) to (I) are contained, but it is presumed that these compounds adhere to the surface of the sulfide solid electrolyte while maintaining their structures.

[0081] The examples confirm that the sulfide solid electrolyte containing at least two compounds selected from the above compounds (A) to (I) has a lower oil absorption than the sulfide solid electrolyte not containing these compounds. It is reasonable to assume that the reduction in oil absorption is caused by the adhesion of multiple specific compounds to the surface of the sulfide solid electrolyte and the blocking of at least a part of the pores possessed by the sulfide solid electrolyte. It is known that in general, in order to improve coating adaptability, the oil absorption is also related to the specific surface area. It is speculated that by allowing multiple specific compounds to adhere to the surface of the sulfide solid electrolyte, the oil absorption is reduced and the coating adaptability is improved.

[0082] Regarding the attachment of various specific compounds on the surface of the sulfide solid electrolyte, it is not clear in what form the attachment is, that is, physical attachment or chemical attachment. However, since heteroatoms such as oxygen atoms have the property of easily bonding with lithium atoms, halogen atoms, etc., it is highly likely that the heteroatoms contained in the above compounds (A) to (I) are bonded with lithium atoms, halogen atoms, etc. constituting the sulfide solid electrolyte and attached to the surface, that is, chemical attachment. Considering the above speculation, it can be considered that the oil absorption is reduced and the coating adaptability is improved regardless of chemical attachment or physical attachment.

[0083] In the modified sulfide solid electrolyte of the present embodiment, regardless of which of the above-mentioned compounds are attached, as long as a plurality of specific compounds such as the above-mentioned compounds (A) to (I) are combined and attached to the surface, the oil absorption amount is likely to be reduced, resulting in improved coating suitability and improved battery performance.

[0084] The modified sulfide solid electrolyte of the second embodiment of the present embodiment is, in the above-mentioned first embodiment,

[0085] comprising at least one compound selected from the compound (B) and at least one compound selected from the compounds (A) and (C) to (I),

[0086] The modified sulfide solid electrolyte of the third embodiment is, in the first or second embodiment,

[0087] It contains at least one compound selected from the compound (B) and at least one compound selected from the compounds (A), (C) and (F).

[0088] In the modified sulfide solid electrolyte of the present embodiment, as long as at least two compounds selected from the above compounds (A) to (I) are used, the coating adaptability when applied as a paste is excellent and the effect of effectively exhibiting excellent battery performance can be exhibited. Among them, if at least one compound selected from the compound (A) and at least one compound selected from the compounds (B) to (I) are used in combination, and further at least one compound selected from the compound (A) and at least one compound selected from the compounds (A), (C) and (F) are used in combination, the coating adaptability is further improved and the excellent battery performance is more effectively exhibited. Among the above compounds (A) to (I), compound (B) is particularly a compound that has a more excellent effect on the oxidation resistance, and the other compounds (A) and (C) to (I) are compounds that have a more excellent effect on the reduction of oil absorption. Therefore, by using compound (B) in combination with other compounds (A) and (C) to (I), it is possible to improve coating adaptability by reducing oil absorption, improve battery performance by increasing the density of the solid electrolyte, and expect improvements in performance such as oxidation resistance, which is one of the battery performances.

[0089] Oxidation resistance refers to a property related to the difficulty of oxidation of a solid electrolyte, and improved oxidation resistance means that the oxidation current measured by the cyclic voltammetry measurement (CV measurement (oxidation current measurement)) described later becomes smaller. By using at least two compounds selected from the above compounds (A) to (I), it is possible to expect not only an improvement in battery performance due to a reduction in oil absorption, but also an improvement in battery performance due to improved oxidation resistance. By using the combination specified in the second and third embodiments, it is possible to further expect an improvement in battery performance due to improved oxidation resistance.

[0090] A modified sulfide solid electrolyte according to a fourth aspect of the present embodiment is, in any one of the first to third aspects,

[0091] The heterocyclic ring containing carbon atoms and oxygen atoms of the compounds (A) and (B) is an oxirane ring.

[0092] As compounds (A) and (B), any compound having a heterocyclic ring can be used without particular limitation, and excellent coating adaptability can be obtained. Among them, by using an oxirane ring as the heterocyclic ring, that is, by using a compound having one or more oxirane rings, compounds (A) and (B) are easily attached to the sulfide solid electrolyte, the oil absorption is further reduced, and excellent coating adaptability is easily obtained, and excellent battery performance can be more effectively obtained.

[0093] A modified sulfide solid electrolyte according to a fifth aspect of the present embodiment is, in any one of the first to fourth aspects,

[0094] The compound (C) is at least one compound selected from the following compounds: 1C (X 1C represents a halogen atom); a compound having a haloformyl group (CX 1C (=O)-(X 1C represents a halogen atom)) compound; having a halogenated silyl group (-SiX 1c n 1C (X 1C Represents a halogen atom, n 1C represents an integer of 1 to 3)).

[0095] As compound (C), any compound other than compound (F) described later, which is an organic halide, i.e., an organic compound partially containing halogen atoms, can be used without particular limitation, and excellent coating adaptability can be obtained. As compound (C), it is considered that if it is an organic halide other than compound (F) and is at least one compound selected from the above three halogen atom-containing groups, compound (C) becomes easy to adhere to the sulfide solid electrolyte, thereby further reducing the oil absorption, becoming easy to obtain excellent coating adaptability and more effectively obtaining excellent battery performance.

[0096] Regarding compound (C), the above-mentioned compound has a -CH2X 1C (X 1C The compound having a halogen atom) does not have two or more -CH2X 1F (X 1F represents a fluorine atom or a bromine atom), and thus does not belong to compound (F). In addition, since the above-mentioned compounds having a haloformyl group and a halosilyl group do not belong to compound (F), the compounds having two or more -CH2X 1F (X 1F Compounds containing a halogen group represented by (representing a fluorine atom or a bromine atom) are not included.

[0097] The modified sulfide solid electrolyte of a sixth aspect of the present embodiment is, in the fourth or fifth aspect,

[0098] The compound (A) is at least one compound selected from an epoxy compound 1A represented by the following general formula (1A), an epoxy compound 2A represented by the following general formula (2A), and an epoxy compound 3A represented by the following general formula (3A).

[0099] [Chemistry 1]

[0100]

[0101] (The general formula will be described later.)

[0102] As compound (A), any compound having a heterocyclic ring can be used without particular limitation, and excellent coating adaptability can be obtained. Among them, it is believed that by using an oxirane ring as the heterocyclic ring, that is, by using a compound having one oxirane ring, compound (A) becomes easy to adhere to the sulfide solid electrolyte, the oil absorption is further reduced, and excellent coating adaptability is easily obtained, and excellent battery performance can be more effectively obtained.

[0103] It is believed that the attachment of compound (A) is preferably moderate attachment. This is because if it is moderate attachment, the coating adaptability is improved by the effect of reducing the oil absorption, thereby improving the battery performance. On the other hand, it is possible to suppress the reduction of ionic conductivity and suppress the reduction of the effect of improving battery performance brought about by the improvement of coating adaptability. Therefore, as compound (A), it is preferably a compound with a specific structure as represented by the above general formula. This is because it is believed that a moderate chemical or physical attachment state can be obtained by moderate steric hindrance.

[0104] A modified sulfide solid electrolyte according to a seventh aspect of the present embodiment is, in any one of the fourth to sixth aspects,

[0105] The compound (B) is an epoxy compound represented by the following general formula (1B), and has at least two groups selected from the group consisting of an epoxy group, a glycidyl group, and a glycidyl ether group.

[0106] [Chemistry 2]

[0107]

[0108] (The general formula will be described later.)

[0109] As compound (B), any compound having a heterocyclic ring can be used without particular limitation, and excellent coating adaptability can be obtained. Among them, it is believed that by using an oxirane ring as a heterocyclic ring and using a compound having two or more oxirane rings, more specifically, using a compound having any one of an epoxy group, a glycidyl group, and a glycidyl ether group as a group having an oxirane ring, compound (B) becomes easy to adhere to the sulfide solid electrolyte, so the oil absorption is further reduced, it is easy to obtain excellent coating adaptability, and excellent battery performance can be more effectively obtained.

[0110] In addition, it is believed that by using a compound having a specific structure represented by the above general formula as compound (B), as described for the above compound (A), a moderate chemical or physical adhesion state can be obtained due to moderate steric hindrance. Therefore, the oil absorption is reduced, excellent coating adaptability is easily obtained, and excellent battery performance can be obtained more effectively.

[0111] The modified sulfide solid electrolyte according to an eighth aspect of the present embodiment is, in any one of the fifth to seventh aspects,

[0112] The compound (C) is at least one compound selected from an organic halide 1a represented by the following general formula (1C), an organic halide 1b represented by the following general formula (2C), an organic halide 1c represented by the following general formula (3C), and an organic halide 1d represented by the following general formula (4C).

[0113] [Chemistry 3]

[0114]

[0115] (The general formula will be described later.)

[0116] As compound (C), any compound other than compound (F) described later, which is an organic halide, i.e., an organic compound partially having a halogen atom, can be used without particular limitation, and excellent coating adaptability can be obtained. Among them, it is believed that if the compound is represented by the above general formula, compound (C) is easily attached to the sulfide solid electrolyte, so the oil absorption is further reduced, and excellent coating adaptability is easily obtained, and excellent battery performance can be more effectively obtained.

[0117] It is believed that by using a compound having a specific structure represented by the above general formula as compound (C), as described for the above compound (A), a moderate chemical or physical adhesion state can be obtained through moderate steric hindrance, thereby reducing the oil absorption, easily obtaining excellent coating adaptability, and more effectively obtaining excellent battery performance.

[0118] As described in the fifth embodiment, the compound (C) represented by the above general formula belongs to a compound having one -CH2X 1C (X 1C represents a halogen atom), a compound having a haloformyl group, and a compound having a halosilyl group. Typically, the compounds represented by the above general formulas (1C) and (2C) are compounds having one -CH2X 1C (X 1Crepresents a halogen atom), the compound represented by the general formula (3C) belongs to the compound having a haloformyl group, and the compound represented by the general formula (4C) belongs to the compound having a halosilyl group. Here, regarding "typically", for example, in the general formula (3C) X 31C or X 32C In the case where the aliphatic hydrocarbon group is a group in which one hydrogen atom connected to the carbon at the end is substituted with a halogen atom, the following matters can be considered: 1C (X 1C represents a halogen atom), that is, a compound represented by the general formula (3C) can belong to a compound having one -CH2X 1C (X 1C represents a halogen atom) and the like.

[0119] A ninth modified sulfide solid electrolyte according to the present embodiment is, in any one of the first to eighth embodiments,

[0120] The compound (D) is a compound represented by the following general formula (1D).

[0121] [Chemistry 4]

[0122]

[0123] (The general formula will be described later.)

[0124] As compound (D), any compound having a formyl group (CH(=O)-) can be used without particular limitation, and excellent coating adaptability can be obtained. Among them, it is considered that if the compound is represented by the above general formula, compound (D) is easily attached to the sulfide solid electrolyte, so the oil absorption is further reduced, and excellent coating adaptability is easily obtained, and excellent battery performance can be more effectively obtained.

[0125] In addition, it is believed that by using a compound having a specific structure represented by the above general formula as compound (D), as described for the above compound (A), a moderate chemical or physical adhesion state can be obtained through moderate steric hindrance, so that the oil absorption is reduced, excellent coating adaptability is easily obtained, and excellent battery performance can be obtained more effectively.

[0126] A tenth modified sulfide solid electrolyte according to the present embodiment is, in any one of the first to ninth embodiments,

[0127] The compound (E) is a compound represented by the following general formula (1E).

[0128] [Chemistry 5]

[0129]

[0130] (The general formula will be described later.)

[0131] As compound (E), any compound having two or more acetyl groups (CH3C(=O)-) can be used without particular limitation, and excellent coating adaptability can be obtained. Among them, it can be considered that if the compound is represented by the above general formula, compound (E) is easily attached to the sulfide solid electrolyte, so the oil absorption is further reduced, it is easy to obtain excellent coating adaptability, and excellent battery performance can be more effectively obtained.

[0132] In addition, it is believed that by using a compound having a specific structure represented by the above general formula as compound (E), as described for the above compound (A), a moderate chemical or physical adhesion state can be obtained through moderate steric hindrance, so that the oil absorption is reduced, excellent coating adaptability is easily obtained, and excellent battery performance can be obtained more effectively.

[0133] The modified sulfide solid electrolyte according to an eleventh aspect of the present embodiment is, in any one of the first to tenth aspects,

[0134] The compound (F) is a compound represented by the following general formula (1F).

[0135] [Chemistry 6]

[0136]

[0137] (The general formula will be described later.)

[0138] As compound (F), any compound having two or more -CH2X 1F (X 1F A compound containing a halogen group and an organic group represented by (representing a fluorine atom or a bromine atom) can be used without particular limitation, and excellent coating adaptability can be obtained. Among them, it is considered that if it is a compound represented by the above general formula, the compound (F) is easily attached to the sulfide solid electrolyte, so the oil absorption is further reduced, it is easy to obtain excellent coating adaptability, and excellent battery performance can be more effectively obtained.

[0139] It is believed that by using a compound having a specific structure represented by the above general formula as compound (F), as described for the above compound (A), a moderate chemical or physical adhesion state can be obtained through moderate steric hindrance, thereby reducing the oil absorption, easily obtaining excellent coating adaptability, and more effectively obtaining excellent battery performance.

[0140] A modified sulfide solid electrolyte according to a twelfth aspect of the present embodiment is, in any one of the first to eleventh aspects,

[0141] The compound (G) is at least one compound selected from a thiol compound 1 represented by the following general formula (1G) and a thiol compound 2 represented by the following general formula (2G).

[0142] [Chemistry 7]

[0143]

[0144] (The general formula will be described later.)

[0145] As compound (G), any thiol compound, i.e., a compound having a thiol group, can be used without particular limitation, and excellent coating adaptability can be obtained. Among them, it is considered that if the compound is represented by the above general formula, compound (G) is easily attached to the sulfide solid electrolyte, so the oil absorption is further reduced, and excellent coating adaptability is easily obtained, and excellent battery performance can be more effectively obtained.

[0146] It is believed that by using a thiol compound having a specific structure represented by the above general formula as compound (G), as described for the above compound (A), a moderate chemical or physical adhesion state can be obtained due to moderate steric hindrance, so that the oil absorption is reduced, excellent coating adaptability is easily obtained, and excellent battery performance can be more effectively obtained.

[0147] A modified sulfide solid electrolyte according to a thirteenth aspect of the present embodiment is, in any one of the first to twelfth aspects,

[0148] The compound (H) is at least one metal-free phosphorus compound selected from a metal-free phosphorus compound 1H represented by the following general formula (1H), a metal-free phosphorus compound 2H represented by the following general formula (2H), and a metal-free phosphorus compound 3H represented by the following general formula (3H).

[0149] [Chemistry 8]

[0150]

[0151] (The general formula will be described later.)

[0152] As compound (H), any metal-free phosphorus compound (wherein the compound does not contain an oxygen atom single-bonded to a phosphorus atom) can be used without particular limitation, and excellent coating adaptability can be obtained. Among them, it is considered that if the compound is represented by the above general formula, compound (H) is easily attached to the sulfide solid electrolyte, the oil absorption is further reduced, and excellent coating adaptability is easily obtained, so that excellent battery performance can be more effectively obtained.

[0153] It is believed that by using a compound having a specific structure represented by the above general formula as compound (H), as described for the above compound (A), a moderate chemical or physical adhesion state can be obtained through moderate steric hindrance, thereby reducing the oil absorption, easily obtaining excellent coating adaptability, and more effectively obtaining excellent battery performance.

[0154] A modified sulfide solid electrolyte according to a fourteenth aspect of the present embodiment is, in any one of the first to thirteenth aspects,

[0155] The compound (I) is a compound represented by the following general formula (1I).

[0156] [Chemistry 9]

[0157]

[0158] (The general formula will be described later.)

[0159] As compound (I), any metal-free boron compound can be used without particular limitation, and excellent coating adaptability can be obtained. Among them, it can be considered that if the compound is represented by the above general formula, compound (I) is easily attached to the sulfide solid electrolyte, the oil absorption is further reduced, and excellent coating adaptability is easily obtained, so that excellent battery performance can be more effectively obtained.

[0160] It is believed that by using a compound having a specific structure represented by the above general formula as compound (I), as described for the above compound (A), a moderate chemical or physical adhesion state can be obtained due to moderate steric hindrance, so that the oil absorption is reduced, excellent coating adaptability is easily obtained, and excellent battery performance can be obtained more effectively.

[0161] A fifteenth modified sulfide solid electrolyte according to the present embodiment is, in any one of the first to fourteenth embodiments,

[0162] The content of the at least two compounds is 0.03 parts by mass or more and 25 parts by mass or less relative to 100 parts by mass of the sulfide solid electrolyte.

[0163] If the content of at least two compounds selected from the compounds (A) to (I) is 0.03 parts by mass or more and 25 parts by mass or less relative to 100 parts by mass of the sulfide solid electrolyte, these compounds are appropriately dispersed and attached to the surface of the sulfide solid electrolyte to reduce the oil absorption, and the ion conductivity can be appropriately maintained, so the coating adaptability is easily improved, and excellent battery performance is easily and effectively manifested. Regarding the content of the compound, as long as the amount of the compound used when manufacturing the modified sulfide solid electrolyte is known, the amount used directly becomes the content.

[0164] The method for producing a modified sulfide solid electrolyte according to the sixteenth aspect of the present embodiment is:

[0165] A method for manufacturing a modified sulfide solid electrolyte comprising: preparing a sulfide solid electrolyte having a BET specific surface area of ​​10 m 2 / g or more sulfide solid electrolyte containing lithium atoms, sulfur atoms, phosphorus atoms and halogen atoms, at least two compounds selected from the following compounds (A) to (I) and an organic solvent; and

[0166] The organic solvent is removed.

[0167] Compound (A) has a heterocyclic ring containing carbon atoms and oxygen atoms;

[0168] Compound (B) a compound having two or more heterocyclic rings containing carbon atoms and oxygen atoms;

[0169] Compound (C) an organic halide other than the following compound (F) 1;

[0170] Compound (D) a compound having a formyl group (CH(=O)-);

[0171] Compound (E) a compound having two or more acetyl groups (CH3C(=O)-);

[0172] Compound (F) has two or more -CH2X 1F An organic halide 2 containing a halogen group and an organic group represented by 1F represents a fluorine atom, a chlorine atom, a bromine atom or an iodine atom;

[0173] Compound (G) a thiol compound;

[0174] Compound (H) is a metal-free phosphorus compound, wherein the compound does not contain an oxygen atom singly bonded to a phosphorus atom;

[0175] Compound (I) contains no metal boron compound.

[0176] As described above, the modified sulfide solid electrolyte of the present embodiment is not particularly limited in its production method as long as it contains at least two compounds selected from compounds (A) to (I). According to the method for producing a modified sulfide solid electrolyte of the sixteenth embodiment of the present embodiment, at least two compounds selected from compounds (A) to (I) can be compounds that exist by adhering to the surface of the sulfide solid electrolyte, so it has excellent coating adaptability, can effectively demonstrate excellent battery performance, and becomes possible to more efficiently produce such a modified sulfide solid electrolyte of the present embodiment.

[0177] By mixing a sulfide solid electrolyte, at least two compounds selected from compounds (A) to (I) and an organic solvent, a solution or slurry mixture can be obtained. However, since the modified sulfide solid electrolyte cannot be used in this state, the organic solvent is removed from the solution or slurry.

[0178] The method for producing a modified sulfide solid electrolyte according to a seventeenth aspect of the present embodiment is that the organic solvent used in the production method according to the sixteenth aspect is:

[0179] At least one solvent selected from aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, aromatic hydrocarbon solvents, ether solvents, ester solvents, and nitrile solvents.

[0180] By using the above solvent as the organic solvent, it is possible to promote the adhesion of a plurality of specific compounds to the surface of the sulfide solid electrolyte, and thus it is easy to improve coating suitability.

[0181] An electrode composite material according to an eighteenth aspect of the present embodiment includes the modified sulfide solid electrolyte or the like according to any one of the first to fifteenth aspects and an electrode active material.

[0182] Furthermore, a lithium ion battery according to a nineteenth aspect of the present embodiment includes at least one of the modified sulfide solid electrolyte or the like according to any one of the first to fifteenth aspects and the electrode active material according to the eighteenth aspect.

[0183] As described above, the modified sulfide solid electrolyte of the present embodiment has excellent coating adaptability when applied as a paste, and can effectively demonstrate excellent battery performance. Therefore, the electrode composite material including the modified sulfide solid electrolyte of the present embodiment also has excellent coating adaptability, so that lithium ion batteries can be efficiently manufactured, and the obtained lithium ion batteries have excellent battery performance.

[0184] 〔Modified sulfide solid electrolyte〕

[0185] The modified sulfide solid electrolyte of this embodiment is:

[0186] A modified sulfide solid electrolyte, comprising: a sulfide solid electrolyte having a BET specific surface area of ​​10 m 2 / g or more and containing a lithium atom, a sulfur atom, a phosphorus atom and a halogen atom; at least two compounds selected from the following compounds (A) to (I).

[0187] Compound (A) has a heterocyclic ring containing carbon atoms and oxygen atoms;

[0188] Compound (B) a compound having two or more heterocyclic rings containing carbon atoms and oxygen atoms;

[0189] Compound (C) an organic halide other than the following compound (F) 1;

[0190] Compound (D) a compound having a formyl group (CH(=O)-);

[0191] Compound (E) a compound having two or more acetyl groups (CH3C(=O)-);

[0192] Compound (F) has two or more -CH2X 1F An organic halide 2 containing a halogen group and an organic group represented by 1F represents a fluorine atom or a bromine atom;

[0193] Compound (G) a thiol compound;

[0194] Compound (H) is a metal-free phosphorus compound, wherein the compound does not contain an oxygen atom singly bonded to a phosphorus atom;

[0195] Compound (I) contains no metal boron compound.

[0196] Hereinafter, the compounds (A) to (I) contained in the modified sulfide solid electrolyte of the present embodiment will be described.

[0197] (Compound (A))

[0198] The compound (A) used in the modified sulfide solid electrolyte of the present embodiment is a compound having one heterocyclic ring containing carbon atoms and oxygen atoms (may also be referred to as a "heteromonocyclic compound").

[0199] As the heterocyclic ring containing carbon atoms and oxygen atoms possessed by compound (A), preferably, there can be mentioned the heterocyclic ring possessed by saturated or unsaturated monocyclic oxygen-containing heterocyclic compounds such as ethylene oxide, oxetane, tetrahydrofuran, dihydrofuran, furan, dioxolane, tetrahydropyran, pyran, etc. By having such a heterocyclic ring, the oil absorption is reduced, excellent coating adaptability is easily obtained, and excellent battery performance can be obtained more effectively.

[0200] Among the above heterocyclic rings, if the availability is also considered, the heterocyclic ring possessed by ethylene oxide, that is, the ethylene oxide ring is preferred. Therefore, as the heteromonocyclic compound of the compound (A) used in the present embodiment, a compound having one ethylene oxide ring is preferred, and the following epoxy compound 1A represented by the general formula (1A), the epoxy compound 2A represented by the general formula (2A), and the epoxy compound 3A represented by the general formula (3A) can be particularly preferably exemplified. In the modified sulfide solid electrolyte of the present embodiment, as the compound (A), the compounds represented by these general formulas can be used alone, or a plurality of them can be used in combination (for example, a plurality of compounds represented by the general formula (1A) can be used in combination).

[0201] [Chemistry 10]

[0202]

[0203] (Epoxy compound 1A)

[0204] The epoxy compound 1A is a compound represented by the above-mentioned general formula (1A).

[0205] In the general formula (1A), X 11A ~X 13A are independently a hydrogen atom, a halogen atom, a hydrocarbon group or a halogenated hydrocarbon group, X 11A ~X 13A At least one of the groups is a hydrocarbon group or a halogenated hydrocarbon group.

[0206] X 11A ~X 13A The hydrocarbon group is a monovalent hydrocarbon group, and examples thereof include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. An aliphatic hydrocarbon group and an alicyclic hydrocarbon group are preferred, and an aliphatic hydrocarbon group is more preferred.

[0207] As the aliphatic hydrocarbon group, preferably an alkyl group and an alkenyl group are mentioned, and an alkyl group is preferred. The carbon number of the aliphatic hydrocarbon group is preferably 1 or more, more preferably 2 or more, further preferably 4 or more, and further preferably 6 or more in the case of an alkyl group, and the upper limit is preferably 24 or less, more preferably 20 or less, and further preferably 16 or less. In addition, in the case of an alkenyl group, it is 2 or more, preferably 4 or more, and the upper limit is preferably 24 or less, more preferably 20 or less, and further preferably 16 or less.

[0208] X 11A ~X 13A The aliphatic hydrocarbon group may be straight chain or branched, preferably straight chain. In addition, part of the aliphatic hydrocarbon group may be substituted by hydroxyl group or the like. 11A ~X 13A When a plurality of aliphatic hydrocarbon groups are aliphatic hydrocarbon groups, the plurality of aliphatic hydrocarbon groups may be the same as or different from each other.

[0209] As X 11A ~X 13A The alicyclic hydrocarbon group may preferably be a cycloalkyl group or a cycloalkenyl group, preferably a cycloalkyl group. The alicyclic hydrocarbon group has a carbon number of 3 or more, preferably 4 or more, and the upper limit is preferably 12 or less, more preferably 8 or less, and further preferably 6 or less.

[0210] X 11A ~X 13A A part of the alicyclic hydrocarbon group of X may be substituted by a hydroxyl group, the above-mentioned aliphatic hydrocarbon group (e.g., an alkyl group, an alkenyl group), etc. 11A ~X 13A When a plurality of alicyclic hydrocarbon groups are alicyclic hydrocarbon groups, the plurality of alicyclic hydrocarbon groups may be the same as or different from each other.

[0211] As X 11A ~X 13A The aromatic hydrocarbon group may, for example, be phenyl, naphthyl, biphenyl, diphenylmethyl, triphenylmethyl, anthracenyl, perylenyl or pyrenyl.

[0212] X 11A ~X 13A A part of the aromatic hydrocarbon group may be substituted by a hydroxyl group, the above-mentioned aliphatic hydrocarbon group (such as an alkyl group, an alkenyl group), etc. 11A ~X 13A When a plurality of are aromatic hydrocarbon groups, the plurality of aromatic hydrocarbon groups may be the same as or different from each other.

[0213] As X 11A ~X 13A The halogenated hydrocarbon group may be exemplified by the above-mentioned X 11A ~X 13A The hydrocarbon group substituted with a halogen atom is a group in which a part of the hydrocarbon group exemplified as a hydrocarbon group is substituted with a halogen atom. Among the above-mentioned hydrocarbon groups, the hydrocarbon group substituted with a halogen atom is preferably an aliphatic hydrocarbon group or an alicyclic hydrocarbon group, more preferably an aliphatic hydrocarbon group, and still more preferably an alkyl group.

[0214] As X 11A ~X 13A The halogen atom contained in the halogenated hydrocarbon group is preferably fluorine, chlorine, bromine or iodine, more preferably fluorine, chlorine or bromine, and further preferably fluorine.

[0215] The number of halogen atoms in the halogenated hydrocarbon group varies depending on the carbon number of the hydrocarbon group and therefore cannot be generalized, but is preferably 1 or more, more preferably 2 or more, further preferably 3 or more, and further preferably 6 or more, and the upper limit is preferably 16 or less, more preferably 12 or less, and further preferably 9 or less.

[0216] As X 11A ~X 13AThe halogen atom is the same as the halogen atom that may be contained in the above-mentioned halogenated hydrocarbon group, preferably fluorine, chlorine, bromine, and iodine, more preferably fluorine, chlorine, and bromine, and further preferably fluorine.

[0217] X 11A ~X 13A At least one of X is a hydrocarbon group or a halogenated hydrocarbon group, that is, 11A ~X 13A One, two or three of them may be a hydrocarbon group or a halogenated hydrocarbon group. From the viewpoint of improving coating suitability, it is preferred that one of them is a hydrocarbon group or a halogenated hydrocarbon group.

[0218] As the epoxy compound 1A represented by the general formula (1A), among them, X 11A is a hydrocarbon group having 1 to 24 carbon atoms or a halogenated hydrocarbon group having 1 to 24 carbon atoms, X 12A and X 13A The hydrocarbon group is preferably an aliphatic hydrocarbon group, more preferably an alkyl group or an alkenyl group, and further preferably an alkyl group. In addition, the carbon number is also as described above, and in the case of an alkyl group, it is preferably 1 or more, more preferably 2 or more, further preferably 4 or more, and further preferably 6 or more, and the upper limit is preferably 24 or less, more preferably 20 or less, and further preferably 16 or less.

[0219] In addition, the halogenated hydrocarbon group is preferably a halogenated hydrocarbon group having three halogen atoms bonded to a carbon atom at the terminal (the terminal on the opposite side of the carbon atom bonded to the ethylene oxide ring) (a halogenated hydrocarbon group in which all hydrogen atoms bonded to the carbon atom are substituted with halogen atoms). Examples of such a halogenated hydrocarbon group include a group obtained by removing one hydrogen from 2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptane, in which 13 hydrogen atoms of heptane as a basic structure of an aliphatic group are substituted with fluorine atoms (1-2,2,3,3,4,4,5,5,6,6,7,7,7-octafluorohexyl) and the like.

[0220] If X 11A ~X 13A If X is a halogenated hydrocarbon group, the epoxy compound 1A may become a compound that can be called an organic halide, such as the compounds (C) and (F) described later. However, in this specification, a compound having a heterocyclic ring containing a carbon atom and an oxygen atom belongs to the compound (A) and is not treated as an organic halide of the compounds (C) and (F). Therefore, in X 11A ~X 13A In the case of a halogenated hydrocarbon group, compound (A) does not belong to compounds (C) and (F) described later, and these compounds should be excluded. In addition, in epoxy compounds 2A and 3A described later, sometimes a part of them also has a halogen atom (for example, in the case of having a halogenated hydrocarbon group, etc.), and in this case, epoxy compounds 2A and 3A are also the same as epoxy compound 1A.

[0221] (Epoxy Compound 2A)

[0222] The epoxy compound 2A is a compound represented by the above-mentioned general formula (2A).

[0223] In the general formula (2A), X 21A ~X 23A are independently a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group or a group represented by the general formula (2Aa), X 21A ~X 23A At least one of the following is a group represented by the general formula (2Aa). In the general formula (2Aa), R 21A is a divalent hydrocarbon group, R 22A It is a hydrogen atom, a halogen atom, a hydrocarbon group or a halogenated hydrocarbon group.

[0224] As X 21A ~X 23A The hydrocarbon group may be exemplified by the above X 11A ~X 13A The hydrocarbon groups exemplified as the hydrocarbon groups of the present invention are the same as the aliphatic hydrocarbon group, the alicyclic hydrocarbon group, and the aromatic hydrocarbon group, preferably the aliphatic hydrocarbon group and the alicyclic hydrocarbon group, and more preferably the aliphatic hydrocarbon group. Among the aliphatic hydrocarbon groups, the alkyl group and the alkenyl group are more preferred, and the alkyl group is further preferred.

[0225] As X 21A ~X 23A The halogenated hydrocarbon group may be exemplified by the above-mentioned X 11A ~X 13A The halogenated hydrocarbon group may be exemplified as the group in which the halogen atom is also exemplified as the above-mentioned X 11A ~X 13A The hydrocarbon groups are exemplified.

[0226] X 21A ~X 23A At least one of X is a group represented by the general formula (2Aa). 21A ~X 23A One, two or three of them may be a group represented by the general formula (2Aa), and one of them is preferred.

[0227] About X 21A ~X 23A The group represented by the general formula (2Aa) as R 21A The divalent hydrocarbon group may be exemplified by the above X 21A ~X 23A A hydrocarbon group obtained by removing a hydrogen atom from a hydrocarbon group. 21A The divalent hydrocarbon group may be a divalent aliphatic hydrocarbon group, an alicyclic hydrocarbon group or an aromatic hydrocarbon group, preferably an aliphatic hydrocarbon group or an alicyclic hydrocarbon group, more preferably an aliphatic hydrocarbon group.

[0228] As the divalent aliphatic hydrocarbon group, an alkanediyl group and an alkenediyl group are preferred, and an alkanediyl group is more preferred. The carbon number in the case of an alkanediyl group is preferably 1 or more, and the upper limit is preferably 8 or less, more preferably 6 or less, further preferably 4 or less, and further preferably 2 or less. In the case of an alkenediyl group, the carbon number is preferably 2 or more, and the upper limit is the same as that of the alkanediyl group.

[0229] About X 21A ~X 23A The group represented by the general formula (2Aa) as R 22A The monovalent hydrocarbon group may be exemplified by the above X 21A ~X 23A The group is the same as the monovalent hydrocarbon group, that is, a monovalent aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group, and an aliphatic hydrocarbon group or an aromatic hydrocarbon group is preferred.

[0230] As the aliphatic hydrocarbon group, an alkyl group or an alkenyl group is preferred, and an alkyl group is more preferred. The aliphatic hydrocarbon group may be linear or branched. In addition, when the aliphatic hydrocarbon group is an alkyl group, the carbon number is preferably 1 or more, more preferably 2 or more, and further preferably 4 or more, and the upper limit is preferably 24 or less, more preferably 16 or less, further preferably 12 or less, and further preferably 10 or less.

[0231] In addition, as the aromatic hydrocarbon group, phenyl, biphenyl, diphenylmethyl, triphenylmethyl can be preferably exemplified, phenyl, diphenylmethyl, triphenylmethyl is more preferred, and phenyl and triphenylmethyl are further preferred. In addition, these aromatic hydrocarbon groups may be aromatic hydrocarbon groups substituted with a halogen atom, a hydroxyl group, a monovalent aliphatic hydrocarbon group (alkyl, alkenyl), etc.

[0232] As R 22A The halogenated hydrocarbon group may be exemplified by the above R 22A A group obtained by replacing part of a hydrocarbon group with a halogen atom. 22A The halogen atoms contained in the halogenated hydrocarbon group, and R 22A The halogen atom is preferably fluorine, chlorine, bromine or iodine, more preferably fluorine, chlorine or bromine, and further preferably fluorine.

[0233] As the epoxy compound 2A represented by the general formula (2A), preferably, X 21A is a group represented by the general formula (2Aa), X 22A and X 23A is a hydrogen atom, and in the general formula (2Aa), R 21A is a hydrocarbon group having 1 to 8 carbon atoms, R 22A is an epoxy compound of a hydrocarbon group having 1 to 24 carbon atoms, R 21A A divalent hydrocarbon group, R 22A The hydrocarbon group is as described above.

[0234] In addition, in R 22A When the monovalent hydrocarbon group is a phenyl group, it is preferably substituted with a monovalent aliphatic hydrocarbon group, and more preferably substituted with an alkyl group. The carbon number of the alkyl group is preferably 1 or more, more preferably 2 or more, and further preferably 4 or more, and the upper limit is preferably 24 or less, more preferably 12 or less, further preferably 8 or less, and further preferably 6 or less. In this case, the aliphatic hydrocarbon group may be either linear or branched, and is preferably branched. 22A , wherein an aliphatic hydrocarbon group having a quaternary carbon atom is preferred, and a tert-butyl group is particularly preferred.

[0235] (Epoxy Compound 3A)

[0236] The epoxy compound 3A is a compound represented by the above-mentioned general formula (3A).

[0237] In the general formula (3A), X 31A ~X 33A are independently a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group or a group represented by the general formula (3Aa), X 31A ~X 33A At least one of the following is a group represented by the general formula (3Aa). In the general formula (3Aa), R 31A and R 32A are independently a single bond or a divalent hydrocarbon group, X 34A ~X 36A are independently a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, -OR 33A Or a group represented by the general formula (3Ab). 33A ~R 36A are each independently a hydrogen atom, a halogen atom, a hydrocarbon group or a halogenated hydrocarbon group.

[0238] As X 31A ~X 33A The hydrocarbon group may be exemplified by the above X 11A ~X 13A The hydrocarbon groups exemplified as the monovalent aliphatic hydrocarbon group, alicyclic hydrocarbon group, and aromatic hydrocarbon group are the same hydrocarbon groups, preferably aliphatic hydrocarbon groups and alicyclic hydrocarbon groups, and more preferably aliphatic hydrocarbon groups. Among the aliphatic hydrocarbon groups, alkyl groups and alkenyl groups are more preferred, and alkyl groups are further preferred.

[0239] As X 31A ~X 33A The halogenated hydrocarbon group may be exemplified by the above-mentioned X 11A ~X 13A The halogenated hydrocarbon group may be exemplified as the group in which the halogen atom is also exemplified as the above-mentioned X 11A ~X 13A The hydrocarbon groups are exemplified.

[0240] X 31A ~X 33A At least one of X is a group represented by the general formula (3Aa). 31A ~X 33A One, two or three of them may be a group represented by the general formula (3Aa), and one of them is preferred.

[0241] About X 31A ~X 33A The group represented by the general formula (3Aa) as R 31A and R 32A The divalent hydrocarbon group may be exemplified by the above X 31A ~X 33A A hydrocarbon group obtained by removing one hydrogen atom from a monovalent hydrocarbon group. 31A The divalent hydrocarbon group may be a divalent aliphatic hydrocarbon group, an alicyclic hydrocarbon group or an aromatic hydrocarbon group, preferably an aliphatic hydrocarbon group or an alicyclic hydrocarbon group, more preferably an aliphatic hydrocarbon group.

[0242] As the divalent aliphatic hydrocarbon group, an alkanediyl group and an alkenediyl group are preferred, and an alkanediyl group is more preferred. The carbon number in the case of an alkanediyl group is preferably 1 or more, and the upper limit is preferably 8 or less, more preferably 6 or less, further preferably 4 or less, and further preferably 2 or less. In the case of an alkenediyl group, the carbon number is preferably 2 or more, and the upper limit is the same as that of the alkanediyl group.

[0243] As X 34A ~X 36A The hydrocarbon group or halogenated hydrocarbon group may be exemplified by the following as X 31A ~X 33A The same groups as those exemplified for the monovalent hydrocarbon group and the halogenated hydrocarbon group.

[0244] About X 34A ~X 36A Of-OR 33A R 33A , R of the general formula (3Ab) 34A ~R 36A The hydrocarbon group, halogenated hydrocarbon group, and the above X 34A ~X 36A The same group as the hydrocarbon group and the halogenated hydrocarbon group.

[0245] As the epoxy compound 3A represented by the general formula (3A), X 31A is a group represented by the general formula (3Aa), X 32A and X 33A is a hydrogen atom, and in the general formula (3Aa), R 31A is a divalent hydrocarbon group having 1 to 8 carbon atoms, R 32Ais a divalent hydrocarbon group having 1 to 8 carbon atoms, X 34A and X 36A is a group represented by the general formula (3Ab), X 35A is a hydrocarbon group having 1 to 24 carbon atoms. In the general formula (3Ab), R 34A ~R 36A It is a hydrocarbon group having 1 to 24 carbon atoms.

[0246] In this case, R 31A and R 32A The divalent hydrocarbon group is as described above, and R 31A The carbon number of the divalent hydrocarbon group is preferably 1 or more, and the upper limit is preferably 8 or less, more preferably 6 or less, further preferably 4 or less, and further preferably 2 or less. 32A The carbon number of the divalent hydrocarbon group is preferably 1 or more, more preferably 2 or more, and the upper limit is preferably 8 or less, more preferably 6 or less, and further preferably 4 or less. 35A , R 34A ~R 36A The hydrocarbon group is as described above, as X 35A The carbon number of the hydrocarbon group is preferably 1 or more, and the upper limit is preferably 24 or less, more preferably 12 or less, further preferably 8 or less, further preferably 4 or less, and particularly preferably 2 or less. 34A ~R 36A The carbon number of the hydrocarbon group is also related to X 35A The carbon numbers of the hydrocarbon groups are the same.

[0247] In addition, as the epoxy compound 3A represented by the general formula (3A), it is preferred that X 31A is a group represented by the general formula (3Aa), X 22A and X 23A is a hydrogen atom, and in the general formula (3Aa), R 31A is a hydrocarbon group having 1 to 8 carbon atoms, R 32A is a single bond, X 34A ~X 36A It is a hydrocarbon group having 1 to 24 carbon atoms.

[0248] In this case, R 31A The hydrocarbon group is as described above, and as R 31A The carbon number of the hydrocarbon group is preferably 1 or more, and the upper limit is preferably 8 or less, more preferably 6 or less, further preferably 4 or less, and further preferably 2 or less. 34A ~X 36A The hydrocarbon group is as described above, as X 34A , X 36AThe carbon number of the hydrocarbon group is preferably 1 or more, and the upper limit is preferably 24 or less, more preferably 12 or less, further preferably 8 or less, further preferably 4 or less, and particularly preferably 2 or less. 35A The carbon number of the monovalent hydrocarbon group is preferably 1 or more, more preferably 2 or more, and further preferably 4 or more, and the upper limit is preferably 24 or less, more preferably 12 or less, further preferably 8 or less, and further preferably 6 or less. In addition, in this case, X 35A The hydrocarbon group may be linear or branched, and is preferably branched. An aliphatic hydrocarbon group having a quaternary carbon atom is preferred, and a tert-butyl group is particularly preferred.

[0249] The molecular weight of the compound (A) contained in the modified sulfide solid electrolyte of the present embodiment is preferably 60 or more, more preferably 70 or more, and the upper limit is preferably 400 or less, more preferably 380 or less, and further preferably 350 or less. When a compound (A) having such a molecular weight is used, coating suitability can be efficiently improved.

[0250] (Compound (B))

[0251] The compound (B) used in the modified sulfide solid electrolyte of the present embodiment is a compound having two or more heterocyclic rings containing carbon atoms and oxygen atoms, and can also be referred to as a "heteropolycyclic compound" in contrast to the heteromonocyclic compound of the compound (A).

[0252] As the heterocyclic ring containing carbon atoms and oxygen atoms possessed by compound (B), preferably, there can be mentioned the heterocyclic ring possessed by saturated or unsaturated monocyclic oxygen-containing heterocyclic compounds such as ethylene oxide, oxetane, tetrahydrofuran, dihydrofuran, furan, dioxolane, tetrahydropyran, pyran, etc. By having such a heterocyclic ring, the oil absorption is reduced, it is easy to obtain excellent coating adaptability, and excellent battery performance can be obtained more effectively.

[0253] Among the above heterocyclic rings, if the availability is also considered, the heterocyclic ring possessed by ethylene oxide, i.e., the ethylene oxide ring, is preferred. Therefore, as the compound (B) used in the present embodiment, a compound having two or more ethylene oxide rings is preferred, and an epoxy compound represented by the following general formula (1B) having at least two or more groups selected from epoxy groups, glycidyl groups, and glycidyl ether groups (hereinafter, sometimes referred to as "epoxy compound 1B") can be particularly preferably exemplified.

[0254] [Chemistry 11]

[0255]

[0256] In the general formula (1B), X 1Bis a single bond or an aliphatic group, an alicyclic group, an aromatic group, an organic group having a siloxane structure, or an organic group consisting of a combination of these, 1B 、m 1B and n 1B are integers greater than 0 and less than 16, satisfying l 1B +m 1B +n 1B ≥2. In addition, as X 1B When the organic group has the alicyclic group, the epoxy group may be a group condensed with the alicyclic ring in the alicyclic group.

[0257] (single bond)

[0258] In the general formula (1B), X 1B When X is a single bond, the epoxy compound 1B preferably includes butadiene diepoxide formed by two epoxy groups bonding, hexadiene diepoxide formed by two glycidyl groups bonding, and the like. In addition, hexadiene diepoxide formed by two glycidyl groups bonding can be regarded as X in the above general formula (1B). 1B For a single bond, m 1B 2, l 1B and n 1B The epoxy compound in which X is 0 can also be regarded as a compound in which two epoxy groups are bonded to both ends of an ethylene group. 1B For ethylene, l 1B =2, m 1B and n 1B 0 epoxy compound.

[0259] (Aliphatic group)

[0260] Regarding X in the general formula (1B) 1B In the case of an aliphatic group, the number corresponding to the number of groups obtained by removing at least two groups selected from epoxy groups, glycidyl groups and glycidyl ether groups from alkanes, alkenes and alkynes (l 1B +m 1B +n 1B ) as a group having a chemical bond after the hydrogen atoms of an alkane are removed. For example, a group having a chemical bond after two hydrogen atoms are removed from an alkane (a divalent aliphatic group) is an alkanediyl group, and a group having a chemical bond after three hydrogen atoms are removed (a trivalent aliphatic group) is an alkanetriyl group.

[0261] Thus, in this embodiment, the name of the group can be based on X 1B The number of chemical bonds (i.e., selected from the 1B The number corresponding to the number of at least two groups of the bonded epoxy group, glycidyl group and glycidyl ether group (l1B +m 1B +n 1B Therefore, in this specification, the basic structure (for example, the above-mentioned alkane, alkene, and alkyne corresponding thereto) which becomes the basis of an aliphatic group and other groups is described below.

[0262] As the basic structure of the aliphatic group, as described above, preferably, alkanes, alkenes, and alkynes can be exemplified. The oil absorption is reduced, excellent coating adaptability is easily obtained, and excellent battery performance can be obtained more effectively. In addition, considering the ease of acquisition, alkanes and alkenes are more preferred, and alkanes are further preferred.

[0263] The carbon number of these aliphatic groups is preferably 1 or more, more preferably 2 or more, and the upper limit is 24 or less, preferably 16 or less, more preferably 10 or less, further preferably 8 or less, and further preferably 6 or less. When the carbon number of the aliphatic group is within the above range, the oil absorption is reduced, excellent coating suitability is easily obtained, and excellent battery performance can be obtained more effectively.

[0264] In the general formula (1B), the aliphatic group as X 1B In the case of the epoxy compound 1B, a typical preferred example is an ethylene group having two glycidyl ether groups (n 1B 2) ethylene glycol diglycidyl ether, the aliphatic group is a butylene group and has two glycidyl ether groups (n 1B 2) butanediol diglycidyl ether, the aliphatic group is hexamethylene and has two glycidyl ether groups (n 1B 2) hexanediol diglycidyl ether, the aliphatic group is ethylene and has two glycidyl groups (m 1B 2) octadiene diepoxide, etc.

[0265] In the present specification, for example, when described as the above-mentioned "butanediol diglycidyl ether", butane (an alkane having 4 carbon atoms) includes both linear and branched butanes, and includes all butanes in which the position of the carbon atom to which the diglycidyl ether group is attached (the position of the diol) is an adoptable position.

[0266] More specifically, "butanediol diglycidyl ether" includes, in addition to 1,4-butanediol diglycidyl ether in which one glycidyl ether is bonded to each of the carbons at positions 1 and 4 of butanediol, compounds in which a glycidyl ether group is bonded to other carbons, such as 1,2-butanediol diglycidyl ether in which one glycidyl ether is bonded to each of the carbons at positions 1 and 2 of butanediol, and 1,3-butanediol diglycidyl ether in which one glycidyl ether is bonded to each of the carbons at positions 1 and 3 of butanediol. In addition, it also includes 2-methyl-1,3-propanediol diglycidyl ether in which the butane of 1,3-butanediol is branched into 2-methylpropane, and 2-methyl-1,3-propanediol diglycidyl ether in which one glycidyl ether is bonded to each of the carbons at positions 1 and 3 of 2-methyl-1,3-propanediol.

[0267] These aliphatic groups may be linear or branched.

[0268] In addition, at least a part of the hydrogen atoms may be substituted by a halogen atom, a hydroxyl group, an amino group, or the like. In this case, a fluorine atom is preferably used as the halogen atom. In the case of an aliphatic group having at least a part of the hydrogen atoms substituted by a halogen atom, similarly to the above-mentioned epoxy compounds 1A to 3A, epoxy compound 1B may sometimes become a compound that can be called an organic halide such as compounds (C) and (F) described later, but a compound having two or more heterocyclic rings containing carbon atoms and oxygen atoms is regarded as a compound belonging to compound (B) and is not treated as an organic halide of compounds (C) and (F). In addition, the case where epoxy compound 1B has a group other than an aliphatic group substituted by a halogen atom is also the same as the case where it has an aliphatic group substituted by a halogen atom.

[0269] In the general formula (1B), X is a branched aliphatic group. 1B In the case of the epoxy compound 1B, a typical preferred example is a compound in which the aliphatic group is a neopentylene group and has two glycidyl ether groups (n 1B The aliphatic group is a group obtained by removing three hydrogen atoms from 2,2-dimethylbutane, which is a branched alkane as a basic structure, and has three glycidyl ether groups (n 1B 3) trimethylolpropane triglycidyl ether, the aliphatic group is a group obtained by removing four hydrogen atoms from pentaerythritol as a basic structure and has four glycidyl groups (m 1B Pentaerythritol trimethylolpropane triglycidyl ether (also referred to as aliphatic group) is a group obtained by removing four hydrogen atoms from 2,2-dimethylbutane as a basic structure and has four glycidyl ether groups (n 1B 4) compound) etc.

[0270] In the general formula (1B), X is an aliphatic group in which at least a part of hydrogen atoms is substituted. 1B In the case of the epoxy compound 1B, the aliphatic group is preferably a group obtained by removing two hydrogen atoms from 2,2,3,3,4,4,5,5-octafluorohexane (2,2,3,3,4,4,5,5-octafluorohexane-1,6-diyl) obtained by replacing eight hydrogen atoms of hexane as a basic structure with fluorine atoms, and having two epoxy groups (1 1B 2,2'-(2,2,3,3,4,4,5,5-octafluorohexane-1,6-diyl)dioxirane of 2).

[0271] The above-mentioned 2,2'-(2,2,3,3,4,4,5,5-octafluorohexane-1,6-diyl)dioxirane is a compound used in the examples, and therefore the position substituted by the fluorine atom is clearly described. However, in this specification, regarding the compound whose position is clearly described, when described in the examples, it refers to itself, but other than the cases described in the examples, as in the case where the compound is described without specifying the above-mentioned position, as hexane (alkane having 6 carbon atoms), it includes any of linear and branched forms, and includes all hexanes in which the position of the carbon atom substituted by fluorine and the position of the carbon atom to which the oxirane ring (epoxy group) is a position that can be adopted.

[0272] (Alicyclic Group)

[0273] Regarding X in the general formula (1B) 1B As the basic structure of the alicyclic group, cycloalkanes and cycloolefins can be preferably exemplified. The oil absorption is reduced, excellent coating adaptability is easily obtained, and excellent battery performance can be obtained more effectively. In addition, considering the ease of acquisition, cycloalkanes are more preferred.

[0274] As the basic structure of the alicyclic group, a basic structure containing multiple alicyclic rings can also be exemplified, for example, a bonded multi-alicyclic structure such as a bicyclohexyl group; a structure obtained by condensing two or more alicyclic rings such as hexahydronaphthalene, octahydronaphthalene, decahydronaphthalene; a cross-linked ring structure such as norbornane, norbornene, adamantane, tricyclodecane, and pinene. In addition to these, as a basic structure having a double bond in an alicyclic ring, basic structures such as pentalylene and azulene can also be exemplified.

[0275] Furthermore, a structure in which any of the above-mentioned single alicyclic basic structure, multiple alicyclic basic structures, and aromatic ring basic structures described later are bonded or condensed can also be exemplified as a basic structure that can be preferably exemplified.

[0276] The basic structure of the alicyclic group may be a structure having a heterocyclic ring in which carbon atoms in the basic structures exemplified above are substituted with hetero atoms such as nitrogen atoms, oxygen atoms, sulfur atoms, and phosphorus atoms.

[0277] In addition, it can also be a structure in which at least a part of the hydrogen atoms is replaced by a halogen atom such as a fluorine atom, a hydroxyl group, an amino group, or the above-mentioned aliphatic group in the basic structure exemplified above. In addition, it can also be a structure replaced by a silicon atom or a group comprising a silicon atom and an aliphatic group. In this case, as the aliphatic group, an alkyl group or an alkenyl group is preferred, and as the carbon number, it is preferably more than 1, and as the upper limit, it is preferably less than 12, more preferably less than 8, further preferably less than 6, and further preferably less than 4.

[0278] The carbon number of the alicyclic group is 3 or more, preferably 4 or more, more preferably 6 or more, and the upper limit is preferably 24 or less, more preferably 20 or less, further preferably 16 or less, and further preferably 12 or less.

[0279] In X 1B In the case of an alicyclic group, an epoxy group (ethylene oxide ring) may be present in a condensed state with an alicyclic ring in the alicyclic group.

[0280] As the basic structure of such an alicyclic group that can be fused with an epoxy group (ethylene oxide ring), cyclopentane, cyclohexane, cyclooctane, etc. can be representatively and preferably exemplified. From the viewpoint of easy availability, cyclohexane is preferred. For example, when the basic structure of the alicyclic group is cyclohexane, if it is fused with an epoxy group, cyclohexyl oxide is formed, and thus as a multifunctional epoxy compound, it becomes a compound having cyclohexyl oxide in a part thereof. As such a multifunctional epoxy compound, for example, 1,3-bis[2-(7-oxabicyclo[4.1.0]heptane-3-yl)ethyl]-1,1,3,3-tetramethyldisiloxane (in the above general formula (1), X 1D The basic structure is 1,3-ethylcyclohexyl-1,1,3,3-tetramethyldisiloxane (a compound obtained by replacing the hydrogen atom connected to the silicon atom in tetramethyldisiloxane with a propyl group). 1B =2, m 1B and n 1B is 0, the epoxy group is condensed with cyclohexane and exists in the form of cyclohexene oxide).

[0281] (Aromatic Group)

[0282] Regarding X in the general formula (1B) 1BAs the basic structure of the aromatic group, preferably exemplified are: monocyclic aromatic compounds such as benzene, toluene, and styrene; polycyclic aromatic compounds such as biphenyl, diphenylmethane (benzylbenzene), diphenylethane (bibenzyl), methylenetriphenol, and triphenylcyclohexane formed by bonding multiple aromatic rings; naphthalene, phenanthrene, anthracene, pyrene, triphenylene, tetracene, pentacene, etc., obtained by condensing multiple aromatic rings, or polycyclic aromatic compounds such as indene, indacene, acenaphthene, dihydronaphthalene, tetrahydronaphthalene, biphenylene, fluorene, and fluoranthene, obtained by condensing aromatic rings with alicyclic rings; etc.

[0283] Furthermore, structures obtained by bonding or condensing any of these aromatic ring basic structures, the above-mentioned single alicyclic basic structures, and multiple alicyclic basic structures, such as diphenylfluorene (9,9-diphenyl-9H-fluorene) in which two benzenes are single-bonded at the 9-position of fluorene, can also be representatively and preferably exemplified as basic structures.

[0284] In the general formula (1B), an aromatic group as X 1B In the case of the epoxy compound 1B, a typical preferred example is a phenylene group having two glycidyl ether groups (n 1B 2) diglycidylresorcinol ether (compound having 1,3-phenylene group) and 1,4-diglycidyloxybenzene (compound having 1,4-phenylene group), the aromatic group is a group obtained by removing three hydrogen atoms from methylenetrisphenol, a bonded polycyclic aromatic compound as a basic structure, and has three glycidyl groups (m 1B 3). Tris(4-hydroxyphenyl)methane triglycidyl ether.

[0285] In addition, the aromatic group is preferably a group obtained by removing two hydrogen atoms from 9,9-bis(4-hydroxyphenyl)fluorene, which is a condensed polycyclic aromatic compound as a basic structure, and has two glycidyl groups (m 1B 2) is 9,9-bis(4-glycidyloxyphenyl)fluorene.

[0286] As a preferred example of the basic structure of the aromatic group, a bisphenol compound can also be mentioned. As the main bisphenol compound, preferably, bisphenol compounds such as bisphenol A (2,2-bis(4-hydroxyphenyl)propane), bisphenol AP (1,1-bis(4-hydroxyphenyl)-1-phenylethane), bisphenol B (2,2-bis(4-hydroxyphenyl)butane), bisphenol BP (bis(4-hydroxyphenyl)diphenylmethane), bisphenol M (1,3-bis(2-(4-hydroxyphenyl)-2-propyl)benzene), bisphenol PH (5,5'-(1-methylethylidene)-bis[1,1'-(bisphenyl)-2-ol]propane), bisphenol Z (1,1-bis(4-hydroxyphenyl)cyclohexane), and compounds containing these bisphenol compounds can be mentioned.

[0287] Examples of the bisphenol compound that are preferred in addition to the above compounds include compounds such as bisphenol AF (2,2-bis(4-hydroxyphenyl)hexafluoropropane) in which a part of the bisphenol is substituted with a halogen atom such as a fluorine atom, and bisphenol S (bis(4-hydroxyphenyl)sulfone) containing an oxygen atom and a sulfur atom in the molecule.

[0288] In the general formula (1B), an aromatic group as X 1B In the case of epoxy compounds 1B having a bisphenol compound as the basic structure of the aromatic group, the aromatic group is preferably a group obtained by removing a hydrogen atom from a hydroxyl group of bisphenol A as the basic structure and having two glycidyl groups (m 1B 2) bisphenol A diglycidyl ether, the aromatic group is a group obtained by removing a hydrogen atom from a propyl group of 2,2-bis((4-propoxyphenyl)propane) obtained by replacing a hydrogen atom of a hydroxyl group of bisphenol A as a basic structure with a propyl group, and having two glycidyl ether groups (n 1B 2) Bisphenol A propoxylated diglycidyl ether, etc.

[0289] As X in the general formula (1B) 1B The basic structure of the aromatic group may be a structure having a heterocyclic ring in which a carbon atom in the basic structure exemplified above is replaced by a heteroatom such as a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom. In the case of having a heterocyclic ring substituted by a phosphorus atom, compound (B) (epoxy compound 1B) does not belong to compound (H) described later, and compound (H) should be excluded.

[0290] It can also be a structure in which at least a part of the hydrogen atoms in the above-exemplified basic structure is replaced by a halogen atom such as a fluorine atom, a hydroxyl group, an amino group, or the above-mentioned aliphatic group. In this case, the aliphatic group is preferably an alkyl group or an alkenyl group, and the carbon number is preferably 1 or more, and the upper limit is preferably 12 or less, more preferably 8 or less, further preferably 6 or less, and further preferably 4 or less.

[0291] In the basic structure of the aromatic group, amino and hydroxyl groups are preferred among these substituents. When the aromatic group is substituted with an amino group, aniline, dimethylaniline, etc. can be preferably exemplified, and when the aromatic group is substituted with a hydroxyl group, phenol, diphenol, etc. can be preferably exemplified. In addition, hydroxyaniline (aminophenol) substituted with an amino group and a hydroxyl group can also be preferably exemplified.

[0292] In the general formula (1B), an aromatic group as X 1BIn the case of epoxy compounds 1B having an aromatic group as a basic structure substituted with an amino group, a hydroxyl group, etc., a typical example of an epoxy compound 1B having an aromatic group as a basic structure substituted with an amino group, a hydroxyl group, etc. is preferably a group obtained by removing hydrogen atoms from the amino group and the hydroxyl group of hydroxyaniline (a compound in which two hydrogen atoms of benzene are substituted with an amino group and a hydroxyl group) as a basic structure and having two glycidyl groups (m 1B The aromatic group is a group obtained by removing a hydrogen atom from an amino group of 4,4'-methylenebis(N,N-dimethylaniline) (a compound obtained by replacing two hydrogen atoms of diphenylmethane with amino groups) as a basic structure and has four glycidyl groups (m 1B 4), 4'-methylenebis(N,N-diglycidylaniline) and the like.

[0293] Furthermore, if the diglycidylresorcinol ether and 1,4-diglycidyloxybenzene cited as the above specific examples are regarded as aromatic groups obtained by removing hydrogen atoms from the hydroxyl groups of a compound (dihydroquinone) in which two hydrogen atoms of benzene as a basic structure are replaced by hydroxyl groups, and the aromatic group has two glycidyl groups (m 1B 2), it can also be considered that in the general formula (1), the compound having an aromatic group as X 1B In the epoxy compound 1B, the basic structure of the aromatic group is substituted by an amino group, a hydroxyl group, or the like.

[0294] The number of carbon atoms in the aromatic group is 6 or more, preferably 8 or more, more preferably 10 or more, and the upper limit is preferably 36 or less, more preferably 32 or less, and further preferably 28 or less.

[0295] (Organic group having a siloxane structure)

[0296] Regarding X in the general formula (1B) 1B As the basic structure of the organic group having a siloxane structure, any one having at least a -Si-O- bond can be used without particular limitation, and preferably includes: alkoxysilanes having one silicon atom, such as dimethylmethoxysilane, dimethoxymethylsilane, trimethoxysilane, trimethoxymethylsilane, and tetramethoxysilane; disiloxane compounds having two silicon atoms, such as tetramethyldisiloxane, hexamethyldisiloxane, and divinyltetramethyldisiloxane; and the like chain siloxane compounds.

[0297] Furthermore, cyclic siloxane compounds such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane, and cage-type siloxane compounds such as silsesquioxane are also preferably mentioned.

[0298] Regarding the above-mentioned chain siloxane compounds and cyclic siloxane compounds, the compounds in which the groups bonded to the silicon atom and the alkyl groups in the alkoxy groups are methyl groups are exemplified, and of course, compounds bonded to groups other than methyl groups, i.e., ethyl groups, propyl groups, etc., the above-mentioned aliphatic groups, alicyclic groups, and aromatic groups can also be included. In this case, the aliphatic group is preferably an alkyl group or an alkenyl group, and the carbon number is preferably 1 or more, and the upper limit is preferably 12 or less, more preferably 8 or less, further preferably 6 or less, and further preferably 4 or less.

[0299] Regarding the above-mentioned chain siloxane compound, as a compound containing a group other than a methyl group, from the perspective of easy availability, for example, the following compounds can be preferably cited as chain siloxane compounds forming a basic structure: a polyfunctional epoxy compound having a basic structure such as siloxane compounds such as 1,3-dipropyl-1,1,3,3-tetramethyldisiloxane in which one methyl group bonded to two silicon atoms is respectively a propyl group, or 1,3-dicyclohexylethyl-1,1,3,3-tetramethyldipropyldisiloxane in which one methyl group bonded to two silicon atoms is respectively a cyclohexylethyl group in hexamethyldisiloxane.

[0300] In the general formula (1B), an organic group having a siloxane structure is provided as X 1B In the case of epoxy compound 1B, the organic group having a siloxane structure is preferably a group obtained by removing two hydrogen atoms from the propyl group of 1,3-dipropyl-1,1,3,3-tetramethyldisiloxane as a basic structure and having two glycidyl ether groups (n 1B 1,3-bis(3-glycidyloxypropyl)tetramethyldisiloxane of 3).

[0301] In addition, 1,3-bis[2-(7-oxabicyclo[4.1.0]heptane-3-yl)ethyl]-1,1,3,3-tetramethyldisiloxane described as a compound having cyclohexene oxide in which an alicyclic group and an epoxy group are condensed can also be preferably exemplified as a representative example of an organic group having a siloxane structure as X of the general formula (1B): 1B Epoxide 1B.

[0302] In addition, regarding the above-mentioned cyclic siloxane compounds, from the perspective of easy availability, the following compounds can be preferably cited as cyclic siloxane compounds having a basic structure: epoxy compound 1B having a basic structure of 2,4,6,8-tetramethyl-2,4,6,8-tetrapropylcyclotetrasiloxane in which one methyl group bonded to four silicon atoms in octamethylcyclotetrasiloxane is respectively converted into a propyl group.

[0303] In the general formula (1B), an organic group as X 1BIn the case where the organic group has a siloxane structure whose basic structure is a cyclic siloxane compound, the organic group having a siloxane structure is preferably a group obtained by removing four hydrogen atoms from the propyl group of 2,4,6,8-tetramethyl-2,4,6,8-tetrapropylcyclotetrasiloxane as a basic structure and having four glycidyl ether groups (n 1B 4) is 1,3-bis(3-glycidyloxypropyl)tetramethyldisiloxane.

[0304] In the general formula (1B), an organic group as X 1B In the case where the organic group has a siloxane structure whose basic structure is a cage-type siloxane compound, the organic group having a siloxane structure is preferably a group obtained by removing one hydrogen atom from each of eight propyl groups in a compound having eight silicon atoms of a silsesquioxane (PSS-octamethyl substituted body) as a basic structure and to which one (a total of eight) propyldimethylsiloxy groups are bonded (also referred to as a "PSS-octa[propyldimethylsiloxy] substituted" compound), and having eight glycidyl ether groups (n 1B The present invention is substituted with PSS-octa[(3-glycidyloxypropyl)dimethylsilyloxy] of 8).

[0305] The number of silicon atoms in the basic structure having a siloxane structure is preferably 1 or more, more preferably 2 or more, and the upper limit is preferably 12 or less, more preferably 8 or less, further preferably 6 or less, and further preferably 4 or less.

[0306] (Bonded Group)

[0307] In epoxy compound 1B, X 1B The group consisting of the combination of these may be a group formed by at least two groups selected from the above-mentioned aliphatic group, the above-mentioned alicyclic group, the above-mentioned aromatic group and the above-mentioned organic group having a siloxane structure bonded via a single bond or a bonding group selected from -O-, -SO2-, -CO-, -C(=O)O-, -N- and -S-. In addition, in this specification, X 1B Since the aliphatic group, alicyclic group, aromatic group and organic group having a siloxane structure are described as being replaced by a basic structure containing these groups, it can be considered that the above basic structure is bonded via a single bond, a bonding group such as -O-.

[0308] In X 1BIn the case of a group formed by single-bonding at least two groups selected from an aliphatic group, an alicyclic group, an aromatic group, and an organic group having a siloxane structure, the following cases are preferably exemplified: a case where one of the above-mentioned groups is substituted by another group, or a case where two benzenes as other basic structures are single-bonded to the 9-position of a basic structure of fluorene such as the above-mentioned diphenylfluorene (9,9-diphenyl-9H-fluorene), etc.

[0309] In addition, as X 1B In the case of a group formed by a single bond, preferably exemplified are: as a basic structure containing aniline, 4,4-methylenedianiline (p-toluidine) formed by a single bond between aniline and 4-methylaniline, 4,4'-methylenebis(N,N-dimethylaniline) formed by a single bond between dimethylaniline and 4,N,N-trimethylaniline, and the like.

[0310] As X 1B In the case of having -O- as a bonding group, for example, when a plurality of aliphatic groups are bonded via -O-, more specifically, for example, representative preferred examples include oxyethylene, oxypropylene, etc. 1B O-(R 1B The basic structure of the repeating unit is a divalent aliphatic group, preferably an alkanediyl group.

[0311] In the basic structure with -R 1B In the case of O-, -R 1B O- may have 1 or more than 2. When having more than 2, the average repetition number (n) is preferably more than 2, more preferably more than 4, and further preferably more than 5, and the upper limit is preferably less than 200, more preferably less than 180, and further preferably less than 170.

[0312] In this case, the number average molecular weight of the epoxy compound 1B can be determined by making -R 1B R in O 1B It varies depending on the reason and cannot be generalized, but it is preferably 200 or more, more preferably 300 or more, and further preferably 350 or more. The upper limit is preferably 10000 or less, more preferably 8000 or less, further preferably 7000 or less, and further preferably 6500 or less.

[0313] As X 1B In the case of a polyfunctional epoxy compound having -O- as a bonding group, representative examples thereof include: 1B O- is oxypropylene (R 1B is propylene) and has 1 glycidyl group and glycidyl ether group (m 1B is 1, n1B 1) polypropylene glycol diglycidyl ether, as -R 1B O- is oxyethylene (R 1B is ethylene) and has 1 glycidyl group and glycidyl ether group (m 1B is 1, n 1B 1) polyethylene glycol diglycidyl ether, etc. The average repeating number (n) of these polyethylene glycol diglycidyl ether and polypropylene glycol diglycidyl ether can be appropriately selected from the above range.

[0314] As X 1B As the basic structure having -O- as a bonding group, compounds in which an aliphatic group such as diethylene glycol and diglycerol is bonded via -O- are also preferably mentioned.

[0315] In addition, as X 1B The basic structure having -O- as a bonding group preferably includes compounds in which alicyclic rings such as dicyclohexyl ether are bonded via -O-; compounds in which aromatic rings such as dihydroxydiphenyl ether and phenylbiphenyl ether are bonded via -O-; and the like.

[0316] As X 1B In the case of the epoxy compound 1B having -O- as a bonding group, representative examples of preferred examples include X having -O- as a bonding group. 1B The group is -CH2CH2-O-CH2CH2- (a group in which the basic structure is diethylene glycol and two hydrogen atoms are removed) formed by two ethylene groups bonded via -O-, and has two glycidyl groups (n 1B 2) diethylene glycol diglycidyl ether, etc.

[0317] As X 1B In the case of having -C(=O)O- as a bonding group, for example, preferably, a compound in which two alicyclic rings are bonded via -C(=O)O-, such as cyclohexylmethyl cyclohexanecarboxylate, etc., can be mentioned.

[0318] (About l 1B 、m 1B and n 1B )

[0319] l 1B 、m 1B and n 1B are integers greater than 0 and less than 16, satisfying l 1B +m 1B +n 1B ≥2.

[0320] As long as l 1B 、m 1B and n 1B Total (l1B +m 1B +n 1B ) is not particularly limited when it is 2 or more, but when it is 1 or more, it is preferably 2 or more, and the upper limit is preferably 10 or less, more preferably 8 or less, and further preferably 4 or less.

[0321] In addition, as l 1B +m 1B +n 1B There is no particular limitation as long as it is 2 or more, but it is preferably 2 or more, and the upper limit is preferably 10 or less, more preferably 8 or less, and further preferably 4 or less.

[0322] If l 1B 、m 1B and n 1B If the above range is satisfied, the oil absorption is reduced, excellent coating adaptability is easily obtained, and excellent battery performance can be obtained more effectively. In addition, considering the ease of obtaining, it is preferred that 1B 、m 1B and n 1B Any one of them is 2 or more, and the other two are 0. That is, from the viewpoint of easy availability, the epoxy compound 1B used in the present embodiment preferably has two or more of any one of epoxy groups, glycidyl groups, and glycidyl ether groups.

[0323] In addition, considering the ease of acquisition, it is also preferred to 1B 、m 1B and n 1B In this case, from the same viewpoint, the epoxy compound 1B having one glycidyl ether group and one or more glycidyl groups is preferred, and the epoxy compound 1B having one glycidyl ether group and two glycidyl groups is more preferred.

[0324] (Other heteropolycyclic compounds)

[0325] As the heteropolycyclic compound having two or more heterocyclic rings containing carbon atoms and oxygen atoms as the compound (B), compounds other than the compound having two or more oxirane rings as heterocyclic rings such as the above-mentioned epoxy compound 1B may be mentioned compounds having a heterocyclic ring other than an oxirane ring among heterocyclic rings consisting of three atoms, and compounds having a heterocyclic ring consisting of four or more atoms. As such heteropolycyclic compounds other than the epoxy compound 1B, compounds represented by the following general formula (2B) may be preferably mentioned.

[0326] [Chemistry 12]

[0327]

[0328] In the general formula (2B), X 2B is a single bond or an aliphatic group, an alicyclic group, an aromatic group, an organic group having a siloxane structure, or an organic group consisting of a combination of these, R 2Ba , R 2Bb and R 2Bc Each independently represents an aliphatic group having 1 or more carbon atoms. 2Ba , R 2Bb and R 2Bc The heterocyclic ring may contain a bonding group selected from -O-, -SO2-, -CO-, -C(=O)O-, -N- and -S-.

[0329] l 2B 、m 2B and n 2B are integers greater than 0 and less than 16, satisfying l 2B +m 2B +n 2B ≥2. In addition, as X 2B When the organic group has the alicyclic group, the heterocyclic group may be a group condensed with the alicyclic ring in the alicyclic group.

[0330] In the above general formula (2B), X 2B A single bond or an aliphatic group, an alicyclic group, an aromatic group, an organic group having a siloxane structure, or an organic group composed of a combination of these and X as the above general formula (1B) 1B The groups described above are the same as those consisting of a single bond, an aliphatic group, an alicyclic group, an aromatic group, an organic group having a siloxane structure, or an organic group consisting of a combination of these.

[0331] In addition, regarding l 2B 、m 2B and n 2B , and the above general formula (1) are respectively as l 1B 、m 1B and n 1B The description is the same.

[0332] In the above general formula (2B), R 2Ba , R 2Bb and R 2Bc The aliphatic group forms an alicyclic structure together with the oxygen atom. 2Ba , R 2Bb and R 2Bc The aliphatic group may be exemplified by the following: 1BThe same group as the group described in the aliphatic group of . For example, divalent aliphatic groups such as alkanediyl, alkenediyl, and alkynyl can be mentioned. In the present embodiment, any of these can be used. Considering the ease of acquisition, alkanediyl and alkenediyl are preferred, and alkanediyl is more preferred.

[0333] In addition, from the same point of view, as R 2Ba , R 2Bb and R 2Bc The carbon number of the aliphatic group is preferably 2 or more, more preferably 3 or more, and the upper limit is preferably 12 or less, more preferably 8 or less, and further preferably 6 or less.

[0334] The compound (B) represented by the general formula (2B) is a heteropolycyclic compound other than the compound having two or more oxirane rings as the heterocyclic ring, such as the above-mentioned epoxy compound 1B. 2Ba , R 2Bb and R 2Bc is an aliphatic group having 2 carbon atoms and 2B 、m 2B and n 2B When each of R is 1, the aliphatic group having 2 carbon atoms is a group other than an alkanediyl group, that is, an alkenediyl group or an alkynyldiyl group. 2Ba , R 2Bb and R 2Bc is an aliphatic group having 2 carbon atoms and 2B 、m 2B and n 2B 1 respectively, and when the heterocyclic ring contains a bonding group described later, the aliphatic group having 2 carbon atoms may also be an alkanediyl group (i.e., ethylene). For example, when the aliphatic group having 2 carbon atoms may be an alkanediyl group (i.e., ethylene), R 2Ba , R 2Bb and R 2Bc An oxathietane ring which is an ethylene group and has -S- as a bonding group.

[0335] R as a heterocyclic ring 2Ba In the case of an alkanediyl group, the heteropolycyclic compound may be preferably represented by X 2B A group obtained by removing two hydrogen atoms from butanediol as a basic structure and having two tetrahydrofuran rings (R 2Ba for butylene)(l 2B 2) bis(tetrahydrofuranyloxy)butane (particularly 1,4-bis(2-tetrahydrofuranyloxy)butane) and the like.

[0336] Contains R 2Ba , R 2Bb and R 2BcThe heterocyclic ring may contain a bonding group selected from -O-, -SO2-, -CO-, -C(=O)O-, -N- and -S-.

[0337] For example, when the heterocyclic ring is a dioxirane ring, R 2Ba , R 2Bb and R 2Bc The aliphatic group is a methylene group having 1 carbon number, and the methylene group is connected to the oxygen atom possessed by the heterocyclic ring through -O-. In addition, for example, when the heterocyclic ring is 1,3-dioxolane, R 2Ba , R 2Bb and R 2Bc The aliphatic group is methylene and ethylene, and these groups are connected to the oxygen atom possessed by the heterocyclic ring through -O-. In addition, for example, when the heterocyclic ring is an oxazolidine ring, R 2Ba , R 2Bb and R 2Bc The aliphatic group is methylene and ethylene, and these groups are connected to the oxygen atom possessed by the heterocyclic ring through -N-. Although several examples are given for explaining the heterocyclic ring containing a bonding group, the present embodiment is not limited to these examples.

[0338] When the heterocyclic ring has a bonding group, the number of carbon atoms in R 2Ba , R 2Bb and R 2Bc The carbon number of the aliphatic group may be within the range.

[0339] The aliphatic group may be a group in which at least a part of hydrogen atoms are replaced by a halogen atom, a hydroxyl group, an amino group, or the like, or a group in which at least a part of hydrogen atoms are replaced by a monovalent aliphatic group. When the heteropolycyclic compound represented by the general formula (2B) has an aliphatic group in which at least a part of hydrogen atoms are replaced by a halogen atom, it may sometimes become a compound that can be called an organic halide like the above-mentioned epoxy compounds 1A to 3A, but the compound having two or more heterocyclic rings containing carbon atoms and oxygen atoms is regarded as a compound belonging to the compound (B) and is not treated as an organic halide of the compounds (C) and (F).

[0340] The heterocyclic ring in the general formula (2B) may be a heterocyclic ring obtained by bonding or condensing an alicyclic ring and an aromatic ring. Here, the heterocyclic ring obtained by bonding is a heterocyclic ring obtained by bonding another alicyclic ring or an aromatic ring to at least one carbon atom of the heterocyclic ring in the general formula (2B), and the heterocyclic ring obtained by condensing is a heterocyclic ring obtained by condensing another alicyclic ring or an aromatic ring to at least one carbon atom of the heterocyclic ring in the general formula (2B). Among the heterocyclic rings in the general formula (2B), the heterocyclic ring obtained by bonding or condensing may be X in the general formula (1B). 1BThe heterocyclic ring is a ring obtained by bonding or condensing any one of the alicyclic group in the above description, the condensed ring in the aromatic group, that is, the basic structure of the single alicyclic ring, the basic structure of multiple alicyclic rings, and the basic structure of the aromatic ring described above.

[0341] In the case where the heterocyclic ring is a heterocyclic ring obtained by bonding or condensing an alicyclic ring and an aromatic ring, the number of carbon atoms in the heterocyclic ring or the aromatic ring is such that the number of carbon atoms in R 2Ba , R 2Bb and R 2Bc The carbon number of the aliphatic group may be within the range.

[0342] In the modified sulfide solid electrolyte of the present embodiment, as the compound (B), the compounds described as the compound (B) above, for example, the compounds represented by the general formulae (1B) and (2B) can be used alone or in combination of two or more.

[0343] (Compound (C))

[0344] The compound (C) used in the modified sulfide solid electrolyte of the present embodiment is the organic halide 1 (excluding the compound (F) described below), and any organic compound other than the compound (F) described below can be used without particular limitation as long as it partially has a halogen atom.

[0345] As compound (C), preferably, there can be mentioned: 1C (X 1C represents a halogen atom); a compound having a haloformyl group (CX 1C (=O)-(X 1C represents a halogen atom)) compound; having a halogenated silyl group (-SiX 1c n 1C (X 1C Represents a halogen atom, n 1C represents an integer of 1 to 3). These halogen atom-containing groups are all groups present at the end of the organic halide 1. Compound (C) becomes easy to adhere to the sulfide solid electrolyte by having a halogen atom-containing group at its end, so the oil absorption is reduced, it is easy to obtain excellent coating adaptability, and excellent battery performance can be obtained more effectively. In addition, as described above, these organic halide 1s having halogen atom-containing groups are different from compound (F) (organic halide 2), and compound (C) is a compound other than compound (F).

[0346] As the compound (C), more specifically, preferably, there can be mentioned an organic halide 1a represented by the following general formula (1C), an organic halide 1b represented by the following general formula (2C), an organic halide 1c represented by the following general formula (3C), and an organic halide 1d represented by the following general formula (4C). In the modified sulfide solid electrolyte of the present embodiment, as the compound (C), the above-mentioned compounds having a halogen atom-containing group or the compounds represented by these general formulas can be used alone, or a plurality of them can be used in combination (for example, a plurality of the above-mentioned compounds having a haloformyl group can be used in combination, and for example, a plurality of compounds represented by the following general formula (1C) can also be used in combination).

[0347] [Chemistry 13]

[0348]

[0349] (Organic halide 1a)

[0350] The organic halide 1a is a compound represented by the above-mentioned general formula (1C).

[0351] In the general formula (1C), X 11C is a halogen atom, X 12C ~X 14C are independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group or an aromatic hydrocarbon group, and the hydrogen atom of the aliphatic hydrocarbon group, the alicyclic hydrocarbon group or the aromatic hydrocarbon group may be substituted by a halogen atom. 11C The halogen atom is an atom selected from chlorine, bromine and iodine atoms, and X 12C ~X 14C The halogen atom is an atom selected from fluorine, chlorine, bromine and iodine.

[0352] X 11C The halogen atom of X is an atom selected from a chlorine atom, a bromine atom and an iodine atom as described above, preferably a bromine atom or an iodine atom, and more preferably a bromine atom. 12C ~X 14C The halogen atom in X is an atom selected from fluorine, chlorine, bromine and iodine as described above, and more preferably a chlorine, bromine or iodine atom. 11C ~X 14C When a plurality of halogen atoms are halogen atoms, the plurality of halogen atoms may be the same as or different from each other.

[0353] When the organic halide 1a is used, it is considered that the adhesion to the sulfide solid electrolyte is mainly caused by the X 11C , and in X 12C ~X 14CWhen it is a halogen atom or a group containing a halogen atom, it is considered that it may be caused by X 12C ~X 14C However, it is known that other halogen atoms tend to adhere to sulfide solid electrolytes more easily than fluorine atoms. 12C ~X 14C In the case of having halogen atoms other than fluorine, it can be said that the adhesion to the sulfide solid electrolyte is caused by X 11C This tendency also applies to the organic halides 1b to 1d represented by the general formulae (2C) to (4C) described later.

[0354] As X 12C ~X 14C The aliphatic hydrocarbon group may be exemplified by the following: 1B The same groups as those described for the aliphatic group are preferably alkyl and alkenyl, and alkyl is preferred.

[0355] The carbon number of the aliphatic hydrocarbon group is preferably 1 or more in the case of an alkyl group, and the upper limit is preferably 24 or less, more preferably 16 or less, and further preferably 12 or less. In the case of an alkenyl group, the carbon number is 2 or more, preferably 3 or more, and the upper limit is preferably 24 or less, more preferably 16 or less, and further preferably 12 or less.

[0356] X 12C ~X 14C The aliphatic hydrocarbon group may be straight chain or branched, and its hydrogen atoms may be substituted by halogen atoms or hydroxyl groups. In the case of being substituted by halogen atoms, as specified in X 12C ~X 14C The halogen atom in X is an atom selected from fluorine atom, chlorine atom, bromine atom and iodine atom. Examples of the halogen atom include the same as those in X 12C ~X 14C The halogen atoms of X 12C ~X 14C When a plurality of aliphatic hydrocarbon groups are aliphatic hydrocarbon groups, the plurality of aliphatic hydrocarbon groups may be the same as or different from each other.

[0357] As X 12C ~X 14C The alicyclic hydrocarbon group may be exemplified by the following: 1B The alicyclic group is the same as the group described in the above. For example, cycloalkyl and cycloalkenyl groups are preferably exemplified, and cycloalkyl is preferred.

[0358] The carbon number of the alicyclic hydrocarbon group is 3 or more, preferably 4 or more, and the upper limit is preferably 12 or less, more preferably 8 or less, and further preferably 6 or less.

[0359] X 12C ~X 14C The hydrogen atoms of the alicyclic hydrocarbon group may be substituted by halogen atoms, and part of them may be substituted by hydroxyl groups, the above-mentioned aliphatic hydrocarbon groups (such as alkyl groups, alkenyl groups), etc. In the case of being substituted by halogen atoms, as specified in X 12C ~X 14C The halogen atom in X is an atom selected from fluorine, chlorine, bromine and iodine atoms. 12C ~X 14C The halogen atom of the alicyclic hydrocarbon group can be preferably exemplified by the following as X 12C ~X 14C The halogen atoms of X are the same atoms as those exemplified above. 12C ~X 14C When a plurality of alicyclic hydrocarbon groups are alicyclic hydrocarbon groups, the plurality of alicyclic hydrocarbon groups may be the same as or different from each other.

[0360] As X 12C ~X 14C The aromatic hydrocarbon group may be exemplified by the following: 1B The same group as the group described above with reference to the aromatic group. For example, preferably exemplified are groups having a portion obtained by removing one hydrogen atom from the basic structure of: monocyclic aromatic compounds such as benzene, toluene, and styrene; polycyclic aromatic compounds such as biphenyl, diphenylmethane (benzylbenzene), diphenylethane (bibenzyl), methylenetriphenol, and triphenylcyclohexane in which multiple aromatic rings are bonded; naphthalene, phenanthrene, anthracene, pyrene, triphenylene, tetracene, and pentacene in which multiple aromatic rings are condensed; or polycyclic aromatic compounds such as indene, indacenes, acenaphthene, dihydronaphthalene, tetrahydronaphthalene, biphenylene, fluorene, and fluoranthene in which aromatic rings are condensed with alicyclic rings; and the like.

[0361] Furthermore, structures obtained by bonding or condensing any of these aromatic ring basic structures, the above-mentioned single alicyclic basic structures, and multiple alicyclic basic structures, such as diphenylfluorene (9,9-diphenyl-9H-fluorene) in which two benzenes are single-bonded at the 9-position of fluorene, can also be representatively and preferably exemplified as basic structures.

[0362] X 12C ~X 14C The hydrogen atoms of the aromatic hydrocarbon group may be substituted by halogen atoms, and part of them may be substituted by hydroxyl groups, the above-mentioned aliphatic hydrocarbon groups (such as alkyl groups, alkenyl groups), etc. In the case of being substituted by halogen atoms, as specified in X 12C ~X 14C The halogen atom in X is an atom selected from fluorine, chlorine, bromine and iodine atoms. 12C ~X14C The halogen atom of the aromatic hydrocarbon group can be preferably exemplified by the following as X 12C ~X 14C The halogen atoms of X are the same atoms as those exemplified above. 12C ~X 14C When a plurality of the alicyclic hydrocarbon groups are aromatic hydrocarbon groups, the plurality of alicyclic hydrocarbon groups may be the same as or different from each other.

[0363] The number of carbon atoms in the aromatic group is 6 or more, preferably 8 or more, and the upper limit is preferably 36 or less, more preferably 28 or less, further preferably 20 or less, and further preferably 14 or less.

[0364] As the organic halide 1a represented by the general formula (1C), it is preferred that X 11C is a halogen atom, X 12C is an aliphatic hydrocarbon group having 2 to 24 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms, and X 13C and X 14C Here, as X 12C As described above, the halogen atom is preferably a chlorine atom, a bromine atom, or an iodine atom, more preferably a bromine atom or an iodine atom, and still more preferably a bromine atom.

[0365] The aliphatic hydrocarbon group is preferably an alkyl group, and the carbon number of the alkyl group is preferably 2 or more, more preferably 3 or more, and the upper limit is preferably 16 or less, more preferably 12 or less. Furthermore, the aromatic hydrocarbon group is preferably a phenyl group or a phenylalkyl group, as described above, and more preferably a phenylalkyl group.

[0366] In addition, as the organic halide 1a represented by the general formula (1C), X 11C is a halogen atom, X 12C and X 13C is an aliphatic hydrocarbon group having 1 to 24 carbon atoms, X 14C A compound in which the halogen atom is a hydrogen atom. Here, as described above, the halogen atom is preferably a chlorine atom, a bromine atom, or an iodine atom, more preferably a bromine atom or an iodine atom, and further preferably a bromine atom. The aliphatic hydrocarbon group is preferably an alkyl group, and the carbon number of the alkyl group is preferably 1 or more, and the upper limit is preferably 24 or less, more preferably 16 or less, further preferably 8 or less, and further preferably 3 or less.

[0367] As described above, the compound represented by the above general formula (1C) is typically a compound having one -CX 1C (X 1C In this case, for example, X in the general formula (1C) may be 11C is a halogen atom, X 12C and X14C is a hydrogen atom, X 13C is a compound of an aliphatic hydrocarbon group, and for example, X 11C is a halogen atom, X 12C and X 14C is an aliphatic hydrocarbon, X 13C is a compound of an aliphatic hydrocarbon group in which at least one hydrogen atom connected to a terminal carbon atom is replaced by a halogen atom. 11C Halogen atoms can form -CX 1C (X 1C represents a halogen atom), X 12C ~X 14C Halogen atoms contained in can also form -CX 1C (X 1C represents a halogen atom).

[0368] (Organic halide 1b)

[0369] The organic halide 1b is a compound represented by the above-mentioned general formula (2C).

[0370] In the general formula (2C), X 21C ~X 26C are independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group or an aromatic hydrocarbon group, X 21C ~X 26C The hydrogen atoms of the aliphatic hydrocarbon group, alicyclic hydrocarbon group, and aromatic hydrocarbon group may be substituted by halogen atoms, and X 21C ~X 26C At least one of X is a halogen atom or a group containing a halogen atom. 21C The halogen atom is an atom selected from chlorine, bromine and iodine atoms, and X 22C ~X 26C The halogen atom is an atom selected from fluorine, chlorine, bromine and iodine.

[0371] As X 21C The halogen atom of X 11C The halogen atom described as X 22C ~X 26C The halogen atom of X can be preferably exemplified by 12C ~X 14C The halogen atoms are the same atoms as those described above. 22C ~X 26C A halogen atom is more preferably a fluorine atom. 21C ~X 26C When a plurality of halogen atoms are halogen atoms, the plurality of halogen atoms may be the same as or different from each other.

[0372] As X 21C ~X 26C The aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group can be preferably exemplified by the above X 12C ~X 14C The group may be an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group, and an aliphatic hydrocarbon group is preferred.

[0373] As the aliphatic hydrocarbon group, an alkyl group or an alkenyl group is preferred, and an alkyl group is more preferred. In the case of an alkyl group, the carbon number is preferably 1 or more, and the upper limit is preferably 24 or less, more preferably 12 or less, further preferably 8 or less, and further preferably 2 or less. In the case of an alkenyl group, the carbon number is preferably 2 or more, and the upper limit is the same as that of the alkyl group. 12C ~X 14C Similarly, the aliphatic hydrocarbon group of X may be straight chain or branched. 22C ~X 26C When a plurality of aliphatic hydrocarbon groups, alicyclic hydrocarbon groups or aromatic hydrocarbon groups are present, the plurality of aliphatic hydrocarbon groups, alicyclic hydrocarbon groups or aromatic hydrocarbon groups may be the same or different.

[0374] X 21C ~X 26C The hydrogen atoms of the aliphatic hydrocarbon group may be substituted by halogen atoms or by hydroxyl groups. The hydrogen atoms of the alicyclic hydrocarbon group may be substituted by halogen atoms, or by hydroxyl groups, or by the above-mentioned aliphatic hydrocarbon groups (e.g., alkyl groups, alkenyl groups), etc. In the case of being substituted by halogen atoms, as specified in X 21C The halogen atom in X is an atom selected from chlorine, bromine and iodine atoms. 22C ~X 26C The halogen atom in X is an atom selected from fluorine, chlorine, bromine and iodine atoms. 21C The halogen atom of the hydrocarbon of X can be preferably exemplified by 21C The same atoms as those exemplified for the halogen atoms as those substituted for X 22C ~X 26C The halogen atom of the hydrocarbon of X can be preferably exemplified by 22C ~X 26C The halogen atom is the same atom as exemplified above.

[0375] As the organic halide 1b represented by the general formula (2C), preferably, X 21C ~X 26C is a halogen atom or a halogenated hydrocarbon group obtained by replacing at least one hydrogen atom with a halogen atom, X 21C ~X 26CAs described above, the halogen atom is preferably a chlorine atom, a bromine atom, or an iodine atom, and the aliphatic hydrocarbon group is preferably an alkyl group, and the carbon number of the alkyl group is preferably 1 or more, and the upper limit is preferably 16 or less, more preferably 8 or less, further preferably 4 or less, and further preferably 2 or less.

[0376] In X 21C ~X 26C When one of the halogenated hydrocarbon groups is a halogenated hydrocarbon group, it is preferred that at least one of the other halogen atoms is a halogen atom or a hydrogen atom, and the number of halogen atoms or hydrogen atoms is more preferably 2 or more, further preferably 3 or more, further preferably 4 or more, and particularly preferably 5. 21C ~X 26C When one of the atoms is a halogenated hydrocarbon group, it is particularly preferred that all of the remaining atoms are halogen atoms or all of the remaining atoms are hydrogen atoms.

[0377] In X 21C ~X 26C In the case where two or more of the halogenated hydrocarbon groups are present, preferably at least one has two or more halogen atoms, more preferably at least one has three or more halogen atoms, and preferably at least one of the other has one halogen atom. In addition, the other are hydrogen atoms or halogen atoms, preferably hydrogen atoms, and more preferably all of the other are hydrogen atoms. Such compounds are also advantageous in that they are easily obtained.

[0378] (Organic halide 1c)

[0379] The organic halide 1c is a compound represented by the above-mentioned general formula (3C).

[0380] In the general formula (3C), X 31C and X 32C are independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group or a group represented by the general formula (3Ca), wherein R 31C is a single bond or an aliphatic hydrocarbon group, R 32C X is a hydrogen atom, a halogen atom or an aliphatic hydrocarbon group. The hydrogen atom of the aliphatic hydrocarbon group, the alicyclic hydrocarbon group, and the aromatic hydrocarbon group may be substituted by a halogen atom. 31C and X 32C At least one of X is a halogen atom or a group containing a halogen atom. 31C The halogen atom is an atom selected from chlorine, bromine and iodine atoms, and X 32C The halogen atom is an atom selected from fluorine, chlorine, bromine and iodine.

[0381] As X 31C The halogen atom of X 11CThe halogen atom described as X 32C The halogen atom of X can be preferably exemplified by 12C ~X 14C The halogen atoms are the same as the atoms described above. 32C The halogen atom of X is more preferably a fluorine atom, a chlorine atom or a bromine atom, and further preferably a chlorine atom. 31C and X 32C In the case of a halogen atom, a plurality of halogen atoms may be the same or different.

[0382] As X 31C and X 32C The aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group can be preferably exemplified by the above X 12C ~X 14C The group may be an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group, and an aliphatic hydrocarbon group is preferred.

[0383] As the aliphatic hydrocarbon group, an alkyl group or an alkenyl group is preferred, and an alkyl group is more preferred. In the case of an alkyl group, the carbon number is preferably 1 or more, more preferably 2 or more, and further preferably 4 or more, and the upper limit is preferably 24 or less, more preferably 16 or less, further preferably 12 or less, and further preferably 10 or less. In the case of an alkenyl group, the carbon number is preferably 2 or more, more preferably 4 or more, and the upper limit is the same as that of the alkyl group. In addition, as in the above X 12C ~X 14C Similarly, the aliphatic hydrocarbon group of X may be either a straight chain or a branched chain. 31C and X 32C In the case of an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group, the plurality of aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, or aromatic hydrocarbon groups may be the same or different, and at least one of the plurality of aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, or aromatic hydrocarbon groups is a group in which a hydrogen atom is substituted by a halogen atom.

[0384] X 31C and X 32C The hydrogen atoms of the aliphatic hydrocarbon group may be substituted by halogen atoms, or by hydroxyl groups, etc. The hydrogen atoms of the alicyclic hydrocarbon group may be substituted by halogen atoms, or by hydroxyl groups, or by the above-mentioned aliphatic hydrocarbon groups (e.g., alkyl groups, alkenyl groups), etc. In the case of being substituted by halogen atoms, as specified in X 31C The halogen atom in X is an atom selected from chlorine, bromine and iodine atoms. 32C The halogen atom in X is an atom selected from fluorine, chlorine, bromine and iodine atoms. 31C The halogen atom of the hydrocarbon of X can be exemplified by the following: 31C The same atoms as those exemplified for the halogen atoms as those substituted for X32C The halogen atom of the hydrocarbon of X can be preferably exemplified by 32C The halogen atom is the same atom as exemplified above.

[0385] As R in the general formula (3Ca) 31C The divalent aliphatic hydrocarbon group may be exemplified by the above X 31C and X 32C Therefore, as the divalent aliphatic hydrocarbon group, an alkanediyl group and an alkenediyl group are preferred, and an alkanediyl group is more preferred.

[0386] The carbon number of the divalent aliphatic hydrocarbon group is preferably 1 or more, and the upper limit is preferably 8 or less, more preferably 6 or less, and further preferably 4 or less.

[0387] As R in the general formula (3Ca) 32C The aliphatic hydrocarbon group may preferably be exemplified by the above-mentioned X 31C and X 32C The aliphatic hydrocarbon group is the same as the aliphatic hydrocarbon group.

[0388] As the aliphatic hydrocarbon group, an alkyl group or an alkenyl group is preferred, and an alkyl group is more preferred. The aliphatic hydrocarbon group may be linear or branched, and is preferably branched. In addition, when the aliphatic hydrocarbon group is an alkyl group, the carbon number is preferably 1 or more, more preferably 2 or more, and further preferably 4 or more, and the upper limit is preferably 24 or less, more preferably 16 or less, further preferably 12 or less, and further preferably 10 or less.

[0389] R 31C , R 32C The hydrocarbon group can be 31C and X 32C The hydrocarbon group is similarly substituted by a halogen atom, and the halogen atom in this case is represented by the general formula (3Ca) as X 31C and X 32C Which one to determine. 31C In the case of the general formula (3Ca), the halogen atom is 31C The halogen atom corresponding to the halogen atom is selected from among chlorine, bromine and iodine atoms, and X 32C In the case of the general formula (3Ca), the halogen atom is 32C The halogen atom corresponding to the present invention is selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0390] As the organic halide 1c represented by the general formula (3C), it is preferred that X 31C is a halogen atom, X 32C is a compound which is an aliphatic hydrocarbon group having 2 or more carbon atoms or a group represented by the general formula (3Ca). 31CThe halogen atom of X is preferably a chlorine atom or a bromine atom, and more preferably a chlorine atom. 32C The aliphatic hydrocarbon group is preferably an alkyl group, and the carbon number is more preferably 4 or more, and the upper limit is preferably 12 or less, and more preferably 10 or less.

[0391] In the general formula (3Ca), R 31C , preferably a single bond or a divalent aliphatic hydrocarbon group, more preferably a single bond. 32C , preferably an aliphatic hydrocarbon group, more preferably an alkyl group or an alkenyl group, further preferably an alkyl group.

[0392] (Organic Halides 1d)

[0393] The organic halide 1d is a compound represented by the above-mentioned general formula (4C).

[0394] In the general formula (4C), X 41C ~X 44C are independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group or an aromatic hydrocarbon group. The hydrogen atom of the aliphatic hydrocarbon group, the alicyclic hydrocarbon group or the aromatic hydrocarbon group may be substituted by a halogen atom. 41C ~X 44C At least one of X is a halogen atom or a group containing a halogen atom. 41C The halogen atom is an atom selected from chlorine, bromine and iodine atoms, and X 42C ~X 44C The halogen atom is an atom selected from fluorine, chlorine, bromine and iodine.

[0395] As X 41C The halogen atom of X 11C The halogen atom described as X 42C ~X 44C The halogen atom of X can be preferably exemplified by 12C ~X 14C The halogen atoms are the same as the atoms described above. 41C The halogen atom of X is preferably a chlorine atom or a bromine atom, and more preferably a chlorine atom. 42C ~X 44C The same is true for the preferred halogen atoms. 41C ~X 44C When a plurality of halogen atoms are halogen atoms, the plurality of halogen atoms may be the same as or different from each other.

[0396] As X 41C ~X 44C The aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group can be preferably exemplified by the above X 12C ~X14C The group may be an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group, and an aliphatic hydrocarbon group is preferred.

[0397] As the aliphatic hydrocarbon group, an alkyl group or an alkenyl group is preferred, and an alkyl group is more preferred. In the case of an alkyl group, the carbon number is preferably 1 or more, and the upper limit is preferably 24 or less, more preferably 12 or less, further preferably 8 or less, further preferably 4 or less, and particularly preferably 2 or less. In the case of an alkenyl group, the carbon number is preferably 2 or more, and the upper limit is the same as that of the alkyl group. 12C ~X 14C Similarly, the aliphatic hydrocarbon group of X may be either a straight chain or a branched chain. 41C ~X 44C In the case of an aliphatic hydrocarbon group, an alicyclic hydrocarbon group or an aromatic hydrocarbon group, a plurality of aliphatic hydrocarbon groups, alicyclic hydrocarbon groups or aromatic hydrocarbon groups may be the same or different.

[0398] X 41C ~X 44C The hydrogen atoms of the aliphatic hydrocarbon group may be substituted by halogen atoms, or by hydroxyl groups, etc. The hydrogen atoms of the alicyclic hydrocarbon group may be substituted by halogen atoms, or by hydroxyl groups, or by the above-mentioned aliphatic hydrocarbon groups (e.g., alkyl groups, alkenyl groups), etc. In the case of being substituted by halogen atoms, as specified in X 41C The halogen atom in X is an atom selected from chlorine, bromine and iodine atoms. 42C ~X 44C The halogen atom in X is an atom selected from fluorine, chlorine, bromine and iodine atoms. 41C The halogen atom of the hydrocarbon of X can be exemplified by the following: 41C The same atoms as those exemplified for the halogen atoms as those substituted for X 42C ~X 44C The halogen atom of the hydrocarbon of X can be preferably exemplified by 42C ~X 44C The halogen atom is the same atom as exemplified above.

[0399] As the organic halide 1d represented by the general formula (4C), it is preferred that X 41C is a halogen atom, X 42C ~X 44C Here, as the halogen atom, a fluorine atom, a chlorine atom, or a bromine atom is preferred, and a chlorine atom is more preferred. 42C ~X 44C The monovalent aliphatic hydrocarbon group is preferably an alkyl group, and the carbon number is preferably 1 or more, and the upper limit is preferably 8 or less, more preferably 4 or less, and further preferably 2 or less.

[0400] (Compound (D))

[0401] The compound (D) used in the modified sulfide solid electrolyte of the present embodiment is a compound having a formyl group (CH(=O)-). As the compound (D), a compound represented by the following general formula (1D) can be preferably exemplified. The compound (D) has a formyl group, and further, by having a formyl group as represented by the following general formula (1D), it becomes easy to adhere to the sulfide solid electrolyte, so the oil absorption is reduced, it is easy to obtain excellent coating adaptability, and excellent battery performance can be obtained more effectively.

[0402] [Chemistry 14]

[0403]

[0404] In the general formula (1D), R 11D and R 12D Each independently represents an organic group or a single bond, X 11D represents an oxygen atom, a sulfur atom or a single bond, n 11D Represents 0 or 1.

[0405] R 11D The organic group is a divalent group, R 12D The organic group in n 11D When it is 0, it is a univalent group. 11D When R is 1, it is a divalent group. 11D and R 12D Examples of the organic group include an aliphatic group, an alicyclic group, an aromatic group and a heterocyclic group, and among them, an aliphatic group and an aromatic group are preferred.

[0406] (Aliphatic group)

[0407] Examples of the monovalent aliphatic group include the following: 1B The aliphatic group of is the same group as that described in the above description. For example, alkyl, alkenyl, and alkynyl groups can be mentioned. From the viewpoint of reducing the oil absorption, easily obtaining excellent coating adaptability, and more effectively obtaining excellent battery performance, alkyl and alkenyl groups are preferred, and alkyl groups are more preferred.

[0408] From the same viewpoint, the carbon number of the monovalent aliphatic group is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more, and the upper limit is preferably 20 or less, more preferably 16 or less, and even more preferably 12 or less.

[0409] As such a monovalent aliphatic group, representative and preferred examples include methyl, ethyl, various propyl, various butyl, various pentyl, various hexyl, various heptyl, various octyl, various nonyl, various decyl, various undecyl, various dodecyl, etc. In the present specification, "various" means including linear, branched and even isomers thereof, for example, if it is various propyl groups, it includes 1-propyl, 2-propyl, 1-methylethyl as linear and branched saturated aliphatic groups having 3 carbon atoms.

[0410] The aliphatic group may be linear or branched, but is preferably linear.

[0411] As the divalent aliphatic group, there can be mentioned groups having a portion obtained by removing one hydrogen atom from the above-mentioned monovalent aliphatic group as a chemical bond, namely, alkanediyl, alkenediyl, and alkynediyl. From the viewpoint of reducing the oil absorption, easily obtaining excellent coating adaptability, and more effectively obtaining excellent battery performance, alkanediyl and alkenediyl are preferred, and alkanediyl is more preferred.

[0412] The carbon number of the divalent aliphatic group is preferably 1 or more, and the upper limit is preferably 12 or less, more preferably 8 or less, further preferably 4 or less, and further preferably 3 or less. The rest is the same as the above-mentioned monovalent aliphatic group.

[0413] Furthermore, at least a part of the hydrogen atoms of the aliphatic group may be substituted with a halogen atom, a hydroxyl group, an amino group or the like.

[0414] (Alicyclic Group)

[0415] Examples of the monovalent alicyclic group include the following: 1B The alicyclic group of the present invention is the same group as the group described in the above description. For example, cycloalkyl, cycloalkenyl, and cycloalkynyl groups can be mentioned. From the viewpoint of reducing the oil absorption, easily obtaining excellent coating adaptability, and more effectively obtaining excellent battery performance, cycloalkyl and cycloalkenyl groups are preferred, and cycloalkyl groups are more preferred.

[0416] From the same viewpoint, the carbon number of the monovalent alicyclic group is preferably 3 or more, more preferably 4 or more, and the upper limit is preferably 20 or less, more preferably 16 or less, and further preferably 12 or less.

[0417] As the alicyclic group, an alicyclic group containing multiple alicyclic rings may also be exemplified, and for example, a group having a chemical bond obtained by removing one hydrogen atom from a basic structure such as: a bonded multi-alicyclic structure such as a bicyclohexyl group; a structure obtained by condensing two or more alicyclic rings such as hexahydronaphthalene, octahydronaphthalene, decahydronaphthalene; a cross-linked cyclic structure such as norbornane, norbornene, adamantane, tricyclodecane, and pinene may also be preferably exemplified. In addition to these, as a basic structure having a double bond in an alicyclic ring, basic structures such as pentalylene and azulene may also be exemplified.

[0418] Furthermore, a structure in which any of the above-mentioned single alicyclic basic structure, multiple alicyclic basic structures, and aromatic ring basic structures described later are bonded or condensed can also be exemplified as a basic structure that can be preferably exemplified.

[0419] One hydrogen atom removed from the above basic structure of the alicyclic group may be a hydrogen atom of the alicyclic ring or a hydrogen atom of a substituent such as an alkyl group (the substituent will be described later) connected to the alicyclic ring.

[0420] The basic structure of the alicyclic group may be an alicyclic group having a heterocyclic ring in which carbon atoms in the alicyclic groups exemplified above are substituted with hetero atoms such as nitrogen atoms, oxygen atoms, sulfur atoms, and phosphorus atoms.

[0421] In addition, the examples of the basic structure of the alicyclic group are representative examples of preferred ones, and the group is not limited to these. For example, a group in which an aromatic group or a heterocyclic group described later is bonded or condensed to an alicyclic group based on the above basic structure may also be included.

[0422] It can also be a structure in which at least a part of the hydrogen atoms in the above-exemplified alicyclic groups or basic structures are replaced by halogen atoms such as fluorine atoms, hydroxyl groups, amino groups, or substituents such as the above-mentioned aliphatic groups. In this case, the aliphatic group is preferably an alkyl group or an alkenyl group, and the carbon number is preferably 1 or more, and the upper limit is preferably 12 or less, more preferably 8 or less, further preferably 6 or less, and further preferably 4 or less.

[0423] The divalent alicyclic group may be a group having a portion obtained by removing one hydrogen atom from the above-mentioned monovalent alicyclic group as a chemical bond. Here, the one hydrogen atom may be a hydrogen atom of an alicyclic ring or a hydrogen atom of a substituent such as an alkyl group connected to the alicyclic ring.

[0424] (Aromatic Group)

[0425] Examples of the monovalent aromatic group include the following: 1B The same group as the group described above with reference to the aromatic group. For example, preferably exemplified are groups having a portion obtained by removing one hydrogen atom from the basic structure of: monocyclic aromatic compounds such as benzene, toluene, and styrene; polycyclic aromatic compounds such as biphenyl, diphenylmethane (benzylbenzene), diphenylethane (bibenzyl), methylenetriphenol, and triphenylcyclohexane in which multiple aromatic rings are bonded; naphthalene, phenanthrene, anthracene, pyrene, triphenylene, tetracene, and pentacene in which multiple aromatic rings are condensed; or polycyclic aromatic compounds such as indene, indacenes, acenaphthene, dihydronaphthalene, tetrahydronaphthalene, biphenylene, fluorene, and fluoranthene in which aromatic rings are condensed with alicyclic rings; and the like.

[0426] The one hydrogen atom removed from the above basic structure of the aromatic group may be a hydrogen atom of an aromatic ring (including the above condensed polycyclic ring, etc.) or a hydrogen atom of a substituent such as an alkyl group connected to the aromatic ring (including the above condensed polycyclic ring, etc.) (the substituent will be described later). From the viewpoint of reducing the oil absorption, easily obtaining excellent coating adaptability, and more effectively obtaining excellent battery performance, a group obtained by removing one hydrogen atom from a hydrogen atom of a substituent such as an alkyl group connected to an aromatic ring (including the above condensed polycyclic ring, etc.) is preferred.

[0427] As the aromatic group, among the above, an aromatic group having a monocyclic aromatic compound as a basic structure is preferred, and preferred examples include: a group having as a chemical bond a portion obtained by removing one hydrogen atom from an aromatic ring such as phenyl, methylphenyl, vinylphenyl, etc.; a group having as a chemical bond a portion obtained by removing one hydrogen atom from an alkyl group connected to an aromatic ring such as benzyl, phenethyl, phenylpropyl, etc., and more preferably a group having as a chemical bond a portion obtained by removing one hydrogen atom from an alkyl group connected to an aromatic ring such as benzyl, phenethyl, phenylpropyl, etc.

[0428] The carbon number of the monovalent aromatic group is preferably 6 or more, more preferably 7 or more, and the upper limit is preferably 36 or less, more preferably 24 or less, further preferably 12 or less, and further preferably 10 or less.

[0429] The basic structure of the aromatic group may be a structure having a heterocyclic ring in which the carbon atoms of the aromatic ring (including the above-mentioned condensed polycyclic ring, etc.) in the above-exemplified basic structure are substituted with heteroatoms such as nitrogen atoms, oxygen atoms, sulfur atoms, and phosphorus atoms.

[0430] In addition, the examples of the basic structure of the aromatic group are representative examples only, and are not limited to these. For example, a group in which the above-mentioned alicyclic group or a heterocyclic group described later is bonded or condensed to an aromatic group based on the above-mentioned basic structure may also be included.

[0431] It may also be a structure in which at least a portion of the hydrogen atoms of the aromatic ring (including the above-mentioned condensed polycyclic ring, etc.) in the above-mentioned basic structure is replaced by a halogen atom such as a fluorine atom, a hydroxyl group, an amino group, or a substituent such as the above-mentioned aliphatic group. In this case, the aliphatic group is preferably an alkyl group or an alkenyl group, more preferably an alkyl group, and the carbon number is preferably 1 or more, and the upper limit is preferably 12 or less, more preferably 8 or less, more preferably 6 or less, and further preferably 4 or less.

[0432] When at least a part of the hydrogen atoms of the aromatic ring (including the above-mentioned condensed polycyclic ring and the like) are substituted, as the substituent, an aliphatic group is preferred among the above-mentioned ones, and an alkyl group is more preferred.

[0433] As a divalent aromatic group, a group having a portion obtained by removing one hydrogen atom from the above-mentioned monovalent aromatic group as a chemical bond can be mentioned. Here, the one hydrogen atom may be a hydrogen atom of an aromatic ring or a hydrogen atom of a substituent such as an alkyl group connected to the aromatic ring.

[0434] (Heterocyclic Group)

[0435] Examples of the monovalent heterocyclic group include: saturated or unsaturated monocyclic oxygen-containing heterocyclic compounds such as oxetane, tetrahydrofuran, dihydrofuran, furan, dioxolane, tetrahydropyran, pyran, etc.; saturated or unsaturated monocyclic nitrogen-containing heterocyclic compounds such as pyrrolidine, pyrroline, imidazolidine, imidazoline, imidazole, piperidine, pyridine, piperazine, pyridazine, pyrimidine, pyrazine, triazine, etc.; saturated or unsaturated monocyclic sulfur-containing heterocyclic compounds such as thietane, tetrahydrothiophene, thiophene, thiazane, thiopyran, etc.; Saturated or unsaturated monocyclic oxygen-nitrogen heterocyclic compounds such as tetrahydrooxazole, oxazole, oxadiazole, succinimide, morpholine, oxazine, etc.; saturated or unsaturated monocyclic nitrogen-sulfur heterocyclic compounds such as tetrahydrothiazole, thiazole, thiomorpholine, thiazine, etc.; saturated monocyclic oxygen-sulfur heterocyclic compounds such as oxathiolane, sulfolane, thioxane, dioxothioxane, etc.; monocyclic heterocyclic groups having a chemical bond as a portion obtained by removing one hydrogen atom from the basic structure of monocyclic heterocyclic compounds.

[0436] In addition, for example, there can be mentioned: saturated or unsaturated condensed polycyclic oxygen-containing heterocyclic compounds such as benzofuran, octahydrobenzofuran, benzopyran, benzodioxane, dibenzofuran, xanthene, dibenzodioxin; saturated or unsaturated condensed polycyclic nitrogen-containing heterocyclic compounds such as indoline, indole, indolizine, benzimidazole, azaindole, decahydroquinoline, quinoline, quinoxaline, carbazole, acridine, phenazine, azaadamantane; benzothiophene, benzothiopyran, dodecahydrodibenzothiophene, hexahydrodibenzothiophene, dihydrodibenzothiophene, Saturated or unsaturated fused polycyclic sulfur-containing heterocyclic compounds such as benzothiophene; fused polycyclic oxygen-nitrogen heterocyclic compounds such as furanpyrrole, benzoxazole, benzoxazine, dihydrobenzoxazine and phenoxazine; fused polycyclic nitrogen-containing heterocyclic compounds such as benzothiazole, benzothiadiazole and phenothiazine; bonded polycyclic or fused polycyclic oxygen-sulfur heterocyclic compounds such as phenylthiochromene and phenoxathiol; and polycyclic heterocyclic groups having a chemical bond as a part obtained by removing one hydrogen atom from the basic structure of polycyclic heterocyclic compounds.

[0437] The number of carbon atoms in the monovalent heterocyclic group is preferably 3 or more, more preferably 4 or more, and the upper limit is preferably 36 or less, more preferably 24 or less, and further preferably 18 or less.

[0438] As polycyclic heterocyclic compounds, polycyclic fused heterocyclic compounds are mainly exemplified, but only preferred heterocyclic compounds are exemplified representatively, and it is of course possible to include, for example, polycyclic bonded heterocyclic compounds as basic structures. In addition, groups obtained by bonding or condensing, for example, the above-mentioned alicyclic groups and aromatic groups to the above-mentioned heterocyclic groups may also be included.

[0439] One hydrogen atom removed from the above basic structure of the heterocyclic group may be a hydrogen atom of the heterocyclic ring or a hydrogen atom of a substituent such as an alkyl group connected to the heterocyclic ring (the substituent will be described later).

[0440] It may also be a structure in which at least a part of the hydrogen atoms of the heterocyclic group in the above-exemplified basic structure is substituted by a halogen atom such as a fluorine atom, a hydroxyl group, an amino group, or a substituent such as the above-mentioned aliphatic group. In this case, the aliphatic group is preferably an alkyl group or an alkenyl group, more preferably an alkyl group, and the carbon number is preferably 1 or more, and the upper limit is preferably 12 or less, more preferably 8 or less, more preferably 6 or less, and further preferably 4 or less.

[0441] As the divalent heterocyclic group, there can be mentioned a group having a portion obtained by removing one hydrogen atom from the above-mentioned monovalent heterocyclic group as a chemical bond. Here, the one hydrogen atom may be a hydrogen atom of the heterocyclic group or a hydrogen atom of a substituent such as an alkyl group connected to the heterocyclic group.

[0442] X 11D represents an oxygen atom, a sulfur atom or a single bond. From the viewpoint of reducing oil absorption, easily obtaining excellent coating adaptability, and more effectively obtaining excellent battery performance, X 11D An oxygen atom and a single bond are preferred.

[0443] n 11D It represents 0 or 1, and is preferably 0 from the viewpoint of reducing the oil absorption, easily obtaining excellent coating suitability, and more effectively obtaining excellent battery performance.

[0444] Regarding R in the above general formula (1D): 11D , R 12D , X 11D 、n 11D , as a preferred combination, in X 11D When it is a single bond, R 11D is a single bond, R 12D is an aliphatic group, n 11D is 0, as R 12D The aliphatic group is preferably an alkyl group, and the carbon number of the alkyl group is as described above.

[0445] As such a compound (D), heptaldehyde (in the general formula (1D), R11D and X 11D is a single bond, n 11D is 0, R 12D is hexyl), undecanal (in the general formula (1D), R 11D and X 11D is a single bond, n 11D is 0, R 12D In addition, compounds having the structure based on this can also obtain the same effect.

[0446] In addition, regarding R in the above general formula (1D), 11D , R 12D , X 11D 、n 11D , as a preferred combination, in X 11D When it is an oxygen atom, R 11D is an aliphatic group, R 12D For aromatic groups, n 11D is 0, as R 11D The aliphatic group is preferably an alkyl group, and the carbon number of the alkyl group is as described above. 12D The aromatic group is preferably an aromatic group with a monocyclic aromatic compound as a basic structure, and more preferably a group in which an aliphatic group (preferably an alkyl group) is connected to the aromatic ring and has a portion obtained by removing one hydrogen atom of the aliphatic group (preferably an alkyl group) as a chemical bond, among which benzyl, phenethyl and phenylpropyl are preferred, and benzyl is more preferred.

[0447] As such a compound (D), benzyloxyacetaldehyde (in the general formula (D), X 11D is an oxygen atom, R 11 is methylene, n 11D is 0, R 12D In addition, compounds having the structure based on this can of course also obtain the same effect.

[0448] In the modified sulfide solid electrolyte of the present embodiment, the above-mentioned compound (D) can be used alone or in combination of two or more.

[0449] (Compound (E))

[0450] The compound (E) used in the modified sulfide solid electrolyte of the present embodiment is a compound having two or more acetyl groups (CH3C(=O)-). As the compound (E), a compound represented by the following general formula (1E) can be preferably exemplified. The compound (E) has two or more acetyl groups, and further has two or more acetyl groups as shown in the following general formula (1E), so that it becomes easy to adhere to the sulfide solid electrolyte, so the oil absorption is reduced, it is easy to obtain excellent coating adaptability, and excellent battery performance can be obtained more effectively.

[0451] [Chemistry 15]

[0452]

[0453] In the general formula (1E), R 11E and R 12E Each independently represents an organic group or a single bond, X 11E represents an oxygen atom, a sulfur atom, or a single bond.

[0454] R 11E and R 12E The organic group is a divalent organic group, and examples thereof include the above-mentioned R 11D and R 12D The divalent aliphatic group, alicyclic group, aromatic group and heterocyclic group in the organic group described for the organic group are preferably a divalent aliphatic group. 11D and R 12D The same groups are described for the organic groups.

[0455] As R in the above general formula (1E) 11E , R 12E , X 11E The preferred combination is preferably R 11E and R 12E One of them is an aliphatic group, the other is a single bond, X 11E is a single bond, as R 11E and R 12E The aliphatic group of any one of , preferably an alkanediyl group.

[0456] The carbon number of the alkanediyl group is the same as that of R 11D and R 12D The content described is based on the carbon number of the divalent aliphatic group, that is, it is preferably 1 or more, and the upper limit is preferably 12 or less, more preferably 8 or less, further preferably 4 or less, and further preferably 3 or less.

[0457] X 11Erepresents an oxygen atom, a sulfur atom or a single bond. From the viewpoint of reducing oil absorption, easily obtaining excellent coating adaptability, and more effectively obtaining excellent battery performance, X 11E Single bonds are preferred.

[0458] As such a compound (E), acetylacetone (in the general formula (1E), R 11E and X 11E is a single bond, R 12E In addition, compounds having a structure based on this can of course also obtain the same effect.

[0459] In the modified sulfide solid electrolyte of the present embodiment, the above-mentioned compound (E) can be used alone or in combination of two or more.

[0460] (Compound (F))

[0461] The compound (F) used in the modified sulfide solid electrolyte of the present embodiment is an organic halide 2 having two or more halogen-containing groups represented by -CH2X (X represents a fluorine atom or a bromine atom) and an organic group. The organic halide 2 of the compound (F) has two or more halogen-containing groups and an organic group represented by -CH2X (X represents a fluorine atom or a bromine atom), and further has two or more halogen-containing groups and an organic group represented by -CH2X (X represents a fluorine atom or a bromine atom) as shown in the following general formula (1F), so that it becomes easy to adhere to the sulfide solid electrolyte, so the oil absorption is reduced, it is easy to obtain excellent coating adaptability, and excellent battery performance can be obtained more effectively.

[0462] [Chemistry 16]

[0463]

[0464] In the general formula (1F), R 11F represents an organic group or a single bond, X 11F and X 12F Each independently represents a fluorine atom or a bromine atom.

[0465] R 11F The organic group is a divalent organic group, and examples thereof include the above-mentioned R 11D and R 12D Among the divalent aliphatic groups, alicyclic groups, aromatic groups and heterocyclic groups explained as organic groups, divalent aliphatic groups are preferred.

[0466] As a divalent aliphatic group, 11D and R 12DSimilarly, the divalent aliphatic group may include a group having a portion obtained by removing one hydrogen atom from the above-mentioned monovalent aliphatic group as a chemical bond, i.e., an alkanediyl group, an alkenediyl group, and an alkenediyl group. From the viewpoint of reducing the oil absorption, easily obtaining excellent coating adaptability, and more effectively obtaining excellent battery performance, an alkanediyl group and an alkenediyl group are preferred, and an alkanediyl group is more preferred.

[0467] The carbon number of the divalent aliphatic group is preferably 1 or more, and the upper limit is preferably 20 or less, more preferably 16 or less, further preferably 12 or less, and further preferably 10 or less.

[0468] The aliphatic group may be straight-chain or branched, preferably straight-chain. 11D and R 12D The aliphatic groups are the same.

[0469] In addition, about the 11F The divalent alicyclic group, aromatic group and heterocyclic group of the organic group as R 11D and R 12D The same applies to the alicyclic group, aromatic group and heterocyclic group in the organic group.

[0470] R 11F The above-mentioned organic group may be used or a single bond may be used. From the viewpoint of reducing the oil absorption, easily obtaining excellent coating suitability, and more effectively obtaining excellent battery performance, the above-mentioned organic group is preferred.

[0471] X 11F and X 12F Each independently represents a fluorine atom or a bromine atom, and X 11F and X 12F They may be the same or different, but are preferably the same from the viewpoint of reducing the oil absorption, easily obtaining excellent coating suitability, and more effectively obtaining excellent battery performance.

[0472] Furthermore, it may be a fluorine atom or a bromine atom, but from the same viewpoint as above, a bromine atom is preferred.

[0473] As such a compound (F), 1,3-dibromopropane (in the general formula (3), R 11F is methylene, X 11F and X 12F is a bromine atom), 1,4-dibromobutane (in the general formula (1F), R 11F is methylene, X 11F and X 12F is a bromine atom), 1,6-dibromohexane (in the general formula (1F), R 11F is 1,4-butanediyl, X 11Fand X 12F is a bromine atom), 1,10-dibromodecane (in the general formula (3), R 11F is 1,8-octanediyl, X 11F and X 12F A dihaloalkyl having a bromine atom bonded to the carbon atoms at both ends as a halogen atom is particularly preferred. In addition, a compound having a structure based on this can of course also obtain the same effect.

[0474] In the modified sulfide solid electrolyte of the present embodiment, the above-mentioned compound (F) can be used alone or in combination of two or more.

[0475] (Compound (G))

[0476] The compound (G) used in the modified sulfide solid electrolyte of the present embodiment is a thiol compound. The thiol compound of the compound (G) is a compound having a thiol group. By having a thiol group as shown in the following general formulas (1G) and (2G), it becomes easy to adhere to the sulfide solid electrolyte, so the oil absorption is reduced, it is easy to obtain excellent coating adaptability, and excellent battery performance can be obtained more effectively. That is, if the compound (G) is each thiol compound 1 and thiol compound 2 represented by the following general formulas (1G) and (2G), the oil absorption is reduced, it is easy to obtain excellent coating adaptability, and excellent battery performance can be obtained more effectively.

[0477] [Chemistry 17]

[0478]

[0479] In the general formula (1G), R 11G , R 12G and R 13G Each independently represents an organic group or a single bond, X 11G represents a hydrogen atom or a thiol group, n 11G represents an integer from 0 to 3. 11G , R 12G and R 13G At least one of the groups is an organic group.

[0480] In the general formula (2G), R 21G , R 22G and R 23G Each independently represents an organic group. 21G 、n 22G Integer from 0 to 3, n 21G and n 22G Satisfy n 21G +n 22G =3. Among them, R 21G , R22G and R 23G At least one of the groups is an organic group.

[0481] R in the general formula (1G) 11G , R 12G and R 13G The organic group is a divalent organic group, and examples thereof include the above-mentioned R 11D and R 12D Among the divalent aliphatic groups, alicyclic groups, aromatic groups and heterocyclic groups explained as organic groups, divalent aliphatic groups are preferred.

[0482] From the perspective of reducing oil absorption, easily obtaining excellent coating adaptability, and more effectively obtaining excellent battery performance, R 11G and R 13G The carbon number of the divalent aliphatic group is preferably 1 or more, and the upper limit is preferably 24 or less, more preferably 20 or less, further preferably 16 or less, and further preferably 12 or less.

[0483] From the same point of view, R 12G The carbon number of the divalent aliphatic group is preferably 1 or more, and the upper limit is preferably 8 or less, more preferably 6 or less, further preferably 4 or less, and further preferably 2 or less. 12G In the case of (n 11G is an integer of 2 to 3), multiple R 12G They may be the same or different, but are preferably the same.

[0484] The aliphatic group may be straight-chain or branched, preferably straight-chain. 11D and R 12D The aliphatic groups are the same.

[0485] In addition, about the 11G , R 12G and R 13G The divalent alicyclic group, aromatic group and heterocyclic group of the organic group as R 11D and R 12D The same applies to the alicyclic group, aromatic group and heterocyclic group in the organic group.

[0486] R 11G , R 12G and R 13G The above-mentioned single bond may be used, but from the viewpoint of reducing the oil absorption, easily obtaining excellent coating suitability, and more effectively obtaining excellent battery performance, it is preferred that at least one of them is the above-mentioned organic group.

[0487] X 11Grepresents a hydrogen atom or a thiol group, and may be either, but a hydrogen atom is preferred from the viewpoint of reducing oil absorption, easily obtaining excellent coating adaptability, and more effectively obtaining excellent battery performance. That is, the thiol compound of compound (G) may be a monothiol compound having one thiol group, or may be a dithiol compound having two thiol groups, and a monothiol compound is preferred.

[0488] In addition, 11G It represents an integer of 0 to 3, and from the same viewpoint as above, 0 and 1 are preferred, and 0 is more preferred.

[0489] R in the general formula (2G) 21G The organic group is a divalent organic group, and examples thereof include the above-mentioned R 11D and R 12D The divalent aliphatic group, alicyclic group, aromatic group and heterocyclic group in the organic group described for the organic group are preferably a divalent aliphatic group or aromatic group, and more preferably a divalent aromatic group. 11D and R 12D The same groups are described for the organic groups.

[0490] From the perspective of reducing oil absorption, easily obtaining excellent coating adaptability, and more effectively obtaining excellent battery performance, R 21G The carbon number of the divalent aliphatic group is preferably 1 or more, more preferably 2 or more, and the upper limit is preferably 12 or less, more preferably 8 or less, and further preferably 4 or less.

[0491] In addition, regarding the general formula (2G), R 22G and R 23G is a monovalent organic group, and examples of the above R 11D and R 12D Among the organic groups explained for the organic groups, monovalent aliphatic groups, alicyclic groups, aromatic groups and heterocyclic groups are preferably monovalent aliphatic groups. 11D and R 12D The same groups are described for the organic groups.

[0492] From the perspective of reducing oil absorption, easily obtaining excellent coating adaptability, and more effectively obtaining excellent battery performance, R 22G and R 23G The number of carbon atoms in the monovalent aliphatic group is preferably 1 or more, and the upper limit is preferably 12 or less, more preferably 8 or less, further preferably 4 or less, and further preferably 2 or less.

[0493] In addition, when there are multiple R 22G or R23G In the case of (n 21G is an integer of 1 or 2), multiple R 22G or R 23G They may be the same or different, but are preferably the same.

[0494] R 21G , R 22G and R 23G The aliphatic group may be straight chain or branched, preferably straight chain. 11D and R 12D The aliphatic groups are the same.

[0495] In addition, about the 21G , R 22G and R 23G The monovalent or divalent alicyclic group, aromatic group or heterocyclic group of the organic group, as the above R 11D and R 12D The same applies to the alicyclic group, aromatic group and heterocyclic group in the organic group.

[0496] As such a compound (G), a typical example of a thiol compound 1 represented by the above general formula (1G) is 1-dodecanethiol (in the general formula (1G), R 11G is a single bond, n 11G is 0, R 13G is 1,12-dodecanediyl, X 11G is a hydrogen atom), 1,10-decanedithiol (in the general formula (1G), R 11G is a single bond, n 11G is 0, R 13G is 1,10-decanediyl, X 11G In addition, as the thiol compound 2 represented by the general formula (2G), 3-mercaptopropyltrimethoxysilane (in the general formula (2G), R 21G is 1,3-propanediyl, R 23G Methyl, n 21G is 0, n 22G 3). In addition, compounds having a structure based on this can of course also obtain the same effect.

[0497] In the modified sulfide solid electrolyte of the present embodiment, the above-mentioned compound (G) can be used alone or in combination of multiple compounds, and at least one compound selected from the compound represented by the above-mentioned general formula (1G) and the compound represented by the general formula (2G) can be used. For example, the compound represented by the above-mentioned general formula (1G) can be used alone, or two compounds represented by the above-mentioned general formula (1G) can be used in combination, and the same is true for the compound represented by the above-mentioned general formula (2G). In addition, for example, the compound represented by the above-mentioned general formula (1G) can be used alone or in combination with the compound represented by the general formula (2G).

[0498] (Compound (H))

[0499] The compound (H) used in the modified sulfide solid electrolyte of the present embodiment is a phosphorus compound that does not contain a metal (wherein the compound does not contain an oxygen atom that is single-bonded to a phosphorus atom). The compound (H) may be a phosphorus compound that does not contain a metal atom, where the compound does not contain an oxygen atom that is single-bonded to a phosphorus atom. That is, the compound (H) does not contain a hydrocarbon group that is bonded to a phosphorus atom via oxygen, for example, a compound in which various organic groups are bonded to a phosphorus atom via an alkoxy group or an ether bond.

[0500] The compound (H) is a compound containing no metal atom and a phosphorus atom. By having a phosphorus atom as shown in the following general formulas (1H) to (3H), it becomes easy to adhere to the sulfide solid electrolyte, so that the oil absorption is reduced, it becomes easy to obtain excellent coating adaptability, and excellent battery performance can be obtained more effectively. That is, as the compound (H), preferably, a metal-free phosphorus compound 1H represented by the following general formula (1H), a metal-free phosphorus compound 2H represented by the following general formula (2H), and a metal-free phosphorus compound 3H represented by the following general formula (3H) can be exemplified. In the modified sulfide solid electrolyte of the present embodiment, as the compound (H), the metal-free phosphorus compounds represented by these general formulas can be used alone or in combination of multiple types (for example, multiple compounds represented by the following general formula (1H) can be used in combination).

[0501] [Chemistry 18]

[0502]

[0503] In the general formula (1H), R 11H , R 12H and R 13H Each independently represents an organic group.

[0504] In the general formula (2H), R 21H , R 22H and R 23H Each independently represents an organic group.

[0505] In the general formula (3H), R 31H , R 32H , R 35H and R 36H R each independently represents an organic group. 33H and R 34H Each independently represents a single bond or an organic group, X 31H represents a single bond or an oxygen atom. In addition, R 33H and R 34H At least one of R is an organic group, 33H With R 34H They may be bonded to each other to form a condensed ring.

[0506] (metal-free phosphorus compound 1H)

[0507] The metal-free phosphorus compound 1H is a compound represented by the above-mentioned general formula (1H).

[0508] In the general formula (1H), R 11H , R 12H and R 13H Each independently represents an organic group.

[0509] R 11H , R 12H and R 13H The organic group is a monovalent organic group, and examples thereof include the above-mentioned R 11D and R 12D Among the organic groups explained for the organic groups, monovalent aliphatic groups, alicyclic groups, aromatic groups and heterocyclic groups are preferably monovalent aliphatic groups. 11D and R 12D The same groups are described for the organic groups.

[0510] About R 11H , R 12H and R 13H The carbon number of the monovalent aliphatic group is preferably 1 or more, more preferably 2 or more, and further preferably 3 or more, from the viewpoint of reducing the oil absorption, easily obtaining excellent coating adaptability, and more effectively obtaining excellent battery performance. The upper limit is preferably 20 or less, more preferably 16 or less, further preferably 12 or less, and further preferably 10 or less.

[0511] The aliphatic group may be straight-chain or branched, preferably straight-chain. 11D and R 12D The aliphatic groups are the same.

[0512] In addition, about the11H , R 12H and R 13H The monovalent alicyclic group, aromatic group and heterocyclic group of the organic group as R 11D and R 12D The same applies to the alicyclic group, aromatic group and heterocyclic group in the organic group.

[0513] In addition, R 11H , R 12H and R 13H It may be an organic group having an oxygen atom, for example, a group having a group selected from the above-mentioned monovalent aliphatic group, alicyclic group, aromatic group, and heterocyclic group via an oxygen atom. In this case, as a monovalent organic group having a group via an oxygen atom, a group having an oxygen atom and an aliphatic group is preferred.

[0514] As such a metal-free phosphorus compound 1H represented by the general formula (1H), tri-n-octylphosphine oxide (in the general formula (1H), R 11H , R 12H and R 13H In addition, compounds having the structure based on this can also obtain the same effect.

[0515] (metal-free phosphorus compounds 2H)

[0516] The metal-free phosphorus compound 2H is a compound represented by the above-mentioned general formula (2H).

[0517] In the general formula (2H), R 21H , R 22H and R 23H Each independently represents an organic group.

[0518] R 21H , R 22H and R 23H The organic group is a monovalent organic group, and examples thereof include the above-mentioned R 11D and R 12D Among the organic groups explained with reference to the organic group of , monovalent aliphatic groups, alicyclic groups, aromatic groups and heterocyclic groups, monovalent aliphatic groups and aromatic groups are preferred. 11D and R 12D The same groups are described for the organic groups.

[0519] About R 21H , R 22H and R 23HThe carbon number of the monovalent aliphatic group is preferably 1 or more, more preferably 2 or more, and further preferably 3 or more, from the viewpoint of reducing the oil absorption, easily obtaining excellent coating adaptability, and more effectively obtaining excellent battery performance. The upper limit is preferably 20 or less, more preferably 16 or less, further preferably 12 or less, and further preferably 10 or less.

[0520] The aliphatic group may be straight-chain or branched, preferably straight-chain. 11D and R 12D The aliphatic groups are the same.

[0521] As R 21H , R 22H and R 23H The monovalent aromatic group of R 11D and R 12D Among the aromatic groups explained as aromatic groups, the aromatic groups having a monocyclic aromatic compound as a basic structure are preferably phenyl groups.

[0522] In addition, R 21H , R 22H and R 23H It may be an organic group having an oxygen atom, for example, a group having a group selected from the above-mentioned monovalent aliphatic group, alicyclic group, aromatic group, and heterocyclic group via an oxygen atom. In this case, as a monovalent organic group having a group via an oxygen atom, a group having an oxygen atom and an aliphatic group is preferred.

[0523] As such a metal-free phosphorus compound 2H represented by the general formula (2H), tri-n-octylphosphine (in the general formula (2H), R 21H , R 22H and R 23H is 1-octyl), triphenylphosphine (in the general formula (2H), R 21H , R 22H and R 23H In addition, compounds having the structure based on this can of course also obtain the same effect.

[0524] (metal-free phosphorus compound 3H)

[0525] The metal-free phosphorus compound 3H is a compound represented by the above-mentioned general formula (3H).

[0526] In the general formula (3H), R 31H , R 32H , R 35H and R 36H R each independently represents an organic group. 33H and R 34HEach independently represents a single bond or an organic group, X 31H represents a single bond or an oxygen atom. In addition, R 33H and R 34H At least one of R is an organic group, 33H With R 34H They may be bonded to each other to form a condensed ring.

[0527] R 31H , R 32H , R 35H and R 36H The organic group is a monovalent organic group, and examples thereof include the above-mentioned R 11D and R 12D The monovalent aliphatic group, alicyclic group, aromatic group and heterocyclic group in the organic group described for the organic group are preferably a monovalent aliphatic group or aromatic group, and more preferably a monovalent aromatic group. The monovalent aliphatic group, alicyclic group, aromatic group and heterocyclic group are the same as those in the above R 11D and R 12D The same groups are described for the organic groups.

[0528] As R 31H , R 32H , R 35H and R 36H The monovalent aromatic group of R 11D and R 12D Among the aromatic groups explained as aromatic groups, the aromatic groups having a monocyclic aromatic compound as a basic structure are preferably phenyl groups.

[0529] In addition, R 31H , R 32H , R 35H and R 36H It may be an organic group having an oxygen atom, for example, a group having a group selected from the above-mentioned monovalent aliphatic group, alicyclic group, aromatic group, and heterocyclic group via an oxygen atom. In this case, as the monovalent organic group having via an oxygen atom, a group having an oxygen atom and an aliphatic group, or a group having an oxygen atom and an aromatic group is preferred.

[0530] R 33H and R 34H The organic group is a divalent organic group, and examples thereof include the above-mentioned R 11D and R 12D The divalent aliphatic group, alicyclic group, aromatic group and heterocyclic group in the organic group described for the organic group are preferably a divalent aliphatic group or aromatic group, and more preferably a divalent aromatic group. 11D and R 12DThe same groups are described for the organic groups.

[0531] From the perspective of reducing oil absorption, easily obtaining excellent coating adaptability, and more effectively obtaining excellent battery performance, R 33H and R 34H The carbon number of the divalent aliphatic group is preferably 1 or more, more preferably 2 or more, further preferably 3 or more, and the upper limit is preferably 16 or less, more preferably 12 or less, further preferably 8 or less, and further preferably 6 or less.

[0532] The aliphatic group may be straight-chain or branched, preferably straight-chain. 11D and R 12D The aliphatic groups are the same.

[0533] As R 33H and R 34H The divalent aromatic group can be used as the above R 11D and R 12D The divalent aromatic group in the aromatic group described above as an aromatic group may be a group having as a chemical bond a portion obtained by removing two hydrogen atoms from the basic structure of the above-mentioned monocyclic aromatic compound, bonded polycyclic aromatic compound, or condensed polycyclic aromatic compound, and is preferably a group having as a chemical bond a portion obtained by removing two hydrogen atoms from the basic structure of the above-mentioned monocyclic aromatic compound or condensed polycyclic aromatic compound.

[0534] R 33H and R 34H At least one of the groups is an organic group.

[0535] R 33H With R 34H can be bonded to each other to form a condensed ring. In this case, X 31H As the condensed ring in this case, there can be exemplified the following: 11D and R 12D The condensed ring described in the alicyclic group, aromatic group and heterocyclic group.

[0536] In addition, in X 31H When R is an oxygen atom, 33H , X 31H With R 34H They may also be bonded to each other to form a condensed ring. In this case, the condensed ring may be exemplified by 11D and R 12D The oxygen-containing condensed polycyclic heterocyclic compound described in the heterocyclic group.

[0537] As such a metal-free phosphorus compound 3H represented by the general formula (3H), 1,4-bis(diphenylphosphino)butane (in the general formula (3H), R 31H , R 32H , R 35H and R 36H is phenyl, R 33H is 1,4-butanediyl, R 34H and X 31H is a single bond), bis[(2-diphenylphosphino)phenyl]ether (in the general formula (3H), R 31H , R 32H , R 35H and R 36H is phenyl, R 33H and R 34H is phenylenediyl, X 31H is an oxygen atom), 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (in the general formula (3H), R 31H , R 32H , R 35H and R 36H is phenyl, R 33H is xanthene-4,5-diyl, R 34H and X 31H is a single bond. In addition, it can also be said that R 33H is dihydrobenzopyranyl, R 34H is phenyl, R 33H With R 34H The compounds having the structure based on this can also obtain the same effect.

[0538] In the modified sulfide solid electrolyte of the present embodiment, the above-mentioned compound (H) can be used alone or in combination of two or more thereof, and at least one metal-free phosphorus compound selected from the metal-free phosphorus compound 1H represented by the above-mentioned general formula (1H), the metal-free phosphorus compound 2H represented by the general formula (2H), and the metal-free phosphorus compound 3H represented by the general formula (3H) can be used. For example, the compound represented by the above-mentioned general formula (1H) can be used alone, or two metal-free phosphorus compounds 1H represented by the above-mentioned general formula (1H) can be used in combination, and the same applies to the metal-free phosphorus compounds 2H and 3H represented by the above-mentioned general formulas (2H) and (3H). In addition, for example, the metal-free phosphorus compound 1H represented by the above-mentioned general formula (1H) can be used alone or in combination with the metal-free phosphorus compound 2H represented by the general formula (2H) alone or in combination with the metal-free phosphorus compound 2H represented by the general formula (2H). The same applies to the metal-free phosphorus compound 2H represented by the general formula (2H) and the metal-free phosphorus compound 3H represented by the general formula (3H), and the metal-free phosphorus compound 1H represented by the general formula (1H) and the metal-free phosphorus compound 3H represented by the general formula (3H).

[0539] From the viewpoint of reducing oil absorption, easily obtaining excellent coating suitability, and more effectively obtaining excellent battery performance, the molecular weight of compound (H) is preferably 3000 or less, more preferably 2000 or less, further preferably 1500 or less, and further preferably 1000 or less.

[0540] (Compound (I))

[0541] The compound (I) used in the modified sulfide solid electrolyte of the present embodiment is a metal-free boron compound. Compound (I) can be any metal-free boron compound. The metal-free boron compound of compound (I) is a compound that does not contain a metal atom and contains a boron atom. By having a boron atom as shown in the following general formula (II), it becomes easy to adhere to the sulfide solid electrolyte, so the oil absorption is reduced, it is easy to obtain excellent coating adaptability, and excellent battery performance can be obtained more effectively. That is, as compound (I), a metal-free boron compound represented by the following general formula (II) can be preferably exemplified.

[0542] [Chemistry 19]

[0543]

[0544] In the general formula (1I), R 11I , R 12I and R 13I Each independently represents an organic group.

[0545] R 11I , R 12Iand R 13I The organic group is a monovalent organic group, and examples thereof include the above-mentioned R 11D and R 12D Among the organic groups explained for the organic groups, monovalent aliphatic groups, alicyclic groups, aromatic groups and heterocyclic groups are preferably monovalent aliphatic groups. 11D and R 12D The same groups are described for the organic groups.

[0546] About R 11I , R 12I and R 13I The carbon number of the monovalent aliphatic group is preferably 1 or more, more preferably 2 or more, further preferably 4 or more, and further preferably 6 or more, from the viewpoint of reducing the oil absorption, easily obtaining excellent coating adaptability, and more effectively obtaining excellent battery performance. The upper limit is preferably 28 or less, more preferably 24 or less, further preferably 20 or less, and further preferably 18 or less.

[0547] The aliphatic group may be straight-chain or branched, preferably straight-chain. 11D and R 12D The aliphatic groups are the same.

[0548] In addition, R 11I , R 12I and R 13I An organic group having an oxygen atom is also preferred. Examples of organic groups having an oxygen atom include groups having a group selected from the above-mentioned monovalent aliphatic group, alicyclic group, aromatic group, and heterocyclic group via an oxygen atom. In this case, as a monovalent organic group having an oxygen atom, a group having an oxygen atom and an aliphatic group is preferred, and a group having an oxygen atom and an alkyl group, i.e., an alkoxy group, is particularly preferred. The carbon number of the aliphatic group is the same as that of the above R 11I , R 12I and R 13I The monovalent aliphatic groups of are preferably the same in carbon number.

[0549] As such a compound (I) represented by the general formula (1I), tri-n-octyl borate (in the general formula (1I), R 11I , R 12I and R 13I is octyloxy), tri-n-octadecyl borate (in the general formula (II), R 11I , R 12I and R 13I In addition, compounds having the structure based on this can also obtain the same effect.

[0550] In the modified sulfide solid electrolyte of the present embodiment, the above-mentioned compound (I) can be used alone or in combination of two or more.

[0551] (Content of compounds (A) to (I), etc.)

[0552] The content of at least two compounds selected from the above compounds (A) to (I) contained in the modified sulfide solid electrolyte of the present embodiment can vary depending on the type of compound used, and therefore cannot be generalized, but is preferably 0.03 parts by mass or more, more preferably 0.05 parts by mass, further preferably 0.1 parts by mass or more, and further preferably 0.5 parts by mass, relative to 100 parts by mass of the sulfide solid electrolyte, and the upper limit is preferably 25 parts by mass or less, and more preferably 20 parts by mass or less. If it is within the above range, the coating adaptability when applied as a paste can be efficiently improved, and excellent battery performance can be obtained more efficiently.

[0553] When at least two compounds selected from the compounds (A) to (I) used in the modified sulfide solid electrolyte of the present embodiment are used, the oil absorption is reduced, excellent coating suitability can be obtained, and excellent battery performance can be effectively obtained.

[0554] As described above, among these compounds (A) to (I), compound (B) is a compound having a more excellent effect on improving oxidation resistance among the above compounds (A) to (I), and the other compounds (A) and (C) to (I) are compounds having a more excellent effect on reducing oil absorption. Therefore, in order to improve coating adaptability by reducing oil absorption, improve battery performance by increasing the density of solid electrolyte, and improve performance such as oxidation resistance as one of battery performance, it is preferred to use a compound that is excellent in improving oxidation resistance and a compound that is excellent in reducing oil absorption in combination. More specifically, it is preferred to use at least one compound selected from compound (B) in combination with at least one compound selected from compounds (A) and (C) to (I), and it is more preferred to use at least one compound selected from compound (B) in combination with at least one compound selected from compounds (A), (C) and (F).

[0555] When a compound excellent in improving oxidation resistance (hereinafter also referred to as "compound α") and a compound excellent in reducing oil absorption (hereinafter also referred to as "compound β") are used in combination, the ratio of compound β to the total amount of compounds α and β is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 35% by mass or more, and further preferably 50% by mass or more, and the upper limit is preferably 95% by mass or less, more preferably 90% by mass or less, and further preferably 85% by mass or less. It is easy to strike a balance between reducing oil absorption and improving oxidation resistance at a higher level.

[0556] Regarding the above-mentioned compounds (A) to (I), the compounds for which the molecular weight is not particularly described (specifically, compounds (B) to (G) and (I), but excluding the epoxy compound 1B for which the number average molecular weight is described for compound (B)) are preferably compounds having a predetermined molecular weight from the viewpoint of easily obtaining excellent coating adaptability and more effectively obtaining excellent battery performance, as with the above-mentioned compound (H). Specifically, for these compounds, from the viewpoint of easily obtaining excellent coating adaptability and more effectively obtaining excellent battery performance, the molecular weight is preferably 3000 or less, more preferably 2000 or less, further preferably 1500 or less, and further preferably 1000 or less.

[0557] The content of at least one compound selected from compounds (A) to (I) and having a molecular weight of 3000 or less is preferably 90% by mass or more, more preferably 95% by mass or more, further preferably 99% by mass or more, and further preferably 100% by mass, relative to the total amount of at least one compound selected from compounds (A) to (I) contained in the modified sulfide solid electrolyte, that is, the total amount is compounds having a number average molecular weight of 3000 or less.

[0558] On the contrary, the content of at least one compound selected from compounds (A) to (I) and having a molecular weight exceeding 3000 is preferably 10% by mass or less, more preferably 5% by mass or less, further preferably 1% by mass or less, and further preferably 0% by mass, relative to the total amount of at least one compound selected from compounds (A) to (I) contained in the modified sulfide solid electrolyte. Compounds having a molecular weight exceeding 3000 are further preferably not contained.

[0559] (Manufacturing of sulfide solid electrolyte)

[0560] Next, the sulfide solid electrolyte forming the modified sulfide solid electrolyte of the present embodiment is described. The sulfide solid electrolyte that can be used in the present embodiment contains lithium atoms, sulfur atoms, phosphorus atoms, and halogen atoms, and has a BET specific surface area of ​​10 m 2 / g or more, it can be used without particular limitation, and a commercially available product can be used as it is or can be produced and used.

[0561] In the case of manufacturing and using a sulfide solid electrolyte that can be used in the present embodiment, a manufacturing method thereof is described. The sulfide solid electrolyte that can be used in the present embodiment can be obtained, for example, by the following manufacturing method: the manufacturing method includes mixing two or more raw materials selected from a compound containing at least one atom of a lithium atom, a sulfur atom, a phosphorus atom, and a halogen atom.

[0562] (raw material)

[0563] As the raw material, two or more compounds selected from compounds containing at least one atom of a lithium atom, a sulfur atom, a phosphorus atom, and a halogen atom can be used.

[0564] The compound that can be used as a raw material is a compound containing at least one of a lithium atom, a phosphorus atom, a sulfur atom and a halogen atom. More specifically, representative examples include: lithium sulfide; lithium halides such as lithium fluoride, lithium chloride, lithium bromide, and lithium iodide; alkali metal halides such as sodium iodide, sodium fluoride, sodium chloride, and sodium bromide; phosphorus sulfides such as phosphorus trisulfide (P2S3) and phosphorus pentasulfide (P2S5); various phosphorus fluorides (PF3, PF5), various phosphorus chlorides (PCl3, PCl5, P2Cl4), various phosphorus bromides (PBr3, PB r5), various phosphorus iodides (PI3, P2I4) and other phosphorus halides; thiophosphoryl fluoride (PSF3), thiophosphoryl chloride (PSCl3), thiophosphoryl bromide (PSBr3), thiophosphoryl iodide (PSI3), thiophosphoryl fluoride dichloride (PSCl2F), thiophosphoryl fluoride dibromide (PSBr2F) and other thiophosphoryl halides; and other raw materials composed of at least two atoms selected from the above four atoms; halogen monomers such as fluorine (F2), chlorine (Cl2), bromine (Br2), iodine (I2), preferably bromine (Br2) and iodine (I2).

[0565] Compounds other than the above that can be used as raw materials include, for example, compounds containing at least one atom selected from the above four atoms and atoms other than the four atoms. More specifically, examples include: lithium compounds such as lithium oxide, lithium hydroxide, and lithium carbonate; alkali metal sulfides such as sodium sulfide, potassium sulfide, rubidium sulfide, and cesium sulfide; metal sulfides such as silicon sulfide, germanium sulfide, boron sulfide, gallium sulfide, tin sulfide (SnS, SnS2), aluminum sulfide, and zinc sulfide; phosphoric acid compounds such as sodium phosphate and lithium phosphate; metal halides such as aluminum halides, silicon halides, germanium halides, arsenic halides, selenium halides, tin halides, antimony halides, tellurium halides, and bismuth halides; halogenated phosphorus oxides such as phosphorus oxychloride (POCl3) and phosphorus oxybromide (POBr3); and the like.

[0566] In this embodiment, from the viewpoint of more easily obtaining a sulfide solid electrolyte with high ionic conductivity, chlorine atoms, bromine atoms, and iodine atoms are preferred among the halogen atoms, and bromine atoms and iodine atoms are more preferred. In addition, these atoms can be used alone or in combination. That is, taking lithium halide as an example, lithium bromide can be used alone, lithium iodide can be used alone, or lithium bromide and lithium iodide can be used in combination.

[0567] In addition, from the same point of view, as compounds that can be used as raw materials, among the above, lithium sulfide is preferred; phosphorus sulfides such as phosphorus trisulfide (P2S3) and phosphorus pentasulfide (P2S5); halogen monomers such as fluorine (F2), chlorine (Cl2), bromine (Br2), and iodine (I2); lithium halides such as lithium fluoride, lithium chloride, lithium bromide, and lithium iodide. Among phosphorus sulfides, phosphorus pentasulfide is preferred; among halogen monomers, chlorine (Cl2), bromine (Br2), and iodine (I2) are preferred; and among lithium halides, lithium chloride, lithium bromide, and lithium iodide are preferred.

[0568] As combinations of compounds that can be used as raw materials, for example, combinations of lithium sulfide, phosphorus pentasulfide and lithium halides, and combinations of lithium sulfide, phosphorus pentasulfide and halogen monomers can be preferably mentioned. Lithium bromide, lithium iodide and lithium chloride are preferred as lithium halides, and chlorine, bromine and iodine are preferred as halogen monomers.

[0569] In the present embodiment, when lithium sulfide is used as the compound containing lithium atoms, the lithium sulfide is preferably in the form of particles.

[0570] The average particle size of lithium sulfide particles (D 50 ) is preferably 10 μm to 2000 μm, more preferably 30 μm to 1500 μm, and even more preferably 50 μm to 1000 μm. In this specification, the average particle size (D 50) is the particle size when the particle size distribution cumulative curve is drawn from the smallest particle to 50% of the total, and the volume distribution is, for example, the average particle size that can be measured using a laser diffraction / scattering particle size distribution measuring device. In addition, among the substances exemplified as the above-mentioned raw materials, the solid raw material preferably has an average particle size of the same degree as the above-mentioned lithium sulfide particles, that is, the average particle size is preferably within the same range as the average particle size of the above-mentioned lithium sulfide particles.

[0571] When lithium sulfide, phosphorus pentasulfide and lithium halide are used as raw materials, from the viewpoint of obtaining higher chemical stability and the viewpoint of increasing the PS4 fraction and obtaining high ion conductivity, the ratio of lithium sulfide to the total of lithium sulfide and phosphorus pentasulfide is preferably 60 mol% or more, more preferably 65 mol% or more, further preferably 68 mol% or more, and the upper limit is preferably 80 mol% or less, more preferably 78 mol% or less, further preferably 76 mol% or less.

[0572] When lithium sulfide, phosphorus pentasulfide, lithium halide, and other raw materials used as needed are used, the content of lithium sulfide and phosphorus pentasulfide relative to the total of these is preferably 60 mol% or more, more preferably 65 mol% or more, and further preferably 70 mol% or more, and the upper limit is preferably 100 mol% or less, more preferably 90 mol% or less, and further preferably 80 mol% or less.

[0573] In addition, when lithium bromide and lithium iodide are used in combination as lithium halides, from the viewpoint of increasing the PS4 fraction and obtaining high ion conductivity, the ratio of lithium bromide to the total of lithium bromide and lithium iodide is preferably 1 mol% or more, more preferably 20 mol% or more, further preferably 40 mol% or more, further preferably 50 mol% or more, and the upper limit is preferably 99 mol% or less, more preferably 90 mol% or less, further preferably 80 mol% or less, further preferably 70 mol% or less.

[0574] When a halogen monomer is used as a raw material and lithium sulfide and phosphorus pentasulfide are used, the ratio of the mole number of lithium sulfide obtained by removing the same mole number of lithium sulfide as the mole number of the halogen monomer to the total mole number of lithium sulfide and phosphorus pentasulfide obtained by removing the same mole number of lithium sulfide as the mole number of the halogen monomer is preferably in the range of 60 to 90%, more preferably in the range of 65 to 85%, further preferably in the range of 68 to 82%, further preferably in the range of 72 to 78%, and particularly preferably in the range of 73 to 77%. This is because higher ion conductivity can be obtained if these ratios are used. In addition, from the same viewpoint, when lithium sulfide, phosphorus pentasulfide and a halogen monomer are used, the content of the halogen monomer relative to the total amount of lithium sulfide, phosphorus pentasulfide and the halogen monomer is preferably 1 to 50 mol%, more preferably 2 to 40 mol%, further preferably 3 to 25 mol%, and further preferably 3 to 15 mol%.

[0575] When lithium sulfide, phosphorus pentasulfide, a halogen monomer and a lithium halide are used, the content of the halogen monomer relative to the total amount of these (α mol%) and the content of the lithium halide relative to the total amount of these (β mol%) preferably satisfy the following formula (1), more preferably satisfy the following formula (2), further preferably satisfy the following formula (3), and further preferably satisfy the following formula (4).

[0576] 2≤2α+β≤100…(1)

[0577] 4≤2α+β≤80…(2)

[0578] 6≤2α+β≤50…(3)

[0579] 6≤2α+β≤30…(4)

[0580] (mix)

[0581] The mixing of two or more raw materials selected from compounds containing at least one of lithium atoms, sulfur atoms, phosphorus atoms and halogen atoms can be performed by mixing the raw materials using, for example, a mixer, a stirrer, a pulverizer or the like.

[0582] This is because the raw materials can be mixed even when a stirrer is used, and when a pulverizer is used, the raw materials are pulverized and mixed at the same time. That is, it can be said that the sulfide solid electrolyte used in the present embodiment can be mixed by stirring, mixing, pulverizing, or any combination of two or more raw materials selected from compounds containing at least one of lithium atoms, sulfur atoms, phosphorus atoms, and halogen atoms.

[0583] As agitators and mixers, for example, a mechanical stirring mixer having stirring blades in a reaction tank and capable of stirring (also referred to as mixing brought by stirring, stirring and mixing) can be exemplified. As mechanical stirring mixers, high-speed stirring mixers, double-arm mixers, etc. can be exemplified. In addition, as high-speed stirring mixers, vertical axis rotating mixers, horizontal axis rotating mixers, etc. can be exemplified, and any type of mixer can also be used.

[0584] The shape of the stirring blade used in the mechanical stirring mixer may be a blade type, an arm type, an anchor type, a paddle type, a stirring paddle type, a belt type, a multi-stage blade type, a double-arm type, a bucket type, a double-shaft blade type, a flat blade type, a C-blade type, etc. From the viewpoint of more efficiently promoting the reaction of the raw materials, a bucket type, a flat blade type, a C-blade type, an anchor type, a paddle type, a stirring paddle type is preferred, and an anchor type, a paddle type, a stirring paddle type is more preferred.

[0585] When a mechanical stirring mixer is used, the rotation speed of the stirring blade can be appropriately adjusted according to the capacity, temperature, shape of the stirring blade, etc. of the fluid in the reaction tank, without any particular limitation, and is usually set to about 5 rpm to about 400 rpm. From the viewpoint of more efficiently promoting the reaction of the raw materials, it is preferably 10 rpm to 300 rpm, more preferably 15 rpm to 250 rpm, and further preferably 20 rpm to 200 rpm.

[0586] The temperature conditions for mixing using a mixer are not particularly limited, and are, for example, usually -30 to 120° C., preferably -10 to 100° C., more preferably 0 to 80° C., and further preferably 10 to 60° C. The mixing time is usually 0.1 to 500 hours, and is preferably 1 to 450 hours, more preferably 10 to 425 hours, further preferably 20 to 400 hours, and further preferably 40 to 375 hours from the viewpoint of making the dispersion state of the raw materials more uniform and promoting the reaction.

[0587] The method of mixing with pulverization using a pulverizer is a method conventionally adopted as a solid phase method (mechanical grinding method). As the pulverizer, for example, a media type pulverizer using pulverizing media can be used.

[0588] The media pulverizer is roughly divided into a container-driven pulverizer and a media-stirring pulverizer. As the container-driven pulverizer, a stirring tank, a crushing tank, or a ball mill or a bead mill in which these are combined can be cited. In addition, as the media-stirring pulverizer, there can be cited: impact pulverizers such as a cutter mill, a hammer mill, and a pin mill; tower-type pulverizers such as a tower mill; stirring tank-type pulverizers such as a grinder, a wet sand mill (aquamizer), and a sand mill; flow-through trough-type pulverizers such as a viscose mill and a coarse crusher; flow-through tube-type pulverizers; annular pulverizers such as a combined ball mill; a continuous dynamic pulverizer; various pulverizers such as a single-shaft or multi-shaft kneading machine. Among them, if the ease of adjusting the particle size of the obtained sulfide is considered, the ball mill and bead mill exemplified as the container-driven pulverizer are preferred, and a planetary pulverizer is preferred.

[0589] These pulverizers can be appropriately selected according to the desired scale, etc. For a relatively small scale, a container-driven pulverizer such as a ball mill or a bead mill can be used. In the case of large-scale or mass production, other types of pulverizers can also be used.

[0590] Furthermore, as described later, when the mixture is in a liquid state accompanied with a liquid such as a solvent or in a slurry state during mixing, a wet pulverizer capable of wet pulverization is preferred.

[0591] As wet pulverizers, wet bead mills, wet ball mills, wet vibration mills, etc. can be representatively cited. From the perspective of being able to freely adjust the conditions of the pulverization operation and being easy to handle materials with smaller particle sizes, wet bead mills using beads as pulverization media are preferred. In addition, dry pulverizers such as dry bead mills, dry ball mills, dry vibration mills, and dry non-media pulverizers such as jet mills can also be used.

[0592] In addition, when the object to be mixed is in a liquid state or a slurry state, a flow-through pulverizer can be used, which can be circulated as needed. Specifically, a pulverizer that circulates between a pulverizer (pulverizing mixer) for pulverizing slurry and a temperature-maintaining tank (reaction container) can be cited.

[0593] The size of the beads or balls used in the above-mentioned ball mill or bead mill can be appropriately selected according to the desired particle size, processing volume, etc. For example, the diameter of the beads is usually 0.05 mmφ or more, preferably 0.1 mmφ or more, more preferably 0.3 mmφ or more, and the upper limit is usually 5.0 mmφ or less, preferably 3.0 mmφ or less, and more preferably 2.0 mmφ or less. In addition, the diameter of the balls is usually 2.0 mmφ or more, preferably 2.5 mmφ or more, and more preferably 3.0 mmφ or more, and the upper limit is usually 20.0 mmφ or less, preferably 15.0 mmφ or less, and more preferably 10.0 mmφ or less.

[0594] In addition, examples of the material include metals such as stainless steel, chrome steel, and tungsten carbide; ceramics such as zirconium oxide and silicon nitride; and minerals such as agate.

[0595] When a ball mill or a bead mill is used, the rotation speed cannot be generally specified because it varies according to the scale of treatment, but is usually 10 rpm or more, preferably 20 rpm or more, and more preferably 50 rpm or more, and the upper limit is usually 1,000 rpm or less, preferably 900 rpm or less, more preferably 800 rpm or less, and further preferably 700 rpm or less.

[0596] The pulverization time in this case cannot be generally stated because it varies depending on the scale of treatment, but is usually 0.5 hours or more, preferably 1 hour or more, more preferably 5 hours or more, and further preferably 10 hours or more, and the upper limit is usually 100 hours or less, preferably 72 hours or less, more preferably 48 hours or less, and further preferably 36 hours or less.

[0597] By selecting the size and material of the medium (beads, balls) used, the rotation speed and time of the rotor, etc., mixing, stirring, pulverization, or any combination of these can be performed, and the particle size of the obtained sulfide can be adjusted.

[0598] (Solvent)

[0599] When the above-mentioned mixing is performed, a solvent may be added to the above-mentioned raw materials for mixing. As the solvent, various solvents called organic solvents and the like can be widely used.

[0600] As the solvent, a wide range of solvents conventionally used in the production of solid electrolytes can be adopted, and examples thereof include hydrocarbon solvents such as aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, and aromatic hydrocarbon solvents.

[0601] Examples of aliphatic hydrocarbons include hexane, pentane, 2-ethylhexane, heptane, octane, decane, undecane, dodecane and tridecane. Examples of alicyclic hydrocarbons include cyclohexane and methylcyclohexane. Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, mesitylene, ethylbenzene, tert-butylbenzene, trifluoromethylbenzene and nitrobenzene.

[0602] In addition to the above-mentioned hydrocarbon solvents, solvents containing atoms other than carbon atoms and hydrogen atoms, such as nitrogen atoms, oxygen atoms, sulfur atoms, halogen atoms and other heteroatoms, can also be exemplified. Such solvents have the property of easily forming complexes with compounds containing lithium atoms, phosphorus atoms, sulfur atoms and halogen atoms used as raw materials (hereinafter, such solvents are also referred to as "complexing agents"), and have the property of making halogen atoms easily remain in the structure of the sulfide solid electrolyte, so they are useful in obtaining higher ion conductivity. As such complexing agents, in addition to ether solvents and ester solvents containing oxygen atoms as heteroatoms, alcohol solvents, aldehyde solvents and ketone solvents can also be preferably exemplified.

[0603] As the ether solvent, for example, preferably there can be mentioned aliphatic ethers such as dimethyl ether, diethyl ether, tert-butyl methyl ether, dimethoxymethane, dimethoxyethane, diethylene glycol dimethyl ether (diglyme), triethylene glycol dimethyl ether (triglyme) or diethylene glycol, triethylene glycol; alicyclic ethers such as ethylene oxide, propylene oxide, tetrahydrofuran, tetrahydropyran, dimethoxytetrahydrofuran, cyclopentyl methyl ether, dioxane; heterocyclic ethers such as furan, benzofuran, benzopyran; aromatic ethers such as methyl phenyl ether (anisole), ethyl phenyl ether, dibenzyl ether, diphenyl ether.

[0604] As the ester solvent, for example, preferably exemplified are methyl formate, ethyl formate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate; aliphatic esters such as methyl propionate, ethyl propionate, dimethyl oxalate, diethyl oxalate, dimethyl malonate, diethyl malonate, dimethyl succinate, diethyl succinate; alicyclic esters such as methyl cyclohexanecarboxylate, ethyl cyclohexanecarboxylate, dimethyl cyclohexanedicarboxylate; heterocyclic esters such as methyl pyridinecarboxylate, methyl pyrimidinecarboxylate, acetyl lactone, propiolactone, butyrolactone, valerolactone; aromatic esters such as methyl benzoate, ethyl benzoate, dimethyl phthalate, diethyl phthalate, butyl benzyl phthalate, dicyclohexyl phthalate, trimethyl trimellitate, triethyl trimellitate.

[0605] In addition, preferably, there can be mentioned alcohol solvents such as ethanol and butanol; aldehyde solvents such as formaldehyde, acetaldehyde and dimethylformamide; ketone solvents such as acetone and methyl ethyl ketone.

[0606] Examples of the solvent containing a nitrogen atom as a hetero atom include solvents having a group containing a nitrogen atom such as an amino group, an amide group, a nitro group or a nitrile group.

[0607] For example, as the solvent having an amino group, preferably exemplified are aliphatic amines such as ethylenediamine, diaminopropane, dimethylethylenediamine, diethylethylenediamine, dimethyldiaminopropane, tetramethyldiaminomethane, tetramethylethylenediamine (TMEDA), and tetramethyldiaminopropane (TMPDA); alicyclic amines such as cyclopropanediamine, cyclohexanediamine, and bisaminomethylcyclohexane; heterocyclic amines such as isophoronediamine, piperazine, dipiperidylpropane, and dimethylpiperazine; and aromatic amines such as phenylenediamine, toluenediamine, naphthalenediamine, methylphenylenediamine, dimethylnaphthalenediamine, dimethylphenylenediamine, tetramethylphenylenediamine, and tetramethylnaphthalenediamine.

[0608] Also preferably, there can be mentioned nitrile solvents such as acetonitrile and acrylonitrile; and solvents containing nitrogen atoms such as dimethylformamide, nitrobenzene and dimethylacetamide.

[0609] As the solvent containing a halogen atom as a hetero atom, preferably, chloroform, carbon tetrachloride, dichloromethane, chlorobenzene, dichlorobenzene, trifluoromethylbenzene, chlorotoluene, bromobenzene and the like are exemplified.

[0610] Furthermore, as the solvent containing a sulfur atom, dimethyl sulfoxide, carbon disulfide, etc. can be preferably exemplified.

[0611] When using a solvent, the usage amount of the solvent is preferably more than 100 mL relative to the total amount 1kg of the raw material, more preferably more than 200 mL, further preferably more than 250 mL, more preferably more than 300 mL, and as the upper limit is preferably below 3000 mL, more preferably below 2500 mL, further preferably below 2000 mL, and further preferably below 1550 mL. If the usage amount of the solvent is within the above range, the raw material reaction can be efficiently made.

[0612] (dry)

[0613] In the case of using a solvent for mixing, the fluid (usually a slurry) obtained by mixing may be dried after mixing. In the case of using a complexing agent as a solvent, the sulfide solid electrolyte can be obtained by removing the complexing agent from the complex containing the complexing agent, and in the case of using a complexing agent and a solvent in combination, by removing the complexing agent from the complex containing the complexing agent and removing the solvent, and in the case of using a solvent other than a complexing agent, by removing the solvent. The obtained sulfide solid electrolyte exhibits ionic conductivity caused by lithium atoms.

[0614] The fluid obtained by mixing can be dried at a temperature corresponding to the type of solvent, for example, at a temperature equal to or higher than the boiling point of the complexing agent.

[0615] Furthermore, the complexing agent and the solvent used as required can be dried by volatilizing them by using a vacuum pump or the like under reduced pressure (vacuum drying) at usually 5 to 100°C, preferably 10 to 85°C, more preferably 15 to 70°C, and still more preferably around room temperature (23°C) (e.g. around room temperature ±5°C).

[0616] The fluid may also be dried by filtration using a glass filter, solid-liquid separation by decantation, or solid-liquid separation using a centrifuge. When a solvent other than a complexing agent is used, a sulfide solid electrolyte can be obtained by solid-liquid separation. In addition, when a complexing agent is used as a solvent, after solid-liquid separation, drying under the above-mentioned temperature conditions is performed to remove the complexing agent introduced into the complex.

[0617] Specifically, as a solid-liquid separation, the fluid is transferred to a container, and after the sulfide (or the complex (a substance that can be called a precursor of a sulfide solid electrolyte)) is precipitated, it is easier to remove the complexing agent and solvent that become the supernatant by decantation or by filtering using, for example, a glass filter with a pore size of about 10 to 200 μm, preferably 20 to 150 μm.

[0618] Drying may be performed after mixing and before the hydrogen treatment described below, or after the hydrogen treatment.

[0619] The sulfide solid electrolyte obtained by the above mixing, or the sulfide solid electrolyte obtained by removing the solvent by the above drying when a solvent is used, expresses ion conductivity due to lithium atoms.

[0620] The sulfide solid electrolyte obtained by the above mixing basically becomes an amorphous sulfide solid electrolyte (glass component) unless the mixture is pulverized to a degree of crystallization using a pulverizer, for example.

[0621] The sulfide solid electrolyte obtained by the above mixing may be an amorphous sulfide solid electrolyte (glass component) or a crystalline sulfide solid electrolyte, and can be appropriately selected as desired. When a crystalline sulfide solid electrolyte is produced, the amorphous sulfide solid electrolyte obtained by the above mixing is heated to produce a crystalline sulfide solid electrolyte.

[0622] As a sulfide solid electrolyte, in order to adjust the particle size of the powder of the crystalline sulfide solid electrolyte, after subjecting it to a treatment such as pulverization described later, a crystalline sulfide solid electrolyte having an amorphous component (glass component) formed on its surface may be included. Therefore, the sulfide solid electrolyte containing an amorphous component also includes an amorphous sulfide solid electrolyte or a crystalline sulfide solid electrolyte having an amorphous component formed on its surface.

[0623] (heating)

[0624] When a crystalline sulfide solid electrolyte is produced, heating may be further included. When an amorphous sulfide solid electrolyte (glass component) is obtained by the above mixing, a crystalline sulfide solid electrolyte can be obtained by heating, and when a crystalline sulfide solid electrolyte is obtained, a crystalline sulfide solid electrolyte with improved crystallinity can be obtained.

[0625] In addition, when a complexing agent is used as a solvent during mixing, although a complex containing the complexing agent is formed, the complexing agent can be removed from the complex by heating without the above-mentioned drying to obtain a sulfide solid electrolyte. Depending on the heating conditions, an amorphous substance can be made, and a crystalline substance can be made.

[0626] Regarding the heating temperature, for example, in the case of obtaining an amorphous sulfide solid electrolyte, the heating temperature may be determined according to the structure of the crystalline sulfide solid electrolyte obtained by heating the amorphous sulfide solid electrolyte. Specifically, the amorphous sulfide solid electrolyte is subjected to differential thermal analysis (DTA) using a differential thermal analyzer (DTA apparatus) under a temperature increase condition of 10°C / min, and the temperature of the peak top of the exothermic peak observed on the lowest temperature side is preferably set to a range of 5°C or less, more preferably 10°C or less, and further preferably 20°C or less, with the lower limit not particularly limited, but may be set to a temperature of the peak top of the exothermic peak observed on the lowest temperature side of about -40°C or more. By setting the temperature in such a range, an amorphous sulfide solid electrolyte can be obtained more efficiently and reliably. The heating temperature for obtaining an amorphous sulfide solid electrolyte varies depending on the structure of the obtained crystalline sulfide solid electrolyte and cannot be generally specified, but is usually preferably 135°C or lower, more preferably 130°C or lower, and further preferably 125°C or lower. The lower limit is not particularly limited, but is preferably 90°C or higher, more preferably 100°C or higher, and further preferably 105°C or higher.

[0627] In addition, when heating an amorphous sulfide solid electrolyte to obtain a crystalline sulfide solid electrolyte, the heating temperature may be determined according to the structure of the crystalline sulfide solid electrolyte, and is preferably higher than the above-mentioned heating temperature for obtaining an amorphous sulfide solid electrolyte. Specifically, the amorphous sulfide solid electrolyte is subjected to differential thermal analysis (DTA) using a differential thermal analyzer (DTA device) under a temperature increase condition of 10°C / min, and the temperature of the peak top of the exothermic peak observed on the lowest temperature side is preferably set to 5°C or more, more preferably 10°C or more, and further preferably 20°C or more. The upper limit is not particularly limited, but may be about 40°C or less. By setting the temperature in such a range, a crystalline sulfide solid electrolyte can be obtained more efficiently and reliably. The heating temperature for obtaining a crystalline sulfide solid electrolyte varies depending on the composition and structure of the obtained crystalline sulfide solid electrolyte and cannot be generally specified, but is usually preferably 130° C. or higher, more preferably 135° C. or higher, and further preferably 140° C. or higher. The upper limit is not particularly limited, but is preferably 600° C. or lower, more preferably 550° C. or lower, and further preferably 500° C. or lower.

[0628] The heating time is not particularly limited as long as it is a time for obtaining the desired amorphous sulfide solid electrolyte or crystalline sulfide solid electrolyte, and is, for example, preferably 1 minute or more, more preferably 10 minutes or more, further preferably 30 minutes or more, and further preferably 1 hour or more. In addition, the upper limit of the heating time is not particularly limited, but is preferably 24 hours or less, more preferably 10 hours or less, further preferably 5 hours or less, and further preferably 3 hours or less.

[0629] In addition, heating is preferably performed in an inert gas atmosphere (e.g., a nitrogen atmosphere, an argon atmosphere) or in a reduced pressure atmosphere (particularly in a vacuum). For example, an inert gas atmosphere containing a certain concentration of hydrogen may also be used. This is because it is possible to prevent degradation (e.g., oxidation) of the crystalline sulfide solid electrolyte.

[0630] The heating method is not particularly limited, and examples thereof include methods using a hot plate, a vacuum heating device, an argon atmosphere furnace, a firing furnace, etc. In addition, in industry, a horizontal dryer or a horizontal vibrating fluidized dryer having a heating unit and a feeding mechanism can also be used, and the method can be selected according to the amount of heating treatment.

[0631] (Sulfide solid electrolyte)

[0632] As described above, the sulfide solid electrolyte used in the present embodiment may be a commercially available product or a manufactured sulfide solid electrolyte.

[0633] The sulfide solid electrolyte obtained by the above method is an amorphous (glass component) or crystalline sulfide solid electrolyte containing lithium atoms, sulfur atoms, phosphorus atoms, and halogen atoms, and is preferably used as the sulfide solid electrolyte in the present embodiment.

[0634] (BET specific surface area)

[0635] Regarding the specific surface area of ​​the sulfide solid electrolyte used in this embodiment, the BET specific surface area is 10 m 2 / g or more. Although the modified sulfide solid electrolyte of this embodiment has a large specific surface area as described above, it has excellent coating adaptability when applied as a paste and can effectively demonstrate excellent battery performance. The higher the BET specific surface area of ​​the sulfide solid electrolyte, the more the advantage of this effect can be further demonstrated. From this point of view, the BET specific surface area is preferably 12m 2 / g or more, more preferably 15m 2 / g or more, more preferably 20m 2 From the same point of view, there is no particular upper limit, but it is actually 100 m 2 / g or less, preferably 75m 2 / g or less, more preferably 50m 2 / g or less.

[0636] In this specification, the BET specific surface area is a specific surface area measured using krypton gas as an adsorbent in accordance with JIS Z 8830:2013 (method for measuring specific surface area of ​​powders (solids) by gas adsorption).

[0637] (Amorphous sulfide solid electrolyte)

[0638] As the amorphous sulfide solid electrolyte obtained by the above method, it contains lithium atoms, sulfur atoms, phosphorus atoms and halogen atoms. As representative amorphous sulfide solid electrolytes, for example, solid electrolytes composed of lithium sulfide, phosphorus sulfide and lithium halide, such as Li2S-P2S5-LiI, Li2S-P2S5-LiCl, Li2S-P2S5-LiBr, Li2S-P2S5-LiI-LiBr, etc., can be preferably exemplified; and solid electrolytes such as Li2S-P2S5-Li2O-LiI, Li2S-SiS2-P2S5-LiI, etc., which contain other atoms such as oxygen atoms and silicon atoms. From the viewpoint of obtaining higher ionic conductivity, solid electrolytes composed of lithium sulfide, phosphorus sulfide and lithium halide, such as Li2S-P2S5-LiI, Li2S-P2S5-LiCl, Li2S-P2S5-LiBr, Li2S-P2S5-LiI-LiBr, etc., can be preferably exemplified.

[0639] The types of atoms constituting the amorphous sulfide solid electrolyte can be confirmed by, for example, an inductively coupled plasma (ICP) emission spectrometer.

[0640] The shape of the amorphous sulfide solid electrolyte is not particularly limited, and may be, for example, a particle shape. The average particle size (D 50 ) For example, the range of 0.01 μm to 500 μm and 0.1 to 200 μm can be exemplified.

[0641] (Crystalline sulfide solid electrolyte)

[0642] The crystalline sulfide solid electrolyte obtained by the above method can be a so-called glass ceramic obtained by heating an amorphous solid electrolyte to a temperature above the crystallization temperature. As its crystal structure, Li3PS4 crystal structure, Li4P2S6 crystal structure, Li7PS6 crystal structure, Li7P3S 11 A crystal structure, a crystal structure having peaks near 2θ=20.2° and 23.6° (for example, Japanese Patent Application Laid-Open No. 2013-16423), and the like.

[0643] In addition, Li 4-x Ge 1-x P x The S4 type sulfide crystalline lithium superion conductor region II (thio-LISICON Region II) type crystal structure (see Kanno et al., Journal of The Electrochemical Society, 148 (7) A742-746 (2001)), and Li 4-x Ge 1-x P x S4 type thio-LISICON Region II type crystal structure (see Solid State Ionics, 177 (2006), 2721-2725). From the perspective of obtaining higher ionic conductivity, the crystal structure of the crystalline sulfide solid electrolyte obtained by the manufacturing method of this embodiment is preferably a thio-LISICON Region II type crystal structure among the above. Here, "thio-LISICON Region II type crystal structure" means Li 4-x Ge 1-x P x S4-type sulfide crystalline lithium superion conductor region II (thio-LISICON Region II) crystal structure, and Li 4-x Ge 1-x Px Any crystal structure similar to the S4 type thio-LISICON Region II type crystal structure. In addition, the crystalline sulfide solid electrolyte obtained by the manufacturing method of this embodiment can be a crystalline sulfide solid electrolyte having the above-mentioned thio-LISICON Region II type crystal structure, or it can be a crystalline sulfide solid electrolyte having the thio-LISICON Region II type crystal structure as the main crystal. From the viewpoint of obtaining higher ionic conductivity, it is preferred to have the thio-LISICON Region II type crystal structure as the main crystal. In this specification, "having as the main crystal" means that the proportion of the crystal structure as the object in the crystal structure is 80% or more, preferably 90% or more, and more preferably 95% or more. In addition, from the viewpoint of obtaining higher ionic conductivity, the crystalline sulfide solid electrolyte obtained by the manufacturing method of this embodiment preferably does not contain crystalline Li3PS4 (β-Li3PS4).

[0644] In the X-ray diffraction measurement using CuKα rays, the diffraction peaks of the Li3PS4 crystal structure appear, for example, at 2θ=17.5°, 18.3°, 26.1°, 27.3°, and 30.0°; the diffraction peaks of the Li4P2S6 crystal structure appear, for example, at 2θ=16.9°, 27.1°, and 32.5°; the diffraction peaks of the Li7PS6 crystal structure appear, for example, at 2θ=15.3°, 25.2°, 29.6°, and 31.0°; and the diffraction peaks of the Li7P3S 11 The diffraction peaks of the crystal structure appear near 2θ=17.8°, 18.5°, 19.7°, 21.8°, 23.7°, 25.9°, 29.6°, and 30.0°, for example. 4-x Ge 1-x P x The diffraction peaks of the S4-type sulfide crystalline lithium superion conductor region II (thio-LISICON Region II) crystal structure appear near 2θ=20.1°, 23.9°, and 29.5°, which are similar to Li 4-x Ge 1-x P x The diffraction peaks of the S4 type thio-LISICON Region II-type crystal structure appear near 2θ=20.2 and 23.6°, for example. These peak positions may fluctuate within a range of ±0.5°.

[0645] As described above, when obtaining the crystal structure of the sulfide crystalline lithium superionic conductor region II in the present embodiment, it is preferably free of crystalline Li3PS4 (β-Li3PS4). The sulfide solid electrolyte obtained by the manufacturing method of the present embodiment does not have diffraction peaks at 2θ = 17.5° and 26.1° that can be observed in crystalline Li3PS4, or even if it has them, it only has a level where the detected peaks are extremely small compared to the diffraction peaks of the crystal structure of the sulfide crystalline lithium superionic conductor region II.

[0646] The above-mentioned crystal structure represented by the composition formula Li 7-x P 1- y Si y S6 and Li 7+x P 1-y Si y S6 (x is -0.6 to 0.6, y is 0.1 to 0.6) is cubic or orthorhombic, preferably cubic, and in X-ray diffraction measurement using CuKα rays, it mainly has peaks appearing at positions of 2θ = 15.5°, 18.0°, 25.0°, 30.0°, 31.4°, 45.3°, 47.0° and 52.0°. The above-mentioned crystal structure represented by the composition formula Li 7-x-2y PS 6-x-y Cl x (0.8 ≤ x ≤ 1.7, 0 < y ≤ -0.25x + 0.5) is preferably cubic, and in X-ray diffraction measurement using CuKα rays, it mainly has peaks appearing at positions of 2θ = 15.5°, 18.0°, 25.0°, 30.0°, 31.4°, 45.3°, 47.0° and 52.0°. In addition, the above-mentioned crystal structure represented by the composition formula Li 7-x PS 6-x Ha x (Ha is Cl or Br, x is preferably 0.2 to 1.8) is preferably cubic, and in X-ray diffraction measurement using CuKα rays, it mainly has peaks appearing at positions of 2θ = 15.5°, 18.0°, 25.0°, 30.0°, 31.4°, 45.3°, 47.0° and 52.0°. These crystal structures that basically have the structural framework of Li7PS6 are also called argyrodite-type crystal structures.

[0647] In addition, these peak positions can fluctuate within a range of ±0.5°.

[0648] As for the shape of the crystalline sulfide solid electrolyte, there is no particular limitation, and for example, particulate form can be cited. The average particle size (D 50) For example, the range of 0.01 μm to 500 μm and 0.1 to 200 μm can be exemplified.

[0649] (Properties of modified sulfide solid electrolyte)

[0650] The BET specific surface area of ​​the modified sulfide solid electrolyte of this embodiment is 10 m 2 / g or more, having a larger specific surface area. The higher the BET specific surface area of ​​the sulfide solid electrolyte, the more advantageous this effect can be shown. From this point of view, the BET specific surface area is preferably 12 m 2 / g or more, more preferably 15m 2 / g or more, more preferably 20m 2 From the same point of view, there is no particular upper limit, but it is actually 100 m 2 / g or less, preferably 75m 2 / g or less, more preferably 50m 2 / g or less.

[0651] Even if lithium halide is attached to the surface, it will not have a significant effect on the BET specific surface area of ​​the sulfide solid electrolyte. The BET specific surface area of ​​the sulfide solid electrolyte used in this embodiment is substantially the same as the BET specific surface area of ​​the modified sulfide solid electrolyte. 2 / g or more sulfide solid electrolyte as the sulfide solid electrolyte, the BET specific surface area of ​​the modified sulfide solid electrolyte will naturally become 10m 2 / g or above.

[0652] Regarding the oil absorption of the modified sulfide solid electrolyte of the present embodiment, the BET specific surface area is large as described above, but due to the effect of the compounds (A) to (I) attached to the surface, it is usually small and is 1.10 mL / g or less, and further 1.00 mL / g or less, 0.95 mL / g or less, 0.90 mL / g or less, 0.85 mL / g or less, 0.80 mL / g or less, and 0.75 mL / g or less. Although the modified sulfide solid electrolyte of the present embodiment has a large BET specific surface area, due to the small oil absorption, when it is made into a paste, the increase in the viscosity of the paste can be suppressed, and the coating adaptability during coating is excellent, and there is no need to use a solvent or the like to suppress the increase in the viscosity of the paste, so it is easy to obtain excellent battery performance.

[0653] In this specification, regarding the oil absorption, 1 g of the modified sulfide solid electrolyte is used as a sample, 1 drop of butyl butyrate is added to a mortar or the like, and then stirred with a spatula, and this operation is repeated until the sample becomes a paste, and the total amount of butyl butyrate added is defined as the oil absorption (mL / g). Here, "paste" refers to a state of "a substance that can be extended without breaking or becoming broken and slightly adheres to a measuring plate" as specified in "7.2 Measurement" of JIS K5101-13-1:2004 (Testing Methods for Pigments - Part 13: Oil Absorption - Section 1: Refined Linseed Oil Method).

[0654] The index of the oil absorption calculated by the following mathematical formula is preferably as small as possible, and is usually 90% or less, further 85% or less, 80% or less, 75% or less, or 70% or less. The lower limit is not particularly limited, but is usually 50% or more.

[0655] Oil absorption index (%) = Oil absorption B / Oil absorption A×100

[0656] Oil absorption A: Oil absorption of sulfide solid electrolyte before modification (mL / g)

[0657] Oil absorption B: Oil absorption of modified sulfide solid electrolyte (mL / g)

[0658] The modified sulfide solid electrolyte of this embodiment generally has an ion conductivity of 0.5 mS / cm or more, and further has an ion conductivity of 1.0 mS / cm or more, 1.5 mS / cm or more, 1.6 mS / cm or more, or 1.7 mS / cm or more, and has extremely high ion conductivity, and can obtain a lithium battery with excellent battery performance.

[0659] Furthermore, the modified sulfide solid electrolyte of the present embodiment has an oxidation current lower than the oxidation current of the sulfide solid electrolyte used, and therefore has excellent oxidation resistance.

[0660] The reduction rate of the oxidation current of the modified sulfide solid electrolyte of this embodiment is usually 15% or more, and further 20% or more, 25% or more, 30% or more, or 35% or more. Here, the reduction rate of the oxidation current is calculated by the following mathematical formula.

[0661] Oxidation current reduction rate (%) = (oxidation current A - oxidation current B) / oxidation current A × 100

[0662] Oxidation current A: Oxidation current of sulfide solid electrolyte before modification (mA)

[0663] Oxidation current B: Oxidation current of modified sulfide solid electrolyte (mA)

[0664] The index of the oxidation current calculated by the following mathematical formula is preferably as small as possible, and is usually 85% or less, further 80% or less, 75% or less, 70% or less, or 65% or less. The lower limit is not particularly limited, but is usually 50% or more.

[0665] Oxidation current index (%) = oxidation current B / oxidation current A × 100

[0666] Oxidation current 1: Oxidation current of modified sulfide solid electrolyte (mA)

[0667] Oxidation current 2: Oxidation current of sulfide solid electrolyte before modification (mA)

[0668] In addition, the absolute value of the oxidation current of the crystalline solid electrolyte obtained by the manufacturing method of this embodiment can be changed according to the measurement conditions, etc., so it cannot be generalized, but when measured by the oxidation current measurement method in the examples described later, it is usually small and is less than 0.55 mA, and further less than 0.45 mA, less than 0.43 mA, less than 0.41 mA, and less than 0.40 mA. In addition, the lower limit is about 0.20 mA.

[0669] (use)

[0670] The modified sulfide solid electrolyte of this embodiment has excellent coating adaptability and can be used in the manufacture of batteries even without using solvents, so it can effectively demonstrate excellent battery performance. In addition, it has high ion conductivity and excellent battery performance, so it is preferably used in batteries.

[0671] The modified sulfide solid electrolyte of this embodiment can be used for the positive electrode layer, the negative electrode layer, or the electrolyte layer. In addition, each layer can be produced by a known method.

[0672] In addition, the battery preferably uses a current collector in addition to the positive electrode layer, the electrolyte layer and the negative electrode layer, and the current collector can use a known current collector. For example, a layer obtained by coating a substance that reacts with the solid electrolyte such as Au, Pt, Al, Ti or Cu can be used.

[0673] [Method for producing modified sulfide solid electrolyte]

[0674] The method for producing the modified sulfide solid electrolyte of this embodiment includes:

[0675] The BET specific surface area is 10m 2 / g or more sulfide solid electrolyte containing lithium atoms, sulfur atoms, phosphorus atoms and halogen atoms, at least two compounds selected from the following compounds (A) to (I) and an organic solvent; and

[0676] The organic solvent is removed.

[0677] According to the production method of the present embodiment, the modified sulfide solid electrolyte of the present embodiment described above can be efficiently produced. That is, the modified sulfide solid electrolyte of the present embodiment is preferably produced by the production method of the present embodiment.

[0678] Compound (A) has a heterocyclic ring containing carbon atoms and oxygen atoms;

[0679] Compound (B) a compound having two or more heterocyclic rings containing carbon atoms and oxygen atoms;

[0680] Compound (C) an organic halide other than the following compound (F) 1;

[0681] Compound (D) a compound having a formyl group (CH(=O)-);

[0682] Compound (E) a compound having two or more acetyl groups (CH3C(=O)-);

[0683] Compound (F) has two or more -CH2X 1F An organic halide 2 containing a halogen group and an organic group represented by 1F represents a fluorine atom, a chlorine atom, a bromine atom or an iodine atom;

[0684] Compound (G) a thiol compound;

[0685] Compound (H) is a metal-free phosphorus compound, wherein the compound does not contain an oxygen atom singly bonded to a phosphorus atom;

[0686] Compound (I) contains no metal boron compound.

[0687] Regarding compound (F) having two or more -CH2X 1F (X 1F represents a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), and a compound containing a halogen group and an organic group, X 1F The halogen atom is preferably a fluorine atom or a bromine atom.

[0688] The BET specific surface area used in the production method of this embodiment is 10 m 2 The sulfide solid electrolyte containing lithium atoms, sulfur atoms, phosphorus atoms and halogen atoms in an amount of 100 g or more is the same sulfide solid electrolyte as that described as being usable in the modified sulfide solid electrolyte of the present embodiment. Therefore, as the sulfide solid electrolyte, a commercially available product can be used, and a sulfide solid electrolyte produced by the method of the sulfide solid electrolyte can also be used.

[0689] As the organic solvent used in the production method of the present embodiment, for example, the solvents described as the solvents that can be used in the method for producing the above-mentioned sulfide solid electrolyte can be exemplified. From the viewpoint of promoting mixing of the sulfide solid electrolyte and the heteropolycyclic compound, efficiently obtaining a modified sulfide solid electrolyte containing the sulfide solid electrolyte and the heteropolycyclic compound, and from the viewpoint of promoting adhesion of the heteropolycyclic compound to the sulfide solid electrolyte, among the above-mentioned solvents, preferably, an aliphatic hydrocarbon solvent, an alicyclic hydrocarbon solvent, an aromatic hydrocarbon solvent, and the ether solvent, ester solvent, and nitrile solvent exemplified as a complexing agent can be exemplified, and an aromatic hydrocarbon solvent is more preferable.

[0690] In the production method of the present embodiment, as the organic solvent, one kind among these can be used alone or in combination of two or more kinds.

[0691] In the production method of the present embodiment, the method of mixing the sulfide solid electrolyte, the heteropolycyclic compound, and the organic solvent can be performed by the same method as the "mixing" in the method of producing the sulfide solid electrolyte described above.

[0692] The organic solvent can be removed by the same method as the “drying” in the method for producing the above-mentioned sulfide solid electrolyte.

[0693] In addition, in the production method of the present embodiment, the “heating” in the method for producing the above-mentioned sulfide solid electrolyte may be performed.

[0694] 〔Electrode composite materials〕

[0695] The electrode composite material of the present embodiment is an electrode composite material including the modified sulfide solid electrolyte of the present embodiment described above and an electrode active material, or an electrode composite material including the modified sulfide solid electrolyte of the other embodiment described above and an electrode active material.

[0696] (Electrode Active Material)

[0697] As the electrode active material, a positive electrode active material or a negative electrode active material is used, depending on whether the electrode composite material is used for a positive electrode or a negative electrode.

[0698] As the positive electrode active material, any positive electrode active material can be used without particular limitation as long as it can promote the battery chemical reaction through the relationship with the negative electrode active material, and the battery chemical reaction is accompanied by the movement of lithium ions caused by the atom adopted as the atom reflecting ionic conductivity, preferably the lithium atom. As the positive electrode active material that can carry out such insertion and extraction of lithium ions, oxide-based positive electrode active materials, sulfide-based positive electrode active materials, etc. can be cited.

[0699] As oxide-based positive electrode active materials, preferred examples include lithium-containing transition metal composite oxides such as LMO (lithium manganese oxide), LCO (lithium cobalt oxide), NMC (lithium nickel manganese cobalt oxide), NCA (lithium nickel cobalt aluminum oxide), LNCO (lithium nickel cobalt oxide), and olivine-type compounds (LiMeNPO4, Me = Fe, Co, Ni, Mn).

[0700] Examples of the sulfide-based positive electrode active material include titanium sulfide (TiS2), molybdenum sulfide (MoS2), iron sulfide (FeS, FeS2), copper sulfide (CuS), and nickel sulfide (Ni3S2).

[0701] In addition to the above-mentioned positive electrode active materials, niobium selenide (NbSe 3 ) or the like can also be used.

[0702] The positive electrode active material can be used alone or in combination of two or more.

[0703] As the negative electrode active material, any negative electrode active material that can promote the battery chemical reaction accompanied by the movement of lithium ions caused by atoms used as atoms that embody ionic conductivity, preferably metals that can form alloys with lithium atoms, their oxides, alloys of the metals and lithium atoms, etc., preferably lithium atoms, can be used without particular limitation. As such a negative electrode active material that can allow lithium ions to be inserted and removed, a substance that is known as a negative electrode active material in the battery field can be used without limitation.

[0704] Examples of such negative electrode active materials include metallic lithium such as metallic lithium, metallic indium, metallic aluminum, metallic silicon, and metallic tin, or metals capable of forming alloys with metallic lithium, oxides of these metals, and alloys of these metals with metallic lithium.

[0705] The electrode active material used in the present embodiment may have a coating layer coated on its surface.

[0706] As a material for forming the coating layer, an atom that exhibits ionic conductivity in the sulfide solid electrolyte, preferably a nitride, an oxide, or an ion conductor such as a composite of lithium atoms, can be cited. Specifically, lithium nitride (Li3N), a Li4GeO4-based structure such as Li 4-2x Zn x Conductors with LISICON crystal structures such as GeO4, and conductors with Li3PO4 skeleton structures such as Li 4-x Ge 1-x P x Conductors with sulfide-LISICON crystal structures such as S4, La 2 / 3- x Li 3xConductors with a perovskite crystal structure such as TiO3, conductors with a NASICON crystal structure such as LiTi2(PO4)3, etc.

[0707] In addition, Li y Ti 3-y O4(0 <y<3)、Li4Ti5O 12 Lithium titanate (LTO), lithium metal oxides of metals belonging to Group 5 of the periodic table such as LiNbO3, LiTaO3, and oxide-based conductors such as Li2O-B2O3-P2O5, Li2O-B2O3-ZnO, and Li2O-Al2O3-SiO2-P2O5-TiO2.

[0708] The electrode active material having a coating layer is obtained by, for example, attaching a solution containing various atoms constituting a material forming the coating layer to the surface of the electrode active material and calcining the attached electrode active material preferably at 200° C. to 400° C.

[0709] Here, as the solution containing various atoms, for example, a solution containing alkoxides of various metals such as lithium ethoxide, titanium isopropoxide, niobium isopropoxide, tantalum isopropoxide, etc. can be used. At this time, as the solvent, an alcohol solvent such as ethanol and butanol; an aliphatic hydrocarbon solvent such as hexane, heptane, octane; an aromatic hydrocarbon solvent such as benzene, toluene, xylene, etc. can be used.

[0710] In addition, the above-mentioned attachment may be performed by dipping, spraying, or the like.

[0711] From the viewpoint of improving manufacturing efficiency and battery performance, the firing temperature is preferably 200° C. to 400° C., more preferably 250° C. to 390° C., and the firing time is usually about 1 minute to 10 hours, preferably 10 minutes to 4 hours.

[0712] As the coating rate of the coating layer, based on the surface area of ​​the electrode active material, it is preferably more than 90%, more preferably more than 95%, and further preferably 100%, that is, preferably the entire surface is coated. In addition, as the thickness of the coating layer, it is preferably more than 1nm, more preferably more than 2nm, and as the upper limit, it is preferably below 30nm, more preferably below 25nm.

[0713] The thickness of the coating layer can be measured by cross-sectional observation using a transmission electron microscope (TEM), and the coverage can be calculated from the thickness of the coating layer, elemental analysis values, and BET specific surface area.

[0714] (Other ingredients)

[0715] The electrode composite material of this embodiment may include other components such as a conductive material and a binder in addition to the modified sulfide solid electrolyte and the electrode active material. That is, the method for manufacturing the electrode composite material of this embodiment may use other components such as a conductive material and a binder in addition to the modified sulfide solid electrolyte and the electrode active material. Other components such as a conductive material and a binder may be further added to the modified sulfide solid electrolyte and the electrode active material in the mixing of the modified sulfide solid electrolyte and the electrode active material and mixed for use.

[0716] As conductive materials, from the viewpoint of improving battery performance by improving electron conductivity, examples include artificial graphite, graphite carbon fiber, resin-fired carbon, pyrolysis vapor-grown carbon, coke, mesophase carbon microbeads, furfuryl alcohol resin-fired carbon, polyphenylene, pitch-based carbon fiber, vapor-grown carbon fiber, natural graphite, and carbon materials that are difficult to graphitize.

[0717] By using a binder, the strength of the positive electrode and the negative electrode can be improved.

[0718] There are no particular restrictions on the binder as long as it can impart functions such as adhesion and flexibility. Examples include fluorine-based polymers such as polytetrafluoroethylene and polyvinylidene fluoride, thermoplastic elastomers such as butene rubber and styrene-butadiene rubber, acrylic resins, acrylic polyol resins, polyvinyl acetal resins, polyvinyl butyral resins, silicone resins and other resins.

[0719] The blending ratio (mass ratio) of the electrode active material and the modified sulfide solid electrolyte in the electrode composite material is preferably 99.5:0.5 to 40:60, more preferably 99:1 to 50:50, and even more preferably 98:2 to 60:40 in consideration of improvement in battery performance and manufacturing efficiency.

[0720] When containing a conductive material, the content of the conductive material in the electrode composite material is not particularly limited. If the battery performance is improved and the manufacturing efficiency is taken into consideration, it is preferably 0.5 mass % or more, more preferably 1 mass % or more, and further preferably 1.5 mass % or more. As an upper limit, it is preferably 10 mass % or less, preferably 8 mass % or less, and further preferably 5 mass % or less.

[0721] In addition, when containing a binder, the content of the binder in the electrode composite material is not particularly limited. If the battery performance is improved and the manufacturing efficiency is taken into consideration, it is preferably 1% by mass or more, more preferably 3% by mass or more, and further preferably 5% by mass or more. As an upper limit, it is preferably 20% by mass or less, preferably 15% by mass or less, and further preferably 10% by mass or less.

[0722] 〔Lithium-ion battery〕

[0723] The lithium ion battery of the present embodiment is a lithium ion battery including at least one selected from the modified sulfide solid electrolyte and the electrode composite material of the present embodiment described above, or including at least one selected from the modified sulfide solid electrolyte and the electrode composite material of the other embodiment described above.

[0724] The lithium ion battery of the present embodiment is not particularly limited in its structure as long as it includes the modified sulfide solid electrolyte of the present embodiment described above, an electrode composite material containing the modified sulfide solid electrolyte, or any one of the modified sulfide solid electrolyte of another embodiment and an electrode composite material containing the modified sulfide solid electrolyte of another embodiment, and has the structure of a general lithium ion battery.

[0725] As the lithium ion battery of the present embodiment, for example, a lithium ion battery having a positive electrode layer, a negative electrode layer, an electrolyte layer and a current collector is preferred. As the positive electrode layer and the negative electrode layer, the positive electrode layer and the negative electrode layer of the electrode composite material of the present embodiment are preferably used, and as the electrolyte layer, the modified sulfide solid electrolyte of the present embodiment or the modified sulfide solid electrolyte of another embodiment is preferably used.

[0726] As the current collector, any known current collector may be used. For example, a layer obtained by coating a substance that reacts with the above-mentioned solid electrolyte, such as Au, Pt, Al, Ti, or Cu, with Au or the like can be used.

[0727] Example

[0728] Next, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples at all.

[0729] Production Example: Preparation of Sulfide Solid Electrolyte

[0730] In a Schlenk bottle (capacity: 100 mL) with a stirrer, 0.59 g of lithium sulfide, 0.95 g of phosphorus pentasulfide, 0.19 g of lithium bromide, and 0.28 g of lithium iodide were introduced under a nitrogen atmosphere. After the stirrer was rotated, 20 mL of tetramethylethylenediamine (TMEDA) as a complexing agent was added, and stirring was continued for 12 hours. The obtained complex-containing material was dried under vacuum (room temperature: 23° C.) to obtain a powdered complex. Next, the powder of the complex was heated at 120° C. for 2 hours under vacuum to obtain an amorphous sulfide solid electrolyte. Furthermore, the amorphous sulfide solid electrolyte was heated at 140° C. for 2 hours under vacuum to obtain a crystalline sulfide solid electrolyte 1 (the heating temperature (140° C. in this example) used to obtain a crystalline sulfide solid electrolyte is sometimes referred to as the "crystallization temperature").

[0731] The BET specific surface areas of the amorphous sulfide solid electrolyte and the crystalline sulfide solid electrolyte were measured to be 40 m 2 / g.

[0732] Example 1

[0733] Under nitrogen atmosphere, 3 g of the crystalline sulfide solid electrolyte obtained in the above manufacturing example was weighed and added to a Schlenk bottle (capacity: 100 mL) with a stirrer, and 22 g of toluene was added for stirring to prepare a slurry-like fluid. In the slurry-like fluid, 2-ethylhexyl glycidyl ether as compound 1 and bisphenol A diglycidyl ether as compound 2 were added in an amount (i.e., 0.15 g) in a mass ratio of 20:80 (i.e., the content of compound 1 relative to the total amount of the used compounds was set to 20% by mass) and in a ratio of 5 parts by mass relative to 100 parts by mass of the above sulfide solid electrolyte. After stirring for 10 minutes, toluene was removed by vacuum drying and distillation to obtain a modified sulfide solid electrolyte.

[0734] The oil absorption, ion conductivity and oxidation current of the obtained modified sulfide solid electrolyte were measured according to the following method. The oil absorption (index) and oxidation current (index) were calculated according to the following method. The measurement results and calculation results are shown in Table 1.

[0735] Embodiments 2 to 5

[0736] A modified sulfide solid electrolyte was prepared in the same manner as in Example 1, except that the ratio of Compound 1 to Compound 2 was set to the ratio shown in Table 1.

[0737] The oil absorption, ion conductivity and oxidation current of the obtained modified sulfide solid electrolyte were measured according to the following method. The oil absorption (index) and oxidation current (index) were calculated according to the following method. The measurement results and calculation results are shown in Table 1.

[0738] Comparative Example 1

[0739] The oil absorption, ion conductivity and oxidation current of the sulfide solid electrolyte obtained in the above production example were measured according to the following methods. The measurement results are shown in Table 1. The oil absorption of the sulfide solid electrolyte was 1.03 mL / g, and the oxidation current was 0.60 mA.

[0740] Comparative Examples 2 and 3

[0741] A modified sulfide solid electrolyte was prepared in the same manner as in Example 1, except that the ratio of Compound 1 to Compound 2 was set to the ratio shown in Table 1.

[0742] The oil absorption, ion conductivity and oxidation current of the obtained modified sulfide solid electrolyte were measured according to the following method. The oil absorption (index) and oxidation current (index) were calculated according to the following method. The measurement results and calculation results are shown in Table 1.

[0743] (Measurement of specific surface area)

[0744] The specific surface area was measured by the BET method based on krypton (Kr) adsorption using a gas adsorption amount measuring device.

[0745] (Measurement of oil absorption)

[0746] 1 g of the solid electrolyte obtained in the examples and comparative examples was used as a sample. One drop of butyl butyrate was added using a dropper in an agate mortar and then stirred with a spatula. This operation was repeated until the sample became a paste. The total amount of butyl butyrate added was defined as the oil absorption (mL / g). The index of the oil absorption is a value calculated by the following mathematical formula.

[0747] (Oil absorption index)

[0748] The oil absorption of the sulfide solid electrolyte obtained in the manufacturing example was measured in the same manner as in the above (Measurement of Oil Absorption). The oil absorption A of the sulfide solid electrolyte and the oil absorption B of the sulfide solid electrolyte obtained in the examples and comparative examples were used to calculate by the following formula, and the calculated value was used as an index of the oil absorption.

[0749] Oil absorption index = oil absorption B / oil absorption A×100(%)

[0750] (Measurement of ionic conductivity)

[0751] In this example, the measurement of ion conductivity was performed as follows.

[0752] The sulfide solid electrolyte is formed into a 10 mm diameter (cross-sectional area S: 0.785 cm 2 ), round particles with a height (L) of 0.1 to 0.3 cm are used to make a sample. The top and bottom of the sample are taken as electrode terminals, and the AC impedance method is used for measurement at 25°C (frequency range: 1 MHz to 100 Hz, amplitude: 10 mV) to obtain a Cole-Cole plot. Near the right end of the arc observed in the high-frequency side area, the real part Z'(Ω) at the point where -Z"(Ω) is the smallest is taken as the bulk resistance R(Ω) of the electrolyte, and the ionic conductivity σ(S / cm) is calculated according to the following formula.

[0753] R=ρ(L / S)

[0754] σ=1 / ρ

[0755] (CV measurement (oxidation current))

[0756] In order to evaluate the oxidation current, the following single cell for CV measurement was used.

[0757] The powders obtained in Examples and Comparative Examples were used and mixed with 100 mg in total of DENKA BLACK granules (particle size: 35 nm, manufactured by DENKA Corporation) in a mortar (powder:DENKA BLACK (mass ratio) = 85:15) for 10 minutes to obtain a powder for measurement (1).

[0758] 100 mg of electrolyte for the separator layer was added to a battery cell with a diameter of 10 mm and the pressure was 10 MPa / cm2 using a SUS mold. 2 After pressing three times with each rotation of 120°, 10 mg of the measuring powder (1) was added and the pressure was adjusted to 20 MPa / cm 2 The pressing was repeated three times with each rotation of 120°. 2 Punch 3 times with each rotation of 120°.

[0759] The electrolyte for the above-mentioned separator layer was synthesized under the following conditions.

[0760] In a 1L reaction vessel with a stirring blade, 20.5g of Li2S, 33.1g of P2S5, 10.0g of LiI, and 6.5g of LiBr were added under a nitrogen atmosphere. After the stirring blade was rotated, 630g of toluene was introduced and the slurry was stirred for 10 minutes. A bead mill capable of circulating operation ("STAR MILL LMZ015 (trade name)", manufactured by Ashizawa Finetech Co., Ltd., bead material: zirconium oxide, bead diameter: 0.5mmφ, bead usage: 456g) was connected to the reaction vessel and subjected to a 45-hour pulverization treatment (pump flow rate: 650mL / min, bead mill peripheral speed: 12m / s, mill jacket temperature: 45°C).

[0761] The obtained slurry was dried at room temperature (25°C) under vacuum and then heated (80°C) to obtain a white powder of an amorphous solid electrolyte. Furthermore, the obtained white powder was heated at 195°C for 2 hours under vacuum to obtain a white powder of a crystalline solid electrolyte. In the XRD spectrum of the crystalline solid electrolyte, crystallization peaks were detected at 2θ=20.2° and 23.6°, confirming that it had a type II crystal structure in the sulfide crystalline lithium superion conductor region. In addition, the average particle size (D 50 ) is 4.5μm and the ionic conductivity is 5.0mS / cm.

[0762] On the opposite side of the measuring powder (1) of the electrolyte for the separator layer, an InLi foil (layer structure, " / " indicates the interval between layers. In: 10 mmφ×0.1 mm / Li: 9 mmφ×0.08 mm / SUS: 10 mmφ×0.1 mm) was formed and heated to 6 MPa / cm 2 Punching was performed once. The single cell was fixed by four bolts sandwiching an insulator so that there was no short circuit between the powder for measurement (1) and the InLi foil, and the bolts were fixed with a tightening torque of 8 N·m, thereby obtaining a single cell for measurement.

[0763] The obtained single cell for measurement was connected to a measuring instrument ("VMP-300 (model)", manufactured by Biologic), and a CV curve was obtained under the following conditions. The maximum current in the CV curve was defined as the oxidation current.

[0764] Measurement temperature: 25℃

[0765] Scan speed: 0.1mV / s

[0766] Potential measurement range: open circuit voltage (+2.1V) → +5.0V → +2.1V

[0767] Number of cycles: 2 times

[0768] The index of the oxidation current was calculated by the following formula using the oxidation current A of the sulfide solid electrolyte and the oxidation current B of the sulfide solid electrolyte obtained in the above-mentioned Examples and Comparative Examples, and the calculated value was used as the index of the oil absorption amount.

[0769] Oxidation current index = oxidation current B / oxidation current A×100(%)

[0770] (Oxidation current (index))

[0771] The oxidation current A of the sulfide solid electrolyte obtained in the manufacturing example and the oxidation current B of the sulfide solid electrolyte obtained in the above-mentioned Examples and Comparative Examples measured based on the above (CV measurement (oxidation current)) were used to calculate by the following formula, and the calculated value was used as the index of the oxidation current.

[0772] Oxidation current index = oxidation current B / oxidation current A×100(%)

[0773] [Table 1]

[0774] Table 1

[0775]

[0776] The details of Compounds 1 and 2 shown in Table 1 are as follows.

[0777] Compound 1: 2-ethylhexyl glycidyl ether (molecular weight: 186.30), an epoxy compound 2A represented by the general formula (2A), X 21A is a group represented by the general formula (2Aa), X 22A and X 23A is a hydrogen atom. In the general formula (2Aa), R 21A is methylene, R 22A It is 2-ethylhexyl. The structural formula is as follows.

[0778] [Chemistry 20]

[0779]

[0780] Compound 2: Bisphenol A diglycidyl ether (molecular weight: 340.42), a compound represented by the general formula (1B), X 1B It is a divalent aromatic group obtained by removing one hydrogen atom from each of the two hydroxyl groups of bisphenol A which is the basic structure. 1B =2, l 1B and n 1B is 0. The structural formula is as follows.

[0781] [Chemistry 21]

[0782]

[0783] It was confirmed from the examples that, if the sulfide solid electrolyte before modification of Comparative Example 1 was set to 100, the oil absorption (index) of the modified sulfide solid electrolyte of the present embodiment was 60 to 84%, and the oil absorption was reduced, although the specific surface area was large, i.e., 10 m 2 / g or more, but the oil absorption is small and the coating adaptability is excellent. It is also confirmed that if the sulfide solid electrolyte before modification of Comparative Example 1 is set to 100, the oxidation current (index) is 57-69%, and the oxidation current is also reduced, which has excellent oxidation resistance. In addition, it is confirmed from the examples that the ion conductivity of the modified sulfide solid electrolyte of this embodiment is 1.7-1.8 mS / cm, which is lower than the sulfide solid electrolyte of Comparative Example 1 in which no compound is used, but still has high ion conductivity.

[0784] On the other hand, the oxidation current (index) of the sulfide solid electrolyte of Comparative Example 3 using Compound 1 alone was as high as 78%, and the oil absorption (index) of the sulfide solid electrolyte of Comparative Example 2 using Compound 2 alone was as high as 88%.

[0785] From the above results, it was confirmed that the modified sulfide solid electrolyte of the present embodiment using compounds 1 and 2 has a small oil absorption, excellent coating adaptability, low oxidation current, and excellent oxidation resistance. That is, it was confirmed that in the method for producing the modified sulfide solid electrolyte of the present embodiment, for a large specific surface area of ​​10 m 2 A sulfide solid electrolyte with a concentration of 0.1 g or more can exhibit the effects of reducing oil absorption and improving coating suitability, and is therefore a preferred production method.

[0786] Figure 1 The oil absorption (index) and oxidation current (index) of the examples and comparative examples are shown in the table as the content of compound 1 relative to the total amount of the compounds ( Figure 1 In the graph of the invention, the ratio of compound 1 (mass %) is plotted as the horizontal axis. According to this graph, it can be said that compared with Comparative Examples 2 and 3 ( Figure 1 In the graph of , the ratio of compound 1 is 0 mass % and 100 mass % respectively), the modified sulfide solid electrolyte of the present embodiment achieves both reduction in oil absorption and reduction in oxidation current in a good balance.

[0787] In addition, it can be seen that compound 1 has an effect by reducing the oil absorption, and compound 2 has an effect by reducing the oxidation current. For example, by adjusting the ratio of compound 1 that exhibits an effect by reducing the oil absorption and compound 2 that exhibits an effect by reducing the oxidation current, a modified sulfide solid electrolyte having desired performance can be prepared.

[0788] (Example 6 and Comparative Example 4)

[0789] A modified sulfide solid electrolyte was prepared in the same manner as in Example 1, except that Compounds 1 and 2 were replaced with Compounds 3 and Compound 4, and the ratio of these compounds was set to the ratio shown in Table 2.

[0790] The oil absorption, ion conductivity and oxidation current of the obtained modified sulfide solid electrolyte were measured based on the above method. The oil absorption (index) and oxidation current (index) were calculated based on the above method. The measurement results and calculation results are shown in Table 2.

[0791] [Table 2]

[0792] Table 2

[0793]

[0794] Compound 3: 4-tert-butylphenyl glycidyl ether (molecular weight: 206.29), an epoxy compound 2A represented by the general formula (2A), X 21Ais a group represented by the general formula (2Aa), X 22A and X 23A is a hydrogen atom. In the general formula (2Aa), R 21A is methylene, R 22A It is 4-tert-butylphenyl. The structural formula is as follows.

[0795] [Chemistry 22]

[0796]

[0797] Compound 4: tri-n-octylphosphine oxide (molecular weight: 386.64), a compound represented by the general formula (1H), R 11H ~R 13H It is octyl. The structural formula is as follows.

[0798] [Chemistry 23]

[0799]

[0800] From the results of Example 6, it was confirmed that, if the sulfide solid electrolyte before modification of Comparative Example 1 was set to 100, the oil absorption (index) of the modified sulfide solid electrolyte of the present embodiment was 59%, and the oil absorption was reduced, although the specific surface area was large, 10 m 2 / g or more, but the oil absorption is small and the coating adaptability is excellent. It is also confirmed that if the sulfide solid electrolyte before modification of Comparative Example 1 is set to 100, the oxidation current (index) is 73%, and the oxidation current is also reduced, which has excellent oxidation resistance. In addition, it is confirmed from the examples that the ion conductivity of the modified sulfide solid electrolyte of this embodiment is 1.7 mS / cm, which is lower than that of the sulfide solid electrolyte of Comparative Example 1 in which no compound is used, but still has high ion conductivity.

[0801] Furthermore, the oxidation current (index) of the sulfide solid electrolyte of Comparative Example 4 using Compound 4 alone was as high as 104%, which resulted in an increase compared with the sulfide solid electrolyte of Comparative Example 1.

[0802] (Examples 7 to 11)

[0803] A modified sulfide solid electrolyte was prepared in the same manner as in Example 1, except that Compound 2 was replaced by Compound 5 and the ratio of these compounds was set to the ratio shown in Table 3.

[0804] The oil absorption, ion conductivity and oxidation current of the obtained modified sulfide solid electrolyte were measured based on the above method. The oil absorption (index) and oxidation current (index) were calculated based on the above method. The measurement results and calculation results are shown in Table 3.

[0805] [Table 3]

[0806] Table 3

[0807]

[0808] Compound 5: Bisphenol A propoxylated diglycidyl ether (molecular weight: 358.43), a compound represented by the general formula (1B), X 1B It is a divalent aromatic group obtained by removing one hydrogen atom from each of the two propyl groups of 2,2-bis(4-propoxyphenyl)propane, which is the basic structure. 1B =2, l 1B and m 1B is 0. The structural formula is as follows.

[0809] [Chemistry 24]

[0810]

[0811] From the results of Examples 7 to 11, it was confirmed that, when the sulfide solid electrolyte before modification of Comparative Example 1 was set to 100, the oil absorption (index) of the modified sulfide solid electrolyte of the present embodiment was 67 to 85%, and the oil absorption was reduced, although the specific surface area was large, i.e., 10 m 2 / g or more, but the oil absorption is small and the coating adaptability is excellent. It is also confirmed that if the sulfide solid electrolyte before modification of Comparative Example 1 is set to 100, the oxidation current (index) is 55-65%, the oxidation current is also reduced, and it has excellent oxidation resistance. In addition, it is confirmed from the examples that the ion conductivity of the modified sulfide solid electrolyte of this embodiment is 1.7-1.8 mS / cm, which is lower than the sulfide solid electrolyte of Comparative Example 1 in which no compound is used, but still has high ion conductivity.

[0812] (Examples 12, 13 and Comparative Example 5)

[0813] A modified sulfide solid electrolyte was prepared in the same manner as in Example 1, except that Compound 1 was replaced with Compound 6 and the ratio of these compounds was set to the ratio shown in Table 4.

[0814] The oil absorption, ion conductivity and oxidation current of the obtained modified sulfide solid electrolyte were measured based on the above method. The oil absorption (index) and oxidation current (index) were calculated based on the above method. The measurement results and calculation results are shown in Table 4.

[0815] [Table 4]

[0816] Table 4

[0817]

[0818] Compound 6: 2-bromopropane (molecular weight: 122.99), a compound represented by the general formula (1C), X 11C is a bromine atom, X 12C and X 13C is methyl, X 14C is a hydrogen atom. The structural formula is as follows.

[0819] [Chemistry 25]

[0820]

[0821] From the results of Examples 12 and 13, it was confirmed that, when the sulfide solid electrolyte before modification of Comparative Example 1 was set to 100, the oil absorption (index) of the modified sulfide solid electrolyte of the present embodiment was 82 to 85%, and the oil absorption was reduced, although the specific surface area was large, i.e., 10 m 2 / g or more, but the oil absorption is small and the coating adaptability is excellent. It is also confirmed that if the sulfide solid electrolyte before modification of Comparative Example 1 is set to 100, the oxidation current (index) is 48 to 66%, and the oxidation current is also reduced, which has excellent oxidation resistance. In addition, it is confirmed from the examples that the ion conductivity of the modified sulfide solid electrolyte of this embodiment is 1.7 mS / cm, which is lower than the sulfide solid electrolyte of Comparative Example 1 in which no compound is used, but still has high ion conductivity.

[0822] In addition, the oxidation current (index) of the sulfide solid electrolyte of Comparative Example 5 using Compound 6 alone was as high as 109%, which was increased compared with the sulfide solid electrolyte of Comparative Example 1.

[0823] (Example 14 and Comparative Example 6)

[0824] A modified sulfide solid electrolyte was prepared in the same manner as in Example 1, except that Compound 1 was replaced with Compound 7 and the ratio of these compounds was set to the ratio shown in Table 5.

[0825] The oil absorption, ion conductivity and oxidation current of the obtained modified sulfide solid electrolyte were measured based on the above method. The oil absorption (index) and oxidation current (index) were calculated based on the above method. The measurement results and calculation results are shown in Table 5.

[0826] [Table 5]

[0827] Table 5

[0828]

[0829] Compound 7: 3-phenylpropyl bromide (molecular weight: 199.09), a compound represented by the general formula (1C), X 11C is a bromine atom, X12C is phenylpropyl, X 13C and X 14C is a hydrogen atom. The structural formula is as follows.

[0830] [Chemistry 26]

[0831]

[0832] From the results of Example 14, it was confirmed that, if the sulfide solid electrolyte before modification of Comparative Example 1 was set to 100, the oil absorption (index) of the modified sulfide solid electrolyte of the present embodiment was 79%, and the oil absorption was reduced, although the specific surface area was large, 10 m 2 / g or more, but the oil absorption is small and the coating adaptability is excellent. It is also confirmed that if the sulfide solid electrolyte before modification of Comparative Example 1 is set to 100, the oxidation current (index) is 77%, and the oxidation current is also reduced, which has excellent oxidation resistance. In addition, it is confirmed from the examples that the ion conductivity of the modified sulfide solid electrolyte of this embodiment is 1.7mS / cm, which is lower than that of the sulfide solid electrolyte of Comparative Example 1 in which no compound is used, but still has high ion conductivity.

[0833] Furthermore, the oxidation current (index) of the sulfide solid electrolyte of Comparative Example 6 using Compound 7 alone was as high as 101%, which resulted in an increase compared with the sulfide solid electrolyte of Comparative Example 1.

[0834] (Example 15)

[0835] A modified sulfide solid electrolyte was prepared in the same manner as in Example 1, except that Compound 1 was replaced with Compound 8 and the ratio of these compounds was set to the ratio shown in Table 6.

[0836] The oil absorption, ion conductivity and oxidation current of the obtained modified sulfide solid electrolyte were measured based on the above method. The oil absorption (index) and oxidation current (index) were calculated based on the above method. The measurement results and calculation results are shown in Table 6.

[0837] [Table 6]

[0838] Table 6

[0839]

[0840] Compound 8: 1-dodecanethiol (molecular weight: 202.40), a compound represented by the general formula (1G), R 11G is a single bond, n 11G is 0, R 13G is 1,12-dodecanediyl, X 11G A hydrogen atom.

[0841] [Chemistry 27]

[0842]

[0843] From the results of Example 15, it was confirmed that, if the sulfide solid electrolyte before modification of Comparative Example 1 was set to 100, the oil absorption (index) of the modified sulfide solid electrolyte of the present embodiment was 79%, and the oil absorption was reduced, although the specific surface area was large, 10 m 2 / g or more, but the oil absorption is small and the coating adaptability is excellent. It is also confirmed that if the sulfide solid electrolyte before modification of Comparative Example 1 is set to 100, the oxidation current (index) is 77%, and the oxidation current is also reduced, which has excellent oxidation resistance. In addition, it is confirmed from the examples that the ion conductivity of the modified sulfide solid electrolyte of this embodiment is 1.7mS / cm, which is lower than that of the sulfide solid electrolyte of Comparative Example 1 in which no compound is used, but still has high ion conductivity.

[0844] (Example 16)

[0845] A modified sulfide solid electrolyte was prepared in the same manner as in Example 1, except that Compound 1 was replaced with Compound 9 and the ratio of these compounds was set to the ratio shown in Table 7.

[0846] The oil absorption, ion conductivity and oxidation current of the obtained modified sulfide solid electrolyte were measured based on the above method. The oil absorption (index) and oxidation current (index) were calculated based on the above method. The measurement results and calculation results are shown in Table 7.

[0847] [Table 7]

[0848] Table 7

[0849]

[0850] Compound 9: tri-n-octadecyl borate (molecular weight: 386.64), a compound represented by the general formula (1I), R 11I ~R 13I is octadecyloxy. The structural formula is as follows.

[0851] [Chemistry 28]

[0852]

[0853] From the results of Example 16, it was confirmed that, when the sulfide solid electrolyte before modification of Comparative Example 1 was set to 100, the oil absorption (index) of the modified sulfide solid electrolyte of the present embodiment was 83%, and the oil absorption was reduced, although the specific surface area was large, 10 m 2 / g or more, but the oil absorption is small and the coating adaptability is excellent. It is also confirmed that if the sulfide solid electrolyte before modification of Comparative Example 1 is set to 100, the oxidation current (index) is 68%, and the oxidation current is also reduced, which has excellent oxidation resistance. In addition, it is confirmed from the examples that the ion conductivity of the modified sulfide solid electrolyte of this embodiment is 1.8mS / cm, which is lower than that of the sulfide solid electrolyte of Comparative Example 1 in which no compound is used, but still has high ion conductivity.

[0854] (Examples 17 and 18)

[0855] A modified sulfide solid electrolyte was prepared in the same manner as in Example 1, except that Compound 1 was replaced with Compound 10 and the ratio of these compounds was set to the ratio shown in Table 8.

[0856] The oil absorption, ion conductivity and oxidation current of the obtained modified sulfide solid electrolyte were measured based on the above method. The oil absorption (index) and oxidation current (index) were calculated based on the above method. The measurement results and calculation results are shown in Table 8.

[0857] [Table 8]

[0858] Table 8

[0859]

[0860] Compound 10: 2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptyloxirane (molecular weight: 376.12), a compound represented by the general formula (1A), X 11A is 2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptyl, X 11B and X 11C is a hydrogen atom. The structural formula is as follows.

[0861] [Chemistry 29]

[0862]

[0863] From the results of Examples 17 and 18, it was confirmed that, when the sulfide solid electrolyte before modification of Comparative Example 1 was set to 100, the oil absorption (index) of the modified sulfide solid electrolyte of the present embodiment was 63 to 77%, and the oil absorption was reduced, although the specific surface area was large, i.e., 10 m 2 / g or more, but the oil absorption is small and the coating adaptability is excellent. It is also confirmed that if the sulfide solid electrolyte before modification of Comparative Example 1 is set to 100, the oxidation current (index) is 65-68%, and the oxidation current is also reduced, which has excellent oxidation resistance. In addition, it is confirmed from the examples that the ion conductivity of the modified sulfide solid electrolyte of this embodiment is 1.7-1.9 mS / cm, which is lower than the sulfide solid electrolyte of Comparative Example 1 in which no compound is used, but still has high ion conductivity.

[0864] (Example 19)

[0865] A modified sulfide solid electrolyte was prepared in the same manner as in Example 1, except that Compound 2 was replaced by Compound 11 and the ratio of these compounds was set to the ratio shown in Table 9.

[0866] The oil absorption, ion conductivity and oxidation current of the obtained modified sulfide solid electrolyte were measured based on the above method. The oil absorption (index) and oxidation current (index) were calculated based on the above method. The measurement results and calculation results are shown in Table 9.

[0867] [Table 9]

[0868] Table 9

[0869]

[0870] Compound 11: tris(4-hydroxyphenyl)methane triglycidyl ether (molecular weight: 460.52), a compound represented by the general formula (1B), X 1B It is a trivalent group obtained by removing one hydrogen atom from each of the three hydroxyl groups of methylenetriphenol, which is the basic structure. 1B and m 1B is 0, n 1B The structural formula is as follows.

[0871] [Chemistry 30]

[0872]

[0873] From the results of Example 19, it was confirmed that, if the sulfide solid electrolyte before modification of Comparative Example 1 was set to 100, the oil absorption (index) of the modified sulfide solid electrolyte of the present embodiment was 78%, and the oil absorption was reduced, although the specific surface area was large, 10 m 2 / g or more, but the oil absorption is small and the coating adaptability is excellent. It is also confirmed that if the sulfide solid electrolyte before modification of Comparative Example 1 is set to 100, the oxidation current (index) is 55%, and the oxidation current is also reduced, which has excellent oxidation resistance. In addition, it is confirmed from the examples that the ion conductivity of the modified sulfide solid electrolyte of this embodiment is 1.5mS / cm, which is lower than that of the sulfide solid electrolyte of Comparative Example 1 in which no compound is used, but still has high ion conductivity.

[0874] (Example 20)

[0875] A modified sulfide solid electrolyte was prepared in the same manner as in Example 1, except that Compound 2 was replaced by Compound 12 and the ratio of these compounds was set to the ratio shown in Table 10.

[0876] The oil absorption, ion conductivity and oxidation current of the obtained modified sulfide solid electrolyte were measured based on the above method. The oil absorption (index) and oxidation current (index) were calculated based on the above method. The measurement results and calculation results are shown in Table 10.

[0877] [Table 10]

[0878] Table 10

[0879]

[0880] Compound 12: 1,3-bis[2-(7-oxabicyclo[4.1.0]heptane-3-yl)ethyl]-1,1,3,3-tetramethyldisiloxane (molecular weight: 382.69), a compound represented by the general formula (1B), X 1B A divalent group obtained by removing one hydrogen atom from each of the three hydrogen atoms bonded to the terminal carbon atom of 1,3-ethylhexyl-1,1,3,3-tetramethyldisiloxane, which is the basic structure. 1B =2, m 1B and n 1B is 0. The structural formula is as follows.

[0881] [Chemistry 31]

[0882]

[0883] From the results of Example 20, it was confirmed that, if the sulfide solid electrolyte before modification of Comparative Example 1 was set to 100, the oil absorption (index) of the modified sulfide solid electrolyte of the present embodiment was 73%, and the oil absorption was reduced, although the specific surface area was large, 10 m 2 / g or more, but the oil absorption is small and the coating adaptability is excellent. It is also confirmed that if the sulfide solid electrolyte before modification of Comparative Example 1 is set to 100, the oxidation current (index) is 47%, and the oxidation current is also reduced, which has excellent oxidation resistance. In addition, it is confirmed from the examples that the ion conductivity of the modified sulfide solid electrolyte of this embodiment is 1.3mS / cm, which is lower than that of the sulfide solid electrolyte of Comparative Example 1 in which no compound is used, but still has high ion conductivity.

[0884] Industrial Applicability

[0885] The modified sulfide solid electrolyte of the present embodiment has excellent coating adaptability when applied as a paste even if it is a sulfide solid electrolyte with a large specific surface area, and can effectively demonstrate excellent battery performance. In addition, the modified sulfide solid electrolyte of the present embodiment has high ion conductivity and is therefore suitable for use in batteries, particularly batteries used in information-related devices or communication devices such as personal computers, video cameras, and mobile phones.

Claims

1. A modified sulfide solid electrolyte, characterized in that: Contains: Sulfide solid electrolyte with a BET surface area of ​​10m 2 / g or more and containing lithium atoms, sulfur atoms, phosphorus atoms and halogen atoms; at least two compounds selected from the following compounds (A) to (I), Compound (A) has a heterocyclic ring containing carbon atoms and oxygen atoms; Compound (B) a compound having two or more heterocyclic rings containing carbon atoms and oxygen atoms; Compound (C) an organic halide other than the following compound (F) 1; Compound (D) a compound having a formyl group (CH(=O)-); Compound (E) a compound having two or more acetyl groups (CH3C(=O)-); Compound (F) has two or more -CH2X 1F An organic halide 2 containing a halogen group and an organic group represented by 1F represents a fluorine atom or a bromine atom; Compound (G) a thiol compound; Compound (H) is a metal-free phosphorus compound, wherein the compound does not contain an oxygen atom singly bonded to a phosphorus atom; Compound (I) contains no metal boron compound.

2. The modified sulfide solid electrolyte according to claim 1, characterized in that It contains at least one compound selected from the compound (B) and at least one compound selected from the compounds (A) and (C) to (I).

3. The modified sulfide solid electrolyte according to claim 1 or 2, characterized in that: It contains at least one compound selected from the compound (B) and at least one compound selected from the compounds (A), (C) and (F).

4. The modified sulfide solid electrolyte according to any one of claims 1 to 3, characterized in that The heterocyclic ring containing carbon atoms and oxygen atoms of the compounds (A) and (B) is an oxirane ring.

5. The modified sulfide solid electrolyte according to any one of claims 1 to 4, characterized in that The compound (C) is at least one compound selected from the following compounds: 1C A compound wherein X 1C Represents a halogen atom; has a haloformyl group (CX 1C (=O)-), wherein X 1C Represents a halogen atom; having a halosilyl group (-SiX 1c n 1C ), wherein X 1C Represents a halogen atom, n 1C Indicates an integer from 1 to 3.

6. The modified sulfide solid electrolyte according to claim 4 or 5, characterized in that The compound (A) is at least one compound selected from an epoxy compound 1A represented by the following general formula (1A), an epoxy compound 2A represented by the following general formula (2A), and an epoxy compound 3A represented by the following general formula (3A), [Chemistry 1] In the general formula (1A), X 11A ~X 13A are independently a hydrogen atom, a halogen atom, a hydrocarbon group or a halogenated hydrocarbon group, X 11A ~X 13A At least one of is a hydrocarbon group or a halogenated hydrocarbon group, In the general formula (2A), X 21A ~X 23A are independently a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group or a group represented by the general formula (2Aa), X 21A ~X 23A At least one of them is a group represented by the general formula (2Aa), in which R 21A is a divalent hydrocarbon group, R 22A is a hydrogen atom, a halogen atom, a hydrocarbon group or a halogenated hydrocarbon group, In the general formula (3A), X 31A ~X 33A are independently a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group or a group represented by the general formula (3Aa), X 31A ~X 33A At least one of them is a group represented by the general formula (3Aa), in which R 31A and R 32A are independently a single bond or a divalent hydrocarbon group, X 34A ~X 36A are independently a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, -OR 33A or a group represented by the general formula (3Ab), R 33A ~R 36A are each independently a hydrogen atom, a halogen atom, a hydrocarbon group or a halogenated hydrocarbon group.

7. The modified sulfide solid electrolyte according to any one of claims 4 to 6, characterized in that The compound (B) is an epoxy compound represented by the following general formula (1B), which has at least two groups selected from epoxy groups, glycidyl groups and glycidyl ether groups. [Chemistry 2] In the general formula (1B), X 1B is a single bond or an aliphatic group, an alicyclic group, an aromatic group, an organic group having a siloxane structure, or an organic group consisting of a combination of these, 1B 、m 1B and n 1B are integers greater than 0 and less than 16, satisfying l 1B +m 1B +n 1B ≥2, in addition, as X 1B When the organic group has the alicyclic group, the epoxy group may be a group condensed with the alicyclic ring in the alicyclic group.

8. The method for producing a modified sulfide solid electrolyte according to any one of claims 5 to 7, wherein: The compound (C) is at least one compound selected from an organic halide 1a represented by the following general formula (1C), an organic halide 1b represented by the following general formula (2C), an organic halide 1c represented by the following general formula (3C), and an organic halide 1d represented by the following general formula (4C), [Chemistry 3] In the general formula (1C), X 11C is a halogen atom, X 12C ~X 14C are independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group or an aromatic hydrocarbon group, and the hydrogen atom of the aliphatic hydrocarbon group, the alicyclic hydrocarbon group or the aromatic hydrocarbon group may be substituted by a halogen atom, In the general formula (2C), X 21C ~X 26C are independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group or an aromatic hydrocarbon group, X 21C ~X 26C The hydrogen atoms of the aliphatic hydrocarbon group, alicyclic hydrocarbon group, and aromatic hydrocarbon group may be substituted by halogen atoms, and X 21C ~X 26C is a halogen atom or a group containing a halogen atom, In the general formula (3C), X 31C and X 32C are independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group or a group represented by the general formula (3Ca), wherein R 31C is a single bond or an aliphatic hydrocarbon group, R 32C is a hydrogen atom, a halogen atom or an aliphatic hydrocarbon group. The hydrogen atom of the aliphatic hydrocarbon group, the alicyclic hydrocarbon group or the aromatic hydrocarbon group may be substituted by a halogen atom. 31C and X 32C is a halogen atom or a group containing a halogen atom, In the general formula (4C), X 41C ~X 44C are independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group or an aromatic hydrocarbon group. The hydrogen atom of the aliphatic hydrocarbon group, the alicyclic hydrocarbon group or the aromatic hydrocarbon group may be substituted by a halogen atom. 41C ~X 44C is a halogen atom or a group containing a halogen atom, In the general formulae (1C) to (4C), X 11C , X 21C , X 31C and X 41C The halogen atom is an atom selected from chlorine, bromine and iodine atoms, and X 12C ~X 14C , X 22C ~X 26C , X 32C and X 42C ~X 44C The halogen atom is an atom selected from a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

9. The modified sulfide solid electrolyte according to any one of claims 1 to 8, characterized in that The compound (D) is a compound represented by the following general formula (1D): [Chemistry 4] In the general formula (1D), R 11D and R 12D Each independently represents an organic group or a single bond, X 11D represents an oxygen atom, a sulfur atom or a single bond, n 11D Represents 0 or 1.

10. The modified sulfide solid electrolyte according to any one of claims 1 to 9, characterized in that The compound (E) is a compound represented by the following general formula (1E): [Chemistry 5] In the general formula (1E), R 11E and R 12E Each independently represents an organic group or a single bond, X 11E represents an oxygen atom, a sulfur atom, or a single bond.

11. The modified sulfide solid electrolyte according to any one of claims 1 to 10, characterized in that The compound (F) is a compound represented by the following general formula (1F): [Chemistry 6] In the general formula (1F), R 11F represents an organic group or a single bond, X 11F and X 12F Each independently represents a fluorine atom or a bromine atom.

12. The modified sulfide solid electrolyte according to any one of claims 1 to 11, characterized in that The compound (G) is at least one compound selected from a thiol compound 1 represented by the following general formula (1G) and a thiol compound 2 represented by the following general formula (2G), [Chemistry 7] In the general formula (1G), R 11G , R 12G and R 13G Each independently represents an organic group or a single bond, X 11G represents a hydrogen atom or a thiol group, n 11G represents an integer from 0 to 3, where R 11G , R 12G and R 13G At least one of is an organic group, In the general formula (2G), R 21G , R 22G and R 23G Each independently represents an organic group, n 21G 、n 22G Integer from 0 to 3, n 21G and n 22G Satisfy n 21G +n 22G =3, where R 21G , R 22G and R 23G At least one of the groups is an organic group.

13. The modified sulfide solid electrolyte according to any one of claims 1 to 12, characterized in that: The compound (H) is at least one metal-free phosphorus compound selected from a metal-free phosphorus compound 1H represented by the following general formula (1H), a metal-free phosphorus compound 2H represented by the following general formula (2H), and a metal-free phosphorus compound 3H represented by the following general formula (3H), [Chemistry 8] In the general formula (1H), R 11H , R 12H and R 13H Each independently represents an organic group, In the general formula (2H), R 21H , R 22H and R 23H Each independently represents an organic group, In the general formula (3H), R 31H , R 32H , R 35H and R 36H Each independently represents an organic group, R 33H and R 34H Each independently represents a single bond or an organic group, X 31H represents a single bond or an oxygen atom. In addition, R 33H and R 34H At least one of R is an organic group, 33H With R 34H They may be bonded to each other to form a condensed ring.

14. The modified sulfide solid electrolyte according to any one of claims 1 to 13, characterized in that The compound (I) is a compound represented by the following general formula (1I): [Chemistry 9] In the general formula (1I), R 11I , R 12I and R 13I Each independently represents an organic group.

15. The modified sulfide solid electrolyte according to any one of claims 1 to 14, characterized in that The content of the at least two compounds is 0.03 parts by mass or more and 25 parts by mass or less relative to 100 parts by mass of the sulfide solid electrolyte.

16. A method for producing a modified sulfide solid electrolyte, characterized in that: include: The BET specific surface area is 10m 2 / g or more and containing lithium atoms, sulfur atoms, phosphorus atoms and halogen atoms, at least two compounds selected from the following compounds (A) to (I) and an organic solvent; as well as removing the organic solvent, Compound (A) has a heterocyclic ring containing carbon atoms and oxygen atoms; Compound (B) a compound having two or more heterocyclic rings containing carbon atoms and oxygen atoms; Compound (C) an organic halide other than the following compound (F) 1; Compound (D) a compound having a formyl group (CH(=O)-); Compound (E) a compound having two or more acetyl groups (CH3C(=O)-); Compound (F) has two or more -CH2X 1F An organic halide 2 containing a halogen group and an organic group represented by 1F represents a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; Compound (G) a thiol compound; Compound (H) is a metal-free phosphorus compound, wherein the compound does not contain an oxygen atom singly bonded to a phosphorus atom; Compound (I) contains no metal boron compound.

17. The method for producing a modified sulfide solid electrolyte according to claim 16, wherein: The organic solvent is at least one solvent selected from aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, aromatic hydrocarbon solvents, ether solvents, ester solvents, and nitrile solvents.

18. An electrode composite material, characterized in that: A modified sulfide solid electrolyte comprising the modified sulfide solid electrolyte according to any one of claims 1 to 15 and an electrode active material.

19. A lithium ion battery, characterized in that: A method comprising at least one of the modified sulfide solid electrolyte according to any one of claims 1 to 15 and the electrode composite material according to claim 18.

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