Solid electrolyte composition, method for producing solid electrolyte composition, and method for producing solid electrolyte member
By combining a solid electrolyte material with ion bond properties with an organic solvent containing chlorine compounds, the shortcomings of the solid electrolyte composition in terms of Dispersion stability and lithium ion conductivity are solved, and the effects of high Dispersion stability and lithium ion conductivity are achieved.
Patent Information
- Application Number
- JP2021567198
- Authority / Receiving Office
- JP · JP
- Patent Type
- Patents
- Current Assignee / Owner
- Priority Date
- 2019-12-27
- Filing Date
- 2020-12-09
- Publication Date
- 2025-05-16
- Estimated Expiration
- 2040-12-09
AI Technical Summary
In the prior art, solid electrolyte compositions have shortcomings in terms of Dispersion stability, and when mixed with an organic solvent, lithium ion conductivity may decrease.
The solid electrolyte material with ionic bond properties is used to combine with the organic solvent of chlorine-containing compounds, and the Dispersion stability and lithium ion conductivity of the solid electrolyte are improved by selecting suitable solvent combinations such as chlorine-containing compounds, ethers and hydrocarbons.
High Dispersion stability and lithium ion conductivity of the solid electrolyte composition are achieved, and the settlement and conductivity of the solid electrolyte are avoided.
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Abstract
Description
[Technical field]
[0001] The present disclosure relates to a solid electrolyte composition used, for example, in the production of an all-solid-state battery, a method for producing a solid electrolyte composition, and a method for producing a solid electrolyte member. [Background technology]
[0002] Patent Document 1 discloses a solid electrolyte composition using a sulfide solid electrolyte.
[0003] Patent Document 2 discloses a battery using a halide solid electrolyte material. [Prior art documents] [Patent documents]
[0004] [Patent Document 1] International Publication No. 2018 / 168505 [Patent Document 2] International Publication No. 2018 / 025582 Summary of the Invention [Problem to be solved by the invention]
[0005] In the prior art, there is a need for a solid electrolyte composition having excellent dispersion stability. [Means for solving the problem]
[0006] One aspect of the present disclosure is A solid electrolyte material having ionic bonding properties; An organic solvent; Equipped with The organic solvent is A compound having a halogen group; At least one member selected from the group consisting of a compound having an ether group and a hydrocarbon; The present invention relates to a solid electrolyte composition comprising:
[0007] Another aspect of the present disclosure is a method for manufacturing a semiconductor device comprising: removing the organic solvent from the solid electrolyte composition; The present invention relates to a method for producing a solid electrolyte member, comprising the steps of: Effect of the Invention
[0008] According to the present disclosure, a solid electrolyte composition having excellent dispersion stability can be provided. [Brief description of the drawings]
[0009] [Figure 1] FIG. 1 is a flow chart showing an example of a method for producing a solid electrolyte composition. [Diagram 2] FIG. 2 is a flow chart showing another example of a method for producing a solid electrolyte composition. [Diagram 3] FIG. 3 is a flowchart showing an example of a method for manufacturing a solid electrolyte member. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0010] (Summary of one aspect of the present disclosure) The solid electrolyte composition according to the first aspect of the present disclosure comprises: A solid electrolyte material having ionic bonding properties; An organic solvent; Equipped with The organic solvent is A compound having a halogen group; At least one member selected from the group consisting of a compound having an ether group and a hydrocarbon; Includes.
[0011] According to the first aspect, a solid electrolyte composition having excellent dispersion stability can be provided.
[0012] In the second aspect of the present disclosure, for example, in the solid electrolyte composition according to the first aspect, the solid electrolyte material may not contain elemental sulfur. With this configuration, a solid electrolyte composition having excellent dispersion stability can be provided.
[0013] In the third embodiment of the present disclosure, for example, the solid electrolyte composition according to the first or second embodiment may further include an organic binder. By using the organic binder, it is possible to improve the adhesion between the solid electrolyte materials, the adhesion between the solid electrolyte and the electrode, or the adhesion between the solid electrolyte and the current collector.
[0014] In a fourth aspect of the present disclosure, for example, in the solid electrolyte composition according to any one of the first to third aspects, the solid electrolyte material may have lithium ion conductivity and may contain at least one selected from the group consisting of Mg, Ca, Sr, Ba, Zn, Sn, Al, Sc, Ga, Bi, Sb, Zr, Hf, Ti, Ta, Nb, W, Y, Gd, Tb, and Sm, and at least one selected from the group consisting of F, Cl, Br, and I.
[0015] In a fifth aspect of the present disclosure, for example, in the solid electrolyte composition according to any one of the first to third aspects, the solid electrolyte material may contain Li, at least one selected from the group consisting of Gd, Ca, Zr, and Y, and at least one selected from the group consisting of F, Cl, Br, and I.
[0016] In a sixth aspect of the present disclosure, for example, in the solid electrolyte composition according to any one of the first to third aspects, the solid electrolyte material may contain Li, Y, and at least one selected from the group consisting of F, Cl, Br, and I.
[0017] In a seventh aspect of the present disclosure, for example, in the solid electrolyte composition according to the fifth aspect, the solid electrolyte material may contain at least one selected from the group consisting of a material containing Li, Y, Cl, and Br, a material containing Li, Ca, Y, Gd, Cl, and Br, and a material containing Li, Zr, Y, and Cl.
[0018] In an eighth aspect of the present disclosure, for example, in the solid electrolyte composition according to the seventh aspect, the solid electrolyte material is Li3YBr2Cl4, Li 2.8 Ca0.1 Y 0.5 Gd 0.5 Br2Cl4, and Li 2.5 Y 0.5 Zr 0.5 Cl6.
[0019] According to the fourth to eighth aspects, the all-solid-state battery can exhibit excellent charge / discharge efficiency.
[0020] In a ninth aspect of the present disclosure, for example, in the solid electrolyte composition according to any one of the first to fourth aspects, the solid electrolyte material may be substantially composed of only Li, at least one selected from the group consisting of Mg, Ca, Sr, Ba, Zn, Sn, Al, Sc, Ga, Bi, Sb, Zr, Hf, Ti, Ta, Nb, W, Y, Gd, Tb, and Sm, and at least one selected from the group consisting of F, Cl, Br, and I. With this configuration, a solid electrolyte member having high lithium ion conductivity can be produced.
[0021] In a tenth aspect of the present disclosure, for example, in the solid electrolyte composition according to any one of the first to ninth aspects, the ratio of the weight of the compound having a halogen group to the total weight of the organic solvent may be 10% by weight or more. With this configuration, a solid electrolyte composition having excellent dispersion stability can be provided.
[0022] In an eleventh aspect of the present disclosure, for example, in the solid electrolyte composition according to any one of the first to tenth aspects, the organic solvent may contain a ring structure.
[0023] In a twelfth aspect of the present disclosure, for example, in the solid electrolyte composition according to the eleventh aspect, the organic solvent may contain an aromatic compound.
[0024] According to the eleventh and twelfth aspects, the solid electrolyte material having ionic bonding properties can be easily dispersed in an organic solvent.
[0025] In a thirteenth aspect of the present disclosure, for example, in the solid electrolyte composition according to any one of the first to tenth aspects, the compound having a halogen group may include at least one selected from the group consisting of 1,2,4-trichlorobenzene, chlorobenzene, 2,4-dichlorotoluene, o-chlorotoluene, 1,3-dichlorobenzene, p-chlorotoluene, 1,2-dichlorobenzene, 1,4-dichlorobutane, and 3,4-dichlorotoluene.
[0026] In a fourteenth aspect of the present disclosure, for example, in the solid electrolyte composition according to any one of the first to tenth aspects, the at least one selected from the group consisting of the compound having an ether group and the hydrocarbon may include at least one selected from the group consisting of tetralin, ethylbenzene, mesitylene, pseudocumene, xylene, cumene, dibutyl ether, and anisole.
[0027] According to the thirteenth and fourteenth aspects, the solid electrolyte material having ionic bonding properties can be easily dispersed in an organic solvent.
[0028] In a fifteenth aspect of the present disclosure, for example, the solid electrolyte composition according to any one of the first to fourteenth aspects may further contain an active material. By including the active material in the solid electrolyte composition, the solid electrolyte composition can have excellent dispersion stability.
[0029] A method for producing a solid electrolyte composition according to a sixteenth aspect of the present disclosure includes the steps of: mixing a solid electrolyte material having ionic bonding properties with a first organic solvent containing a compound having a halogen group, and a second organic solvent containing at least one selected from the group consisting of a compound having an ether group and a hydrocarbon; Includes.
[0030] According to the sixteenth aspect, the fluidity of the solid electrolyte composition can be improved while maintaining the dispersibility and stability of the solid electrolyte material.
[0031] In a seventeenth aspect of the present disclosure, for example, the method for producing a solid electrolyte composition according to the sixteenth aspect may include preparing a mixture containing the solid electrolyte material and the first organic solvent, and then mixing the mixture with the second organic solvent.
[0032] In an eighteenth aspect of the present disclosure, for example, in the method for producing a solid electrolyte composition according to the sixteenth aspect, when the solid electrolyte material, the first organic solvent, and the second organic solvent are mixed, an organic binder may be mixed together with the solid electrolyte material, the first organic solvent, and the second organic solvent.
[0033] In a nineteenth aspect of the present disclosure, for example, in the method for producing a solid electrolyte composition according to the seventeenth aspect, when the mixture and the second organic solvent are mixed, the second organic solvent and an organic binder may be mixed to prepare an organic binder solution, and the mixture and the organic binder solution may be mixed.
[0034] According to the seventeenth to nineteenth aspects, the fluidity of the solid electrolyte composition can be improved while maintaining the dispersibility and stability of the solid electrolyte material.
[0035] In the twentieth embodiment of the present disclosure, for example, in the method for producing a solid electrolyte composition according to any one of the sixteenth to nineteenth embodiments, at least one selected from the group consisting of a compound having a halogen group, a compound having an ether group, and a hydrocarbon may be further mixed into the solid electrolyte composition obtained from the solid electrolyte material, the first organic solvent, and the second organic solvent. According to this configuration, the solid electrolyte composition can have an appropriate viscosity while maintaining the dispersibility and stability of the solid electrolyte material.
[0036] A method for producing a solid electrolyte member according to a twenty-first aspect of the present disclosure includes the steps of: removing the organic solvent from the solid electrolyte composition according to any one of the first to fifteenth aspects; Includes.
[0037] According to the twenty-first embodiment, a homogeneous solid electrolyte membrane can be produced.
[0038] Hereinafter, embodiments of the present disclosure will be described with reference to the drawings.
[0039] <Inventor's viewpoint> In the field of secondary batteries, where high energy density and large capacity are required, the mainstream approach has been to use an organic electrolyte solution in which an electrolyte salt is dissolved in an organic solvent. In secondary batteries using an organic electrolyte solution, there is a concern about leakage, and it has also been pointed out that the amount of heat generated may be large if a short circuit occurs.
[0040] On the other hand, all-solid-state secondary batteries that use inorganic solid electrolytes instead of organic electrolytes are gaining attention. All-solid-state secondary batteries do not leak. Because inorganic solid electrolytes are not flammable, it is expected that heat generation in the event of a short circuit will be suppressed.
[0041] Known inorganic solid electrolytes for use in all-solid-state secondary batteries include sulfide-based solid electrolytes containing sulfur as a main component and oxide-based solid electrolytes containing metal oxide as a main component. However, sulfide-based solid electrolytes can generate toxic hydrogen sulfide when reacting with moisture. Oxide-based solid electrolytes have low ionic conductivity. Therefore, there is a need to develop new solid electrolyte materials with excellent ionic conductivity.
[0042] As a new solid electrolyte material, for example, Patent Document 2 discloses a solid electrolyte material containing lithium element, yttrium element, and at least one kind of halogen element.
[0043] In order to put an all-solid-state secondary battery using a solid electrolyte material having ionic bonding properties into practical use, it is necessary to prepare a composition that contains a solid electrolyte material having ionic bonding properties and has fluidity, and further, a technique is required for forming a solid electrolyte member by applying the composition having fluidity to the surface of an electrode or a current collector.
[0044] In order to prepare a composition having fluidity, it is necessary to mix a solid electrolyte material having ionic bonding properties with an organic solvent. However, when an organic solvent is mixed with a solid electrolyte material having ionic bonding properties, the lithium ion conductivity of the solid electrolyte material having ionic bonding properties may decrease depending on the type of organic solvent. Alternatively, when an organic solvent is mixed with a solid electrolyte material having ionic bonding properties, the dispersion stability of the solid electrolyte material having ionic bonding properties may decrease depending on the type of organic solvent.
[0045] The configuration of the present disclosure was achieved from the above perspective.
[0046] According to the present disclosure, it is possible to suppress the solidification or precipitation of a solid electrolyte material. As a result, it is possible to provide a solid electrolyte composition having excellent dispersion stability. Furthermore, such a solid electrolyte composition can suppress the decrease in ion conductivity.
[0047] (Embodiment 1) In the first embodiment, the solid electrolyte composition includes a solid electrolyte material having ionic bonding properties and an organic solvent.
[0048] The solid electrolyte material having ionic bonding is not particularly limited as long as it has ionic bonding and ionic conductivity. In general, a bond between atoms with a large difference in electronegativity is called an ionic bond. For example, a metal element has a small electronegativity. A nonmetal element has a large electronegativity. The solid electrolyte material having ionic bonding may be, for example, a solid electrolyte material having a bond between a metal element other than lithium and a nonmetal element. The solid electrolyte material having ionic bonding does not include, for example, a sulfur element.
[0049] The organic solvent contains a compound having a halogen group and at least one selected from the group consisting of a compound having an ether group and a hydrocarbon. According to this configuration, the solid electrolyte material having ionic bonding properties can be easily dispersed in the organic solvent, and the viscosity of the solid electrolyte composition can be appropriately adjusted. For example, the organic solvent contains a compound having a halogen group, so that the solid electrolyte material having ionic bonding properties can be easily dispersed, and therefore a solid electrolyte composition having excellent dispersibility can be obtained. For example, the organic solvent contains at least one selected from the group consisting of a compound having an ether group and a hydrocarbon, so that the interaction between the solid electrolyte materials having ionic bonding properties can be appropriately adjusted. As a result, the viscosity of the solid electrolyte composition can be appropriately adjusted.
[0050] The compound having a halogen group may be composed of only carbon and hydrogen except for the halogen group. That is, the compound having a halogen group may be a compound in which at least one hydrogen atom contained in a hydrocarbon is substituted with a halogen group. Examples of the halogen group include F, Cl, Br, and I. As the halogen group, at least one selected from the group consisting of F, Cl, Br, and I may be used, or a plurality of types may be used. From the viewpoint of boiling point or drying property, the halogen group may be a chloro group. The compound having a halogen group may have high polarity. By using the compound having a halogen group, the solid electrolyte material having ionic bonding property can be easily dispersed, so that a solid electrolyte composition having excellent dispersibility can be obtained. As a result, the solid electrolyte composition has excellent lithium ion conductivity and can form a denser solid electrolyte member.
[0051] The number of carbon atoms contained in the compound having a halogen group is not particularly limited, and may be 7 or more. As a result, the compound having a halogen group is less likely to volatilize, so that the solid electrolyte composition can be stably produced. In addition, the compound having a halogen group may have a large molecular weight. That is, the compound having a halogen group may have a high boiling point.
[0052] The compound having a halogen group may have a ring structure. The compound having a halogen group may have an aromatic ring. The ring structure may be an alicyclic hydrocarbon or an aromatic hydrocarbon. The ring structure may be a monocyclic or a polycyclic. By the compound having a halogen group having a ring structure, the solid electrolyte material having ionic bonding properties can be easily dispersed in the compound having a halogen group. These compounds can easily disperse, in particular, halide solid electrolyte materials. The compound having a halogen group may include an aromatic hydrocarbon. The compound having a halogen group may be an aromatic compound.
[0053] The compound having a halogen group may have only a halogen group as a functional group. In this case, the number of halogens contained in the compound having a halogen group is not particularly limited. At least one selected from the group consisting of F, Cl, Br, and I may be used as the halogen, and a plurality of types may be used. By using such a compound, a solid electrolyte material having ionic bonding properties can be easily dispersed in the solid electrolyte composition. Therefore, a solid electrolyte composition having excellent suspension stability of the solid electrolyte material can be obtained. As a result, the solid electrolyte composition has excellent lithium ion conductivity and can form a denser solid electrolyte member. By using such a compound, the solid electrolyte composition can easily form, for example, a dense solid electrolyte membrane with few pinholes, unevenness, etc.
[0054] As described above, the compound having a halogen group may be a compound in which at least one of the hydrogen atoms contained in the hydrocarbon is replaced with a halogen group. That is, the compound having a halogen group may be a halogenated hydrocarbon. The compound having a halogen group may be a compound in which all hydrogen atoms contained in the hydrocarbon are replaced with halogen atoms. By using a halogenated hydrocarbon, a solid electrolyte material having ionic bonding properties can be easily dispersed in the solid electrolyte composition. Therefore, a solid electrolyte composition having excellent suspension stability of the solid electrolyte material can be obtained. As a result, the solid electrolyte composition has excellent lithium ion conductivity and can form a denser solid electrolyte member. By using a halogenated hydrocarbon, the solid electrolyte composition can easily form, for example, a dense solid electrolyte membrane with few pinholes, unevenness, etc.
[0055] A hydrocarbon is a compound consisting of only carbon and hydrogen. A hydrocarbon may be a saturated or unsaturated hydrocarbon. A hydrocarbon may be a straight chain or a branched chain. The number of carbon atoms contained in a hydrocarbon is not particularly limited and may be 7 or more.
[0056] The hydrocarbon may have a ring structure. The hydrocarbon may have an aromatic ring. The ring structure may be an alicyclic hydrocarbon or an aromatic hydrocarbon. The ring structure may be a monocyclic or a polycyclic. By the hydrocarbon having a ring structure, the solid electrolyte material having ionic bonding properties can be easily dispersed in an organic solvent. These compounds can easily disperse, in particular, halide solid electrolyte materials. From the viewpoint of increasing the suspension stability of the solid electrolyte material having ionic bonding properties in the solid electrolyte composition, the hydrocarbon may contain an aromatic hydrocarbon. The hydrocarbon may be an aromatic hydrocarbon.
[0057] The compound having an ether group may be composed of only carbon and hydrogen in the portion other than the ether group. That is, the compound having an ether group may be a hydrocarbon containing an ether bond. In this case, the hydrocarbon may be a saturated hydrocarbon or an unsaturated hydrocarbon. The hydrocarbon may be a straight chain or a branched chain. The number of carbon atoms contained in the hydrocarbon is not particularly limited, and may be 7 or more.
[0058] The compound having an ether group may have a ring structure. That is, the hydrocarbon group contained in the compound having an ether group may have a ring structure. The compound having an ether group may have an aromatic ring. The ring structure may be an alicyclic hydrocarbon or an aromatic hydrocarbon. The ring structure may be a monocyclic or a polycyclic. By the hydrocarbon group having a ring structure, the solid electrolyte material having ionic bonding properties can be easily dispersed in an organic solvent. These compounds can easily disperse, in particular, a halide solid electrolyte material. From the viewpoint of increasing the suspension stability of the solid electrolyte material having ionic bonding properties in the solid electrolyte composition, the hydrocarbon group may contain an aromatic hydrocarbon. The hydrocarbon group may be an aromatic hydrocarbon.
[0059] In order to enhance the suspension stability of the solid electrolyte material having ionic bonding properties, the organic solvent may contain a ring structure.The organic solvent may contain an aromatic compound.
[0060] More specifically, the compound having a halogen group may include at least one selected from the group consisting of 1,2,4-trichlorobenzene, chlorobenzene, 2,4-dichlorotoluene, o-chlorotoluene, 1,3-dichlorobenzene, p-chlorotoluene, 1,2-dichlorobenzene, 1,4-dichlorobutane, and 3,4-dichlorotoluene. These compounds can easily disperse solid electrolyte materials having ionic bonding properties. These compounds can easily disperse, in particular, halide solid electrolyte materials.
[0061] The compound having a halogen group may include p-chlorotoluene. The compound having a halogen group may be p-chlorotoluene. These compounds can easily disperse solid electrolyte materials having ionic bonding properties. These compounds can easily disperse, in particular, halide solid electrolyte materials.
[0062] More specifically, the at least one selected from the group consisting of a compound having an ether group and a hydrocarbon may include at least one selected from the group consisting of tetralin, ethylbenzene, mesitylene, pseudocumene, xylene, cumene, dibutyl ether, and anisole. These compounds can easily disperse a solid electrolyte material having ionic bonding properties. These compounds can easily disperse, in particular, a halide solid electrolyte material. Furthermore, by using these compounds, the solid electrolyte composition can have an appropriate viscosity.
[0063] More specifically, the at least one selected from the group consisting of a compound having an ether group and a hydrocarbon may include at least one selected from the group consisting of tetralin, xylene, cumene, and anisole. The at least one selected from the group consisting of a compound having an ether group and a hydrocarbon may be at least one selected from the group consisting of tetralin, xylene, cumene, and anisole. These compounds can easily disperse a solid electrolyte material having ionic bonding properties. These compounds can easily disperse a halide solid electrolyte material, in particular.
[0064] The weight ratio of the compound having a halogen group to the total weight of the organic solvent contained in the solid electrolyte composition may be 10% by weight or more, or may be 50% by weight or more. This makes it possible to obtain a solid electrolyte composition having excellent suspension stability of the solid electrolyte material. The upper limit of the weight ratio of the compound having a halogen group to the total weight of the organic solvent contained in the solid electrolyte composition is not particularly limited. The upper limit of the weight ratio of the compound having a halogen group to the total weight of the organic solvent contained in the solid electrolyte composition may be 99% by weight. For example, a gas chromatograph-mass spectrometer (GC-MS) can be used to calculate the weight ratio of the compound having a halogen group to the total weight of the organic solvent contained in the solid electrolyte composition.
[0065] The boiling point of the organic solvent is not particularly limited, and may be 100°C or higher, 130°C or higher, or 200°C or higher. The upper limit of the boiling point of the organic solvent is not particularly limited. The upper limit of the boiling point of the organic solvent may be 250°C. The organic solvent may be a liquid that can disperse the solid electrolyte material having ionic bonding properties, and the solid electrolyte material having ionic bonding properties does not have to be completely dissolved in the organic solvent.
[0066] According to the above configuration, it is possible to obtain a solid electrolyte composition having excellent suspension stability of the solid electrolyte material while suppressing a decrease in ion conductivity. That is, when a solid electrolyte composition containing a solid electrolyte material having ion bonding properties and an organic solvent is dried to remove the organic solvent, a solid electrolyte member having high ion conductivity can be obtained. The solid electrolyte member can be a solid electrolyte membrane or an active material membrane.
[0067] The solid electrolyte material having ionic bonding properties may have, for example, lithium ion conductivity.
[0068] The solid electrolyte material having ionic bonding properties may contain at least one element selected from the group consisting of Mg, Ca, Sr, Ba, Zn, Sn, Al, Sc, Ga, Bi, Sb, Zr, Hf, Ti, Ta, Nb, W, Y, Gd, Tb, and Sm. These elements can generate cations in water.
[0069] The solid electrolyte material having ionic bonding properties may further contain at least one element selected from the group consisting of F, Cl, Br, and I. These elements can generate anions in water.
[0070] The solid electrolyte material having ionic bonding properties may contain Li, at least one selected from the group consisting of Gd, Ca, Zr, and Y, and at least one selected from the group consisting of F, Cl, Br, and I.
[0071] The solid electrolyte material having ionic bonding properties may contain Li, Y, and at least one selected from the group consisting of F, Cl, Br, and I.
[0072] According to the above-mentioned configuration, the solid electrolyte composition can further suppress the decrease in lithium ion conductivity, thereby making it possible to produce a solid electrolyte member having higher lithium ion conductivity.
[0073] More specifically, the solid electrolyte material having ionic bonding properties may include at least one selected from the group consisting of a material containing Li, Y, Cl, and Br, a material containing Li, Ca, Y, Gd, Cl, and Br, and a material containing Li, Zr, Y, and Cl. The solid electrolyte material having ionic bonding properties may be a material containing Li, Y, Cl, and Br, a material containing Li, Ca, Y, Gd, Cl, and Br, or a material containing Li, Zr, Y, and Cl.
[0074] Specifically, the solid electrolyte material having ionic bonding is Li3YBr2Cl4, Li 2.8 Ca 0.1 Y 0.5Gd 0.5 Br2Cl4, and Li 2.5 Y 0.5 Zr 0.5 The solid electrolyte material having ionic bonding may contain at least one selected from the group consisting of Li3YBr2Cl4, Li 2.8 Ca 0.1 Y 0.5 Gd 0.5 Br2Cl4, or Li 2.5 Y 0.5 Zr 0.5 The solid electrolyte material having these ionic bonds may be Cl6. The solid electrolyte material having these ionic bonds has high ionic conductivity. By using the solid electrolyte material having these ionic bonds, the all-solid-state battery can exhibit excellent charge and discharge efficiency.
[0075] The solid electrolyte material having ionic bonding may be a material consisting essentially of Li, at least one selected from the group consisting of Mg, Ca, Sr, Ba, Zn, Sn, Al, Sc, Ga, Bi, Sb, Zr, Hf, Ti, Ta, Nb, W, Y, Gd, Tb, and Sm, and at least one selected from the group consisting of F, Cl, Br, and I. According to this configuration, the solid electrolyte composition can further suppress the decrease in lithium ion conductivity. This makes it possible to manufacture a solid electrolyte member having excellent lithium ion conductivity more reliably.
[0076] In the present disclosure, "consisting essentially of only Li, at least one selected from the group consisting of Mg, Ca, Sr, Ba, Zn, Sn, Al, Sc, Ga, Bi, Sb, Zr, Hf, Ti, Ta, Nb, W, Y, Gd, Tb, and Sm, and at least one selected from the group consisting of F, Cl, Br, and I" means "including only Li, at least one selected from the group consisting of Mg, Ca, Sr, Ba, Zn, Sn, Al, Sc, Ga, Bi, Sb, Zr, Hf, Ti, Ta, Nb, W, Y, Gd, Tb, and Sm, and at least one selected from the group consisting of F, Cl, Br, and I, excluding unavoidable impurities that are unintentionally mixed. Therefore, for example, "consisting essentially of only Li, Y, Cl, and Br" means "including only Li, Y, Cl, and Br, excluding unavoidable impurities that are unintentionally mixed. Hereinafter, the same expressions have the same meanings. An example of the unavoidable impurities is oxygen element.
[0077] The solid electrolyte material having ionic bonding properties may be a material consisting essentially of Li, Y, Cl, and Br. The solid electrolyte material having ionic bonding properties may be a material consisting essentially of Li, Ca, Y, Gd, Cl, and Br. The solid electrolyte material having ionic bonding properties may be a material consisting essentially of Li, Zr, Y, and Cl.
[0078] The solid electrolyte material having ionic bonding properties may be a halide solid electrolyte material. In the present disclosure, the term "halide solid electrolyte material" refers to a solid electrolyte material that contains a halogen element and does not contain sulfur. In the present disclosure, the term "sulfur-free solid electrolyte material" refers to a solid electrolyte material represented by a composition formula that does not contain sulfur element. Therefore, a solid electrolyte material containing a very small amount of sulfur component, for example, 0.1 mass % or less of sulfur, is included in the solid electrolyte material that does not contain sulfur. The halide solid electrolyte material may further contain oxygen as an anion other than the halogen element.
[0079] The halide solid electrolyte material may be represented by the following composition formula (1). In the composition formula (1), α, β, and γ are each independently a value greater than 0. M is at least one selected from the group consisting of metal elements and semimetal elements other than Li. X is at least one selected from the group consisting of Cl, Br, and I. The halide solid electrolyte material represented by the composition formula (1) has high ionic conductivity. By using the halide solid electrolyte material, the all-solid-state battery can exhibit excellent charge and discharge efficiency.
[0080] Li α M β X γ (1)
[0081] In the present disclosure, the term "metalloid element" refers to at least one element selected from the group consisting of B, Si, Ge, As, Sb, and Te.
[0082] In the present disclosure, a "metal element" refers to all elements in Groups 1 to 12 of the periodic table excluding hydrogen, and all elements in Groups 13 to 16 of the periodic table excluding B, Si, Ge, As, Sb, Te, C, N, P, O, S, and Se. In other words, a "metalloid element" or a "metal element" refers to a group of elements that can become a cation when forming an inorganic compound with a halogen element.
[0083] In the composition formula (1), M may contain Y (yttrium). That is, the halide solid electrolyte material may contain Y as the metal element M. The halide solid electrolyte material has high ionic conductivity. By using the halide solid electrolyte material, the all-solid-state battery can exhibit excellent charge and discharge efficiency.
[0084] The halide solid electrolyte material containing Y is Li a Me b Y cIt may also be a compound represented by the composition formula of X6. Here, a + mb + 3c = 6 and c > 0 are satisfied. Me is at least one selected from the group consisting of metal elements other than Li and Y and metalloid elements. m is the valence of Me.
[0085] Me is, for example, at least one selected from the group consisting of Mg, Ca, Sr, Ba, Zn, Sc, Al, Ga, Bi, Zr, Hf, Ti, Sn, Ta, and Nb. In this case, the ionic conductivity of the halide solid electrolyte material can be further improved.
[0086] The halide solid electrolyte material may be a material represented by the following composition formula (A1).
[0087] Li 6-3d Y d X6···(A1)
[0088] In the composition formula (A1), X is at least one selected from the group consisting of Cl, Br, and I. In the composition formula (A1), d may satisfy 0 < d < 2.
[0089] In the composition formula (A1), d may satisfy d = 1. That is, the halide solid electrolyte material may be a material represented by the composition formula (A2).
[0090] Li3YX6···(A2)
[0091] The halide solid electrolyte material may be a material represented by the composition formula (A3).
[0092] Li 3-3δ Y 1+δ Cl6···(A3)
[0093] In the composition formula (A3), δ may satisfy 0 < δ ≤ 0.15.
[0094] The halide solid electrolyte material may be a material represented by the compositional formula (A4).
[0095] Li 3-3δ Y 1+δ Br6···(A4)
[0096] In the compositional formula (A4), δ may satisfy 0 < δ ≦ 0.25.
[0097] The halide solid electrolyte material may be a material represented by the compositional formula (A5).
[0098] Li 3-3δ+a Y 1+δ-a Me a Cl 6-x-y Br x I y ···(A5)
[0099] In the compositional formula (A5), Me may be at least one selected from the group consisting of Mg, Ca, Sr, Ba, and Zn. In the compositional formula (A5), -1 < δ < 2, 0 < a < 3, 0 < (3 - 3δ + a), 0 < (1 + δ - a), 0 ≦ x ≦ 6, 0 ≦ y ≦ 6, and (x + y) ≦ 6 are satisfied.
[0100] The halide solid electrolyte material may be a material represented by the compositional formula (A6).
[0101] Li 3-3δ Y 1+δ-a Me a Cl 6-x-y Br x I y ···(A6)
[0102] In the compositional formula (A6), Me may be at least one selected from the group consisting of Al, Sc, Ga, and Bi. In the compositional formula (A6), -1 < δ < 1, 0 < a < 2, 0 < (1 + δ - a), 0 ≦ x ≦ 6, 0 ≦ y ≦ 6, and (x + y) ≦ 6 are satisfied.
[0103] The halide solid electrolyte material may be a material represented by the compositional formula (A7).
[0104] Li 3-3δ-a Y 1+δ-a Me a Cl 6-x-y Br x I y ···(A7)
[0105] In the compositional formula (A7), Me may be at least one selected from the group consisting of Zr, Hf, and Ti. In the compositional formula (A7), -1 < δ < 1, 0 < a < 1.5, 0 < (3 - 3δ - a), 0 < (1 + δ - a), 0 ≤ x ≤ 6, 0 ≤ y ≤ 6, and (x + y) ≤ 6 are satisfied.
[0106] The halide solid electrolyte material may be a material represented by the compositional formula (A8).
[0107] Li 3-3δ-2a Y 1+δ-a Me a Cl 6-x-y Br x I y ···(A8)
[0108] In the compositional formula (A8), Me may be at least one selected from the group consisting of Ta and Nb. In the compositional formula (A8), -1 < δ < 1, 0 < a < 1.2, 0 < (3 - 3δ - 2a), 0 < (1 + δ - a), 0 ≤ x ≤ 6, 0 ≤ y ≤ 6, and (x + y) ≤ 6 are satisfied.
[0109] The halide solid electrolyte materials of the compositional formulas (A1) to (A8) have high ionic conductivity. All-solid-state batteries using the halide solid electrolyte materials of the compositional formulas (A1) to (A8) can exhibit excellent charge and discharge efficiency.
[0110] The shape of the ion-bonding solid electrolyte material is not particularly limited, and may be particulate. The average particle size of the ion-bonding solid electrolyte material is not particularly limited, and may be 0.1 μm or more and 2 μm or less, or 0.1 μm or more and 1 μm or less. With this configuration, the surface roughness of the film can be reduced when the solid electrolyte composition is applied to form a solid electrolyte member. This makes it possible to form a thin film.
[0111] In the present disclosure, the average particle size of particles means a particle size (d50) corresponding to 50% cumulative volume, determined from a particle size distribution measured on a volume basis by a laser diffraction scattering method. The particle size distribution can also be measured, for example, using an image analyzer. The same applies to other materials.
[0112] The solid electrolyte composition may further include an organic binder. By including the organic binder, it is possible to improve the adhesion between the solid electrolyte materials, between the solid electrolyte and an electrode, or between the solid electrolyte and a current collector.
[0113] The solid electrolyte composition includes an organic solvent. The organic solvent includes at least one selected from the group consisting of a compound having a halogen group, a compound having an ether group, and a hydrocarbon. Therefore, even if the solid electrolyte composition further includes an organic binder, a solid electrolyte composition having excellent suspension stability of the solid electrolyte material can be obtained.
[0114] The material of the organic binder is not particularly limited, and materials generally used as binders for batteries can be used. Examples of the organic binder include thermoplastic resins, rubbers, and styrene-butadiene elastomers. Examples of the thermoplastic resins include acrylic resins, urethane resins, imide resins, amide resins, urea resins, and fluorine-containing resins. Examples of the rubbers include styrene-butadiene rubbers, butylene rubbers, and isoprene rubbers.
[0115] The solid electrolyte composition may further include an active material. The active material may be a positive electrode active material. The positive electrode active material can reversibly insert and release lithium ions. Examples of the positive electrode active material include LiCoO2 (lithium cobalt oxide, LCO), LiNi2O2 (lithium nickel oxide), LiNi 0.85 Co 0.1 Al 0.05 O2 (Lithium Nickel Cobalt Aluminum Oxide, NCA), LiNi 0.5 Co 0.2 Mn 0.3 O2 (Lithium Nickel Manganese Cobalt Oxide, NMC), LiNi 0.5 Mn 0.5 O2 (lithium manganese nickel oxide), and LiMn2O4 (lithium manganese oxide, LMO) can be used.
[0116] The shape of the active material is not particularly limited, and may be particulate. The average particle size of the active material is not particularly limited, and may be, for example, 0.1 μm or more and 30 μm or less. The content of the active material contained in the solid electrolyte composition is not particularly limited. The ratio of the content of the active material to the content of the solid content contained in the solid electrolyte composition may be 30 wt % or more and 95 wt % or less, or 50 wt % or more and 85 wt % or less. According to such a configuration, the solid electrolyte member formed on the current collector can exhibit excellent charge and discharge efficiency as a positive electrode.
[0117] (Embodiment 2) Hereinafter, the second embodiment will be described. The same description as in the first embodiment will be omitted as appropriate. Fig. 1 is a flow chart showing an example of a method for producing a solid electrolyte composition.
[0118] The method for producing the solid electrolyte composition includes, for example, mixing a solid electrolyte material having ionic bonding properties with an organic solvent. The organic solvent includes, for example, a first organic solvent and a second organic solvent. The first organic solvent includes, for example, a compound having a halogen group. The second organic solvent includes, for example, at least one selected from the group consisting of a compound having an ether group and a hydrocarbon. In the solid electrolyte composition, the content of the solid electrolyte material having ionic bonding properties, the content of the first organic solvent, and the content of the second organic solvent are not particularly limited. The ratio of the weight of the first organic solvent to the weight of the solid electrolyte material having ionic bonding properties may be 6.5% by weight or more and 560% by weight or less, or may be 23% by weight or more and 230% by weight or less. The ratio of the weight of the second organic solvent to the weight of the solid electrolyte material having ionic bonding properties may be 0.67% by weight or more and 510% by weight or less, or may be 2.3% by weight or more and 210% by weight or less. As a result, the solid electrolyte material having ionic bonding properties can be easily dispersed, so that a solid electrolyte composition having excellent suspension stability of the solid electrolyte material can be obtained. As a result, the solid electrolyte composition has excellent lithium ion conductivity and can form a denser solid electrolyte member. By using such a compound, the solid electrolyte composition can easily form, for example, a dense solid electrolyte membrane with few pinholes, irregularities, etc.
[0119] The method for producing a solid electrolyte composition may include steps S101 and S102. Step S101 is a step of mixing the solid electrolyte material having ionic bonding properties in the above-mentioned first embodiment with a first organic solvent containing a compound having a halogen group. Step S102 is a step of mixing a second organic solvent containing at least one selected from the group consisting of a compound having an ether group and a hydrocarbon. Steps S101 and S102 may be performed in this order.
[0120] A mixture can be obtained by mixing a solid electrolyte material having ionic bonding properties with a first organic solvent containing a compound having a halogen group. The mixture includes a solid electrolyte material having ionic bonding properties and a first organic solvent containing a compound having a halogen group. The mixture can have excellent dispersibility and stability. A solid electrolyte composition can be obtained by mixing the mixture with a second organic solvent containing at least one selected from the group consisting of a compound having an ether group and a hydrocarbon. According to this method, the fluidity of the solid electrolyte composition can be improved while maintaining the dispersibility and stability of the solid electrolyte material. According to this method, a homogeneous solid electrolyte membrane can be produced, and a denser solid electrolyte member can be formed.
[0121] The method of mixing the ionic solid electrolyte material with the first organic solvent containing the compound having a halogen group is not particularly limited. It is sufficient that the ionic solid electrolyte material can be uniformly dispersed in the first organic solvent. For example, a ball mill, a bead mill, a planetary mixer, an ultrasonic mixer, a homogenizer, or a rotation / revolution mixer can be used for mixing.
[0122] (Embodiment 3) Hereinafter, the third embodiment will be described. The same explanation as in the first and second embodiments will be omitted as appropriate. Fig. 2 is a flow chart showing an example of another method for producing a solid electrolyte composition.
[0123] The method for producing the solid electrolyte composition includes, for example, mixing a solid electrolyte material having ionic bonding properties, an organic solvent, and an organic binder. The organic solvent includes, for example, a first organic solvent and a second organic solvent. The first organic solvent includes, for example, a compound having a halogen group. The second organic solvent includes, for example, at least one selected from the group consisting of a compound having an ether group and a hydrocarbon. When the solid electrolyte composition includes an organic binder, the content of the solid electrolyte material having ionic bonding properties, the content of the first organic solvent, the content of the second organic solvent, and the content of the organic binder are not particularly limited. The ratio of the weight of the first organic solvent to the weight of the solid electrolyte material having ionic bonding properties may be 6.5% by weight or more and 560% by weight or less, or may be 23% by weight or more and 230% by weight or less. The ratio of the weight of the second organic solvent to the weight of the solid electrolyte material having ionic bonding properties may be 0.67% by weight or more and 510% by weight or less, or may be 2.3% by weight or more and 210% by weight or less. The weight ratio of the organic binder to the weight of the solid electrolyte material having ionic bonding properties may be 0.2% by weight or more and 5% by weight or less, or 0.4% by weight or more and 3% by weight or less. This allows the solid electrolyte material having ionic bonding properties to be easily dispersed in the solid electrolyte composition. Therefore, a solid electrolyte composition having excellent suspension stability of the solid electrolyte material can be obtained. As a result, the solid electrolyte composition has excellent lithium ion conductivity and can form a denser solid electrolyte member. By using such a compound, the solid electrolyte composition can easily form, for example, a dense solid electrolyte membrane with few pinholes, unevenness, etc.
[0124] The method for producing a solid electrolyte composition may include steps S201, S202, and S203. Step S201 is a step of preparing a mixture of a solid electrolyte having ionic bonding properties and a first organic solvent containing a compound having a halogen group. Step S202 is a step of preparing an organic binder solution by mixing an organic binder with a second organic solvent containing at least one selected from the group consisting of a compound having an ether group and a hydrocarbon. Step S203 is a step of mixing the mixture with the organic binder solution. Steps S201, S202, and S203 may be performed in this order.
[0125] By mixing a solid electrolyte having ionic bonding properties with a first organic solvent containing a compound having a halogen group, a mixture having excellent dispersibility and stability can be produced. By mixing the mixture with an organic binder solution, the fluidity of the solid electrolyte composition can be improved while maintaining the dispersibility and stability of the solid electrolyte material. According to this method, a solid electrolyte composition in which the organic binder is homogeneously mixed can be obtained.
[0126] When only an organic binder is added to the mixture, or when the mixture is mixed with an organic binder and a first organic solvent containing a compound having a halogen group, the viscosity of the mixture increases. This reduces the dispersion stability of the solid electrolyte material and reduces the moldability of the solid electrolyte member. In the present disclosure, an organic binder solution obtained by mixing an organic binder and a second organic solvent is added to the mixture. This makes it possible to improve the fluidity of the solid electrolyte composition while maintaining the dispersibility and stability of the solid electrolyte material. Furthermore, it is possible to obtain a solid electrolyte composition in which the organic binder is homogeneously mixed.
[0127] The mixture preparation process can be carried out in the same manner as in the second embodiment.
[0128] In the step of preparing the organic binder solution, the organic binder solution may be further heated to promote dissolution of the organic binder. The heating temperature is not particularly limited and can be determined in consideration of the boiling point of the organic solvent or the solubility of the organic binder. The heating temperature may be 40°C or higher and 100°C or lower.
[0129] The solid electrolyte composition may further include at least one selected from the group consisting of a compound having a halogen group, a compound having an ether group, and a hydrocarbon. This allows the solid electrolyte composition to have an appropriate viscosity while maintaining the dispersibility and stability of the solid electrolyte material. As a result, the solid electrolyte composition has excellent moldability and can form a coating film having, for example, a uniform thickness.
[0130] (Embodiment 4) Hereinafter, the fourth embodiment will be described. Descriptions that are the same as those in the first to third embodiments will be omitted as appropriate. Fig. 3 is a flow chart showing an example of a method for producing a solid electrolyte member.
[0131] The method for producing a solid electrolyte member includes a step S301 of removing an organic solvent from the solid electrolyte composition in the above-mentioned first embodiment. The solid electrolyte member is a member containing a solid electrolyte material having ionic bonding properties. The solid electrolyte member may be, for example, a member such as a solid electrolyte layer containing a solid electrolyte material having ionic bonding properties, a solid electrolyte membrane, or an electrode layer containing a solid electrolyte material having ionic bonding properties.
[0132] For example, a homogeneous solid electrolyte membrane can be produced by removing the organic solvent from a solid electrolyte composition containing a solid electrolyte material having ionic bonding properties and an organic solvent. As a result, the solid electrolyte member can have high lithium ion conductivity.
[0133] In step S301, the organic solvent is removed from the solid electrolyte composition. At this time, the organic solvent may be removed by drying under reduced pressure. The solid electrolyte composition before the organic solvent is removed has fluidity, and therefore has excellent moldability and can form, for example, a coating film having a uniform thickness. By drying such a coating film, for example, a dense solid electrolyte film with few pinholes, unevenness, etc. can be easily obtained.
[0134] The vacuum drying refers to removing the organic solvent from the solid electrolyte composition in a pressure atmosphere lower than atmospheric pressure. The pressure atmosphere lower than atmospheric pressure may be, for example, -0.01 MPa or less in gauge pressure. In the vacuum drying, the solid electrolyte composition or the solid electrolyte member may be heated, for example, to 50°C or more and 250°C or less. The organic solvent may be removed by vacuum drying. The vacuum drying refers to removing the organic solvent from the solid electrolyte composition at a vapor pressure or less at a temperature 20°C lower than the boiling point of the organic solvent. The removal of the organic solvent can be confirmed, for example, by Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), gas chromatography (GC), or gas chromatography mass spectrometry (GC / MS). It is sufficient that the solid electrolyte material after drying has ionic conductivity, and the organic solvent does not have to be completely removed. EXAMPLES
[0135] The details of the present disclosure will be described below using examples.
[0136] (Sample 1) 2 g of powdered Li3YBr2Cl4 (hereinafter referred to as LYBC) was weighed and placed in a commercially available glass sample tube. 4.4 g of o-chlorotoluene and 0.23 g of cumene were weighed and added to the sample tube. A solid electrolyte composition was prepared by stirring and mixing using a homogenizer (manufactured by AS ONE Corporation). The ratio of the weight of the solid content to the weight of the solid electrolyte composition was 30 wt%. The ratio of the weight of o-chlorotoluene to the total weight of the organic solvent was 95 wt%.
[0137] When the solid electrolyte composition was observed, no separation between the solid content and the solvent was observed, and good dispersibility was observed. When the solid electrolyte composition was left to stand for one day, no particularly noticeable changes were observed.
[0138] (Evaluation of Dispersion Stability) Into another sample tube, 2 g of the solid electrolyte composition according to Sample 1 was weighed and placed. The sample tube was left to stand for 3 hours. Thereafter, 1 g of the upper layer of the solid electrolyte composition was taken out, and the solid concentration was measured. Similarly, 1 g of the lower layer of the solid electrolyte composition was taken out, and the solid concentration was measured. Furthermore, the difference between the solid concentration of the upper layer and the solid concentration of the lower layer was calculated. A heat-drying moisture meter (manufactured by A&D Co., Ltd.) was used to measure the solid concentration of the upper layer of the sample tube and the solid concentration of the lower layer of the sample tube. The results are shown in Table 1.
[0139] (Sample 2) 2 g of powdered LYBC was weighed out and placed in a commercially available glass sample tube. 3.55 g of p-chlorotoluene was weighed out and added to the sample tube, and the mixture was stirred and mixed using a spatula to prepare a mixture.
[0140] 2 g of hydrogenated styrene-based thermoplastic elastomer (Tuftec, Asahi Kasei Corporation) was weighed and placed in a separate sample tube. 38 g of p-chlorotoluene was weighed and added to the sample tube. The mixture was stirred and dissolved using a magnetic stirrer on a hot plate at 80°C to prepare an organic binder solution with a concentration of 5 wt%.
[0141] 1.2 g of the organic binder solution was weighed out and added to the sample tube containing the mixture, and stirred and mixed in the same manner as in Sample 1. 0.047 g of tetralin was further weighed out and added to the sample tube, and stirred and mixed in the same manner as in Sample 1 to prepare a solid electrolyte composition. The ratio of the weight of the solid content to the weight of the solid electrolyte composition was 30 wt %. The ratio of the weight of p-chlorotoluene to the total weight of the organic solvent was 99 wt %.
[0142] When the solid electrolyte composition was observed, no separation between the solid content and the solvent was observed, and good dispersibility was shown. When the solid electrolyte composition was left to stand for one day and observed, no particularly noticeable changes were observed. The dispersion stability was evaluated in the same manner as in Sample 1. The results are shown in Table 1.
[0143] (Viscosity evaluation) For the solid electrolyte composition of Sample 2, the viscosity of the solid electrolyte composition immediately after preparation and the viscosity of the solid electrolyte composition after standing for one day were measured. A cone-plate type viscoelasticity measuring device (HAKE MARS, manufactured by Thermo Scientific) was used for the viscosity measurement. The solid electrolyte composition was stirred with a spatula before the measurement. The viscosity was measured at a shear rate of 10 / sec. The results are shown in Table 1.
[0144] (Sample 3) A solid electrolyte composition was prepared in the same manner as in Sample 2, except that 3.46 g of p-chlorotoluene and 0.14 g of tetralin were weighed out.
[0145] (Sample 4) A solid electrolyte composition was prepared in the same manner as in Sample 2, except that 1.23 g of p-chlorotoluene and 2.37 g of tetralin were weighed out.
[0146] (Sample 5) A solid electrolyte composition was prepared in the same manner as in Sample 2, except that 0.28 g of p-chlorotoluene and 3.32 g of tetralin were weighed out.
[0147] (Sample 6) A solid electrolyte composition was prepared in the same manner as in Sample 2, except that 0.47 g of p-chlorotoluene and 3.12 g of tetralin were weighed out.
[0148] (Sample 7) A solid electrolyte composition was prepared in the same manner as Sample 2, except that xylene was used instead of tetralin.
[0149] (Sample 8) A solid electrolyte composition was prepared in the same manner as Sample 3, except that xylene was used instead of tetralin.
[0150] (Sample 9) A solid electrolyte composition was prepared in the same manner as in Sample 8, except that 2.42 g of p-chlorotoluene and 1.19 g of xylene were weighed out.
[0151] (Sample 10) A solid electrolyte composition was prepared in the same manner as Sample 2, except that anisole was used instead of tetralin.
[0152] (Sample 11) A solid electrolyte composition was prepared in the same manner as in Sample 2, except that 3.6 g of p-chlorotoluene was weighed out and tetralin was not used.
[0153] Table 1 shows the measurement results of the solid content concentration and the viscosity of the solid electrolyte composition according to the sample.
[0154] [Table 1]
[0155] The solid electrolyte compositions according to Samples 1 to 10 exhibited excellent dispersion stability and excellent flow stability. On the other hand, when the solid electrolyte composition according to Sample 11 was left to stand and observed one day later, the viscosity of the solid electrolyte composition had increased and it was in a solid state. [Industrial Applicability]
[0156] The solid electrolyte composition according to the present disclosure can be used, for example, in the production of an all-solid-state lithium secondary battery.
Claims
1. A solid electrolyte material having ionic bonding properties; An organic solvent; Equipped with The organic solvent is A compound having a halogen group; At least one member selected from the group consisting of a compound having an ether group and a hydrocarbon; Including, The solid electrolyte material is in a particulate form and dispersed in the organic solvent, and contains at least one element selected from the group consisting of F, Cl, Br, and I. Solid electrolyte composition.
2. The solid electrolyte material does not contain sulfur element. The solid electrolyte composition according to claim 1 .
3. further comprising an organic binder; The solid electrolyte composition according to claim 1 or 2.
4. The solid electrolyte material has lithium ion conductivity, and At least one selected from the group consisting of Mg, Ca, Sr, Ba, Zn, Sn, Al, Sc, Ga, Bi, Sb, Zr, Hf, Ti, Ta, Nb, W, Y, Gd, Tb, and Sm; At least one selected from the group consisting of F, Cl, Br, and I; Including, The solid electrolyte composition according to claim 1 .
5. The solid electrolyte material is Li and At least one selected from the group consisting of Gd, Ca, Zr, and Y; At least one selected from the group consisting of F, Cl, Br, and I; Including, The solid electrolyte composition according to claim 1 .
6. The solid electrolyte material is Li and Y and At least one selected from the group consisting of F, Cl, Br, and I; Including, The solid electrolyte composition according to claim 1 .
7. The solid electrolyte material includes at least one selected from the group consisting of a material containing Li, Y, Cl, and Br, a material containing Li, Ca, Y, Gd, Cl, and Br, and a material containing Li, Zr, Y, and Cl. The solid electrolyte composition according to claim 5 .
8. The solid electrolyte material is Li 3 YBr 2 C 4 , Li 2.8 Ca 0.1 Y 0.5 G.D. 0.5 B 2 C 4 , and Li 2.5 Y 0.5 Zr 0.5 C 6 At least one selected from the group consisting of The solid electrolyte composition according to claim 7.
9. The solid electrolyte material is substantially Li and At least one selected from the group consisting of Mg, Ca, Sr, Ba, Zn, Sn, Al, Sc, Ga, Bi, Sb, Zr, Hf, Ti, Ta, Nb, W, Y, Gd, Tb, and Sm; At least one selected from the group consisting of F, Cl, Br, and I; Consists of only The solid electrolyte composition according to claim 1 .
10. A solid electrolyte material having ionic bonding properties; An organic solvent; Equipped with The organic solvent is A compound having a halogen group; At least one member selected from the group consisting of a compound having an ether group and a hydrocarbon; Including, The solid electrolyte material includes at least one selected from the group consisting of a material containing Li, Y, Cl, and Br, a material containing Li, Ca, Y, Gd, Cl, and Br, and a material containing Li, Zr, Y, and Cl. Solid electrolyte composition.
11. the ratio of the weight of the compound having a halogen group to the total weight of the organic solvent is 10% by weight or more; The solid electrolyte composition according to claim 1 .
12. The organic solvent contains a ring structure. The solid electrolyte composition according to claim 1 .
13. The organic solvent comprises an aromatic compound. The solid electrolyte composition according to claim 12.
14. The compound having a halogen group includes at least one selected from the group consisting of 1,2,4-trichlorobenzene, chlorobenzene, 2,4-dichlorotoluene, o-chlorotoluene, 1,3-dichlorobenzene, p-chlorotoluene, 1,2-dichlorobenzene, 1,4-dichlorobutane, and 3,4-dichlorotoluene. The solid electrolyte composition according to claim 1 .
15. The at least one selected from the group consisting of the compound having an ether group and the hydrocarbon includes at least one selected from the group consisting of tetralin, ethylbenzene, mesitylene, pseudocumene, xylene, cumene, dibutyl ether, and anisole. The solid electrolyte composition according to claim 1 .
16. Further comprising an active material, The solid electrolyte composition according to claim 1 .
17. mixing a solid electrolyte material having ionic bonding properties with a first organic solvent containing a compound having a halogen group, and a second organic solvent containing at least one selected from the group consisting of a compound having an ether group and a hydrocarbon; A method for producing a solid electrolyte composition comprising: In the solid electrolyte composition, the solid electrolyte material is in a particulate form and dispersed in the first organic solvent and the second organic solvent, and contains at least one selected from the group consisting of F, Cl, Br, and I. A method for producing a solid electrolyte composition.
18. A method for producing a solid electrolyte material having ionic bonding properties, a first organic solvent containing a compound having a halogen group, and a second organic solvent containing at least one selected from the group consisting of a compound having an ether group and a hydrocarbon, Including, The solid electrolyte material includes at least one selected from the group consisting of a material containing Li, Y, Cl, and Br, a material containing Li, Ca, Y, Gd, Cl, and Br, and a material containing Li, Zr, Y, and Cl. A method for producing a solid electrolyte composition.
19. preparing a mixture containing the solid electrolyte material and the first organic solvent; Then, the mixture is mixed with the second organic solvent. A method for producing the solid electrolyte composition according to claim 17 or 18.
20. When the solid electrolyte material, the first organic solvent, and the second organic solvent are mixed, an organic binder is mixed with the solid electrolyte material, the first organic solvent, and the second organic solvent. A method for producing the solid electrolyte composition according to claim 17 or 18.
21. When the mixture is mixed with the second organic solvent, the second organic solvent is mixed with an organic binder to prepare an organic binder solution, and the mixture is mixed with the organic binder solution. The method for producing the solid electrolyte composition according to claim 19.
22. further mixing at least one selected from the group consisting of a compound having a halogen group, a compound having an ether group, and a hydrocarbon with the solid electrolyte composition obtained by the solid electrolyte material, the first organic solvent, and the second organic solvent; A method for producing the solid electrolyte composition according to any one of claims 17 to 21.
23. Removing the organic solvent from the solid electrolyte composition according to any one of claims 1 to 16; A method for producing a solid electrolyte member comprising the steps of:
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