Ionic Conductive Layer and Method for Forming the Same

Abstract

To set the HLB value of a binder material contained in a solid ion conductive layer to a maximum of 10 to ensure hydrophilicity, and to set the reactivity value to a maximum of 20 to prevent the decomposition of an ion conductive material caused by the reaction between the binder material and the ion conductive material.SOLUTION: In a solid ion conductive layer, a binder material 1301 comprises polyvinyl chloride, poly(acrylonitrile), hydrogenated nitrile butadiene rubber, styrene-butadiene rubber, poly(methyl methacrylate), polyvinyl pyrrolidone, polyisobutylene, poly(vinylidene fluoride), paraffin wax, polyethylene, polydimethylsiloxane, poly(ethylene oxide), or any combination thereof. An ion conductive material is a halide-based material 1303.SELECTED DRAWING: Figure 13

Description

Technical Field

[0001] Technical Field The following relates to an ion conductive layer, a device including the ion conductive layer, and a method of forming the same, and particularly to a solid ion conductive layer, a device including the same, and a method of forming the same.

Background Art

[0002] Background Art Solid lithium batteries are expected to be high-energy-density, short-charging-time, and high-safety batteries compared to conventional lithium-ion batteries by using a lithium metal negative electrode. A solid electrolyte has been demonstrated to be useful for improving the performance of a lithium metal negative electrode.

Summary of the Invention

[0003] There is a continuing need in the industry for solid batteries with improved performance.

Brief Description of the Drawings

[0004] Brief Description of the Drawings The present disclosure will be better understood by reference to the accompanying drawings, and numerous features and advantages will be apparent to those skilled in the art.

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[0005] Those skilled in the art will understand that the elements in the figures are illustrated for simplicity and clarity and are not necessarily drawn to scale. For example, the dimensions of some of the elements in the figures may be exaggerated relative to other elements to improve understanding of the embodiments of the present invention. The use of the same reference numerals in different drawings indicates similar or identical items. For example, the dimensions of some of the elements in the figures may be exaggerated relative to other elements to improve understanding of the embodiments of the present invention. The use of the same reference numerals in different drawings indicates similar or identical items.

DETAILED DESCRIPTION OF THE INVENTION

[0006] Detailed Description of the Preferred Embodiments The following description is provided in conjunction with the figures to assist in understanding the teachings disclosed herein. The following discussion focuses on specific implementations and embodiments of the present teachings. This focus is provided to aid in explaining the teachings and should not be construed as limiting the scope or applicability of the teachings. The following discussion focuses on specific implementations and embodiments of the present teachings. This focus is provided to aid in explaining the teachings and should not be construed as limiting the scope or applicability of the teachings. This focus is provided to assist in explaining the teachings and should not be construed as limiting the scope or applicability of the teachings. When used herein, the terms "comprising," "including," "containing," "having," "possessing," or other variations thereof are intended to cover non-exclusive inclusion. For example, a process, method, article, or apparatus composed of a list of features is not necessarily limited to only those features but may include other features not explicitly listed or features inherent to such a process, method, article, or apparatus. Further, unless explicitly stated to the contrary, "or" refers to an inclusive "or" and not an exclusive "or." For example, condition A or B is satisfied by any one of the following: A is true (or exists) and B is false (or does not exist), A is false (or does not exist) and B is true (or exists), or both A and B are true (or exist).

[0007] When used herein, the terms "comprising," "including," "containing," "having," "possessing," or other variations thereof are intended to cover non-exclusive inclusion. For example, a process, method, article, or apparatus composed of a list of features is not necessarily limited to only those features but may include other features not explicitly listed or features inherent to such a process, method, article, or apparatus. Further, unless explicitly stated to the contrary, "or" refers to an inclusive "or" and not an exclusive "or." For example, condition A or B is satisfied by any one of the following: A is true (or exists) and B is false (or does not exist), A is false (or does not exist) and B is true (or exists), or both A and B are true (or exist). Further, unless explicitly stated to the contrary, "or" refers to an inclusive "or" and not an exclusive "or." For example, condition A or B is satisfied by any one of the following: A is true (or exists) and B is false (or does not exist), A is false (or does not exist) and B is true (or exists), or both A and B are true (or exist). For example, condition A or B is satisfied by any one of the following: A is true (or exists) and B is false (or does not exist), A is false (or does not exist) and B is true (or exists), or both A and B are true (or exist). A is true (or exists) and B is false (or does not exist), A is false (or does not exist) and B is true (or exists), or both A and B are true (or exist). A is true (or exists) and B is false (or does not exist), A is false (or does not exist) and B is true (or exists), or both A and B are true (or exist). A is true (or exists) and B is false (or does not exist), A is false (or does not exist) and B is true (or exists), or both A and B are true (or exist).

[0008] The use of "one" or "a" is employed to describe the elements and components described herein. This is done merely for convenience and to give a general sense of the scope of the invention. This specification should be read to include one or at least one unless the contrary is apparent, and the singular form includes the plural form, or vice versa. This is done merely for convenience and to give a general sense of the scope of the invention. This specification should be read to include one or at least one unless the contrary is apparent, and the singular form includes the plural form, or vice versa. This specification should be read to include one or at least one unless the contrary is apparent, and the singular form includes the plural form, or vice versa. or vice versa.

[0009] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The materials, methods, and examples are illustrative only and not intended to be limiting. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The materials, methods, and examples are illustrative only and not intended to be limiting. The materials, methods, and examples are illustrative only and not intended to be limiting.

[0010] Embodiments herein relate to a layer comprising an inorganic solid ion-conductive material and an organic material. The layer may be in the form of a film, tape, sheet, etc. In particular, the layer may be an ion-conductive layer, and in particular, a solid ion-conductive layer. For example, the ion-conductive layer can have an ion conductivity of at least 0.05 mS / cm. The ion-conductive layer can include a hygroscopic ion-conductive material, in particular, a halide-based material. In certain embodiments, the ion-conductive material can have lithium ion conductivity. In an embodiment, the ion-conductive layer is porous and can have specific pore structure features that can promote the improvement of the properties and / or performance of the ion-conductive layer. Embodiments herein relate to a layer comprising an inorganic solid ion-conductive material and an organic material. The layer may be in the form of a film, tape, sheet, etc. In particular, the layer may be an ion-conductive layer, and in particular, a solid ion-conductive layer. Embodiments herein relate to a layer comprising an inorganic solid ion-conductive material and an organic material. The layer may be in the form of a film, tape, sheet, etc. In particular, the layer may be an ion-conductive layer, and in particular, a solid ion-conductive layer. For example, the ion-conductive layer can have an ion conductivity of at least 0.05 mS / cm. The ion-conductive layer can include a hygroscopic ion-conductive material, in particular, a halide-based material. For example, the ion-conductive layer can have an ion conductivity of at least 0.05 mS / cm. The ion-conductive layer can include a hygroscopic ion-conductive material, in particular, a halide-based material. The ion-conductive layer can include a hygroscopic ion-conductive material, in particular, a halide-based material. In certain embodiments, the ion-conductive material can have lithium ion conductivity. In an embodiment, the ion-conductive layer is porous and can have specific pore structure features that can promote the improvement of the properties and / or performance of the ion-conductive layer. In an embodiment, the ion-conductive layer is porous and can have specific pore structure features that can promote the improvement of the properties and / or performance of the ion-conductive layer. In another embodiment, the ion-conductive layer may include a specific organic material that can promote the improvement of the properties and / or performance of the ion-conductive layer. For example, the ion-conductive layer can be improved. In another embodiment, the ion-conductive layer may include a specific organic material that can promote the improvement of the properties and / or performance of the ion-conductive layer. resulting ionic current resistance, pore structure, compatibility (miscibility), flexibility, chemical stability, electrochemistry can have stability, or any combination thereof.

[0011] Embodiments further relate to a method of forming an ion conductive layer. This method enables the formation of a solid ion conductive layer having a controlled thickness, porosity, and / or improved properties. In particular, the method can enable an improved formation of a solid ion conductive layer including a hygroscopic ion conductive material, more particularly a halide-based material. The method can include tape casting a green layer including a hygroscopic ion conductive material, a binder material, and optionally a pore forming material. As used herein, a green layer is intended to refer to an unfinished ion conductive layer, and at least one or more processes are required to convert the green layer into a finally formed ion conductive layer. Such processes can include curing, heating, sintering, cooling, drying, pressing, shaping, casting, punching, or any combination thereof, but are not limited thereto. In embodiments, the ion conductive layer can be a component of an electrochemical device. For example, the ion conductive layer can be a solid electrolyte layer. In another example, the ion conductive layer can be a composite layer such as an electrode layer having mixed ionic conductivity and electronic conductivity. In yet another example, the anode, cathode, or both can include an ion conductive layer. In certain embodiments, the electrochemical device can include a solid state battery. In a more particular example, the solid state battery can include a solid lithium battery. can include, but is not limited to, curing, heating, sintering, cooling, drying, pressing, shaping, casting, punching, or any combination thereof. In embodiments, the ion conductive layer can be a component of an electrochemical device. For example, the ion conductive layer can be a solid electrolyte layer. In another example, the ion

[0012] conductive layer can be a composite layer such as an electrode layer having mixed ionic conductivity and electronic conductivity. In yet another example, the anode, cathode, or both can include an ion conductive layer. In certain embodiments, the electrochemical device can include a solid state battery. For example, the ion conductive layer can be a solid electrolyte layer. In another example, the ion conductive layer can be a composite layer such as an electrode layer having mixed ionic conductivity and electronic conductivity. In yet another example, the anode, cathode, or both can include an ion conductive layer. In certain embodiments, the electrochemical device can include a solid state battery. In a more particular example, the solid state battery can include a solid lithium battery. In certain embodiments, the electrochemical device can include a solid state battery. In a more particular example, the solid state battery can include a solid lithium battery.

[0013] In an embodiment, the ion conductive layer can include an ion conductive material containing a hygroscopic material. In certain embodiments, the ion conductive material can have lithium ion conductivity. In one aspect, the hygroscopic material can include a halide-based material. In another aspect, the hygroscopic material can include a sulfide-based material. In yet another aspect, the hygroscopic material can include an oxyhalide, a halogenated hydroxide, or a combination thereof.

[0014] In an embodiment, the ion conductive layer is M 3-δ (Me k+ ) f X 3-δ+k*f (Formula I) and can include a halide-based material. -3 ≦ δ < 3; k is the valence of Me; 2 ≦ k < 6; and 0 ≦ f ≦ 1. In certain embodiments, the halide-based material is M 3 -δ Me k+ X 3-δ+k (Formula II), where -0.95 ≦ δ ≦ 0. 95.

[0015] M can include an alkali metal element including Li, Na, Rb, Cs, K, or any combination thereof. In a specific example, M can include Li. In one example M can include Li and another alkali metal element. In another example, M can consist of Li. In another example, M can consist of at least one of Li, Na, Cs, Rb, and K, and in a specific example, M can consist of Li, as well as at least one of Cs and N a.

[0016] ​Me can include a divalent element, a trivalent element, a tetravalent element, a pentavalent element, a hexavalent element, or a combination thereof. When Me is a combination of elements, k can be the average valence of the elements. For example, when Me contains x moles of a trivalent element and y moles of a tetravalent element, k = (3x + 4y) / (x + y). When Me contains equimolar amounts of a trivalent element and a tetravalent element, k = 3.5. In more specific examples, k can be 3 or 4 or 5. When Me is a combination of elements, k can be the average valence of the elements. For example, when Me contains x moles of a trivalent element and y moles of a tetravalent element, k = (3x + 4y) / (x + y). When Me contains equimolar amounts of a trivalent element and a tetravalent element, k = 3.5. In more specific examples, k can be 3 or 4 or 5. For example, when Me contains x moles of a trivalent element and y moles of a tetravalent element, k = (3x + 4y) / (x + y). When Me contains equimolar amounts of a trivalent element and a tetravalent element, k = 3.5. In more specific examples, k can be 3 or 4 or 5. For example, when Me contains x moles of a trivalent element and y moles of a tetravalent element, k = (3x + 4y) / (x + y). When Me contains equimolar amounts of a trivalent element and a tetravalent element, k = 3.5. In more specific examples, k can be 3 or 4 or 5. When Me contains equimolar amounts of a trivalent element and a tetravalent element, k = 3.5. In more specific examples, k can be 3 or 4 or 5. In more specific examples, k can be 3 or 4 or 5.

[0017] Further examples of Me can include alkaline earth elements such as Mg, Ca, Sr, and / or Ba, Group 12 elements such as Zn, or any combination thereof. Refer to the IUPAC Periodic Table of the Elements published on December 1, 2018 for the groups of elements pointed out in this disclosure. Further examples of Me can include alkaline earth elements such as Mg, Ca, Sr, and / or Ba, Group 12 elements such as Zn, or any combination thereof. Refer to the IUPAC Periodic Table of the Elements published on December 1, 2018 for the groups of elements pointed out in this disclosure. Refer to the IUPAC Periodic Table of the Elements published on December 1, 2018 for the groups of elements pointed out in this disclosure. Refer to the IUPAC Periodic Table of the Elements published on December 1, 2018 for the groups of elements pointed out in this disclosure.

[0018] X can include a halogen. For example, X can include one or more of Br, Cl, I, and F. For example, X can include Cl, Br, or a combination thereof. In another example, X can include F. In an example, X can include an anion group in addition to the halogen. Such anion groups can include amide (-NH ), hydroxide (-OH), -BF ), -BH 2 (borohydride), or a combination thereof. The anion group can be included as an impurity or a dopant. In a particular aspect, X can consist of one or more halogens, or a combination of one or more halogens and an anion group. In a particular aspect, X can consist of a halogen element. ), -BF 4 ), -BH 4 (borohydride), or a combination thereof. The anion group can be included as an impurity or a dopant. In a particular aspect, X can consist of one or more halogens, or a combination of one or more halogens and an anion group. In a particular aspect, X can consist of a halogen element. The anion group can be included as an impurity or a dopant. In a particular aspect, X can consist of one or more halogens, or a combination of one or more halogens and an anion group. In a particular aspect, X can consist of a halogen element. In a particular aspect, X can consist of one or more halogens, or a combination of one or more halogens and an anion group. In a particular aspect, X can consist of a halogen element. In a particular aspect, X can consist of one or more halogens, or a combination of one or more halogens and an anion group. In a particular aspect, X can consist of a halogen element. For example, X can consist of Cl, Br, or a combination thereof. Further In another example, X can consist of two or more of Cl, Br, F, and I, In a further example, X can consist of F.

[0019] In another example, Me can contain one or more trivalent elements. For example, Me can contain Group 13 elements such as In and / or Al, Group 3 elements, Sc, Y, and / or rare earth elements such as lanthanoids, or any combination thereof. In yet another example, Me can contain one or more tetravalent elements such as Group 4 elements (i.e., Zr and / or Hf), Sn, one or more pentavalent elements such as Group 5 elements (i.e., Nb and / or Ta), Bi, or any combination thereof. In a particular example, Me can contain rare earth elements such as Y, Sc, La, Ce, Pr, Nd, Pm, Sm , Eu, Tm, Gd, Tb, Dy, Ho, Lu, or any combination thereof.

[0020] In certain embodiments, the halide-based material can include (Li 1-d Na d )Li 2 REX 6 ( Formula III), where RE is one or more rare earth elements and 0 ≦ d < 1. Specific examples of RE can include Y, Gd, Er, or a combination thereof. For example, RE can consist of Y, and in another specific example, RE can consist of Y and at least one other rare earth element.

[0021] In another specific embodiment, the halide-based material is Li 3 Y​Z RE 1-Z X 6 (Formula IV) may be included, where 0 < Z ≤ 1, and RE is one or more rare earth elements other than Y. elements.

[0022] Specific examples of the halide-based ion conductive material may include the following: Li 3 YBr 6 , Li 3 YCl 6 , Li 3 (Al, Ga, In)X 6 , (Li 0.5 ,Na 0.5 ) 2 LiYCl 6 , Li 3 YBr 6 , Li 2.5 Y 0.5 Zr 0 .5 Cl 6 , Li 3 Y 0.95 Sm 0.05 Br 3 Cl 3 , Li 3 Y 0.9 Sm 0.1 Br 3 Cl 3 , Li 3 YBr 3 Cl 3 , Li 3 Y 0.9 Er 0.1 Br 3 Cl 3 , Li 3 Y 0.9 Lu 0.1 Br 3 Cl 3 , Li 3 Y 0.9 Tb 0.1 Br 3 Cl 3 , Li 3 Y 0.95 Bi 0.05 Br 6 , Li3 Y 0.9 Dy 0.1 Br 3 Cl 3 , Li 3 Y 0.9 Eu 0.1 Br 3 Cl 3 , Li 3.1 Y 0.9 Ba 0.1 Br 6 , Li 2.8 Y 0.9 Ta 0.1 Br 2 Cl 2 I 2 , Li 3.2 Y 0.9 Sr 0.2 Br 6 , LiCsCl 2 , Li 3 YCl 3 Br 3 , etc., or combinations thereof.

[0023] In an embodiment, the solid ion conductive layer can include ammonium halides such as NH 4 Cl, NH 4 Br, or combinations thereof. In one aspect, the dense ion conductive material can have performance improved by the presence of ammonium halides. For example, ammonium halides can be dopants for hygroscopic materials such as halide-based materials. In another example, ammonium halides can improve the ion conductivity of ion conductive materials. In another aspect, ammonium halides can be residual impurities remaining in the solid ion conductive layer from the step of forming the solid ion conductive layer. As an example, ammonium halides are added as pore-forming materials to the starting materials and removed to form pores for a solid ion conductive layer having improved pore characteristics. materials. In another aspect, ammonium halides can be residual impurities remaining in the solid ion conductive layer from the step of forming the solid ion conductive layer. For example, ammonium halides are added as pore-forming materials to the starting materials and removed to form pores for a solid ion conductive layer having improved pore characteristics. For example, ammonium halides are added as pore-forming materials to the starting materials and removed to form pores for a solid ion conductive layer having improved pore characteristics. For example, ammonium halides are added as pore-forming materials to the starting materials and removed to form pores for a solid ion conductive layer having improved pore characteristics. It may be formed. Exemplary pore characteristics can include porosity, average pore diameter, pore shape, pore orientation, aspect ratio, pore size distribution, or any combination thereof.

[0024] In certain embodiments, the ammonium halide may be complexed (chelated) with a hygroscopic material to promote improved formation and performance of the ion conductive layer. In an exemplary embodiment, the ammonium halide is used as a raw material in the process of forming a halide-based material such that the ammonium halide can be complexed with the halide-based material. Subsequent sublimation of the ammonium halide can promote the formation of improved pore characteristics of the ion conductive layer. In embodiments, the ammonium halide can be present in the ion conductive layer in an amount that promotes improved properties and performance of the solid ion conductive layer. In one aspect, the ion conductive layer can contain up to 20 vol% of ammonium halide, such as up to 18 vol%, 15 vol%, 10 vol%, 8 vol%, up to 5 vol%, up to 3 vol% %, up to 1 vol%, or up to 0.5 vol% with respect to the total volume of the solid ion conductive layer. In a further aspect, the ion conductive layer may contain at least 0.05 vol%, at least 0.1 vol%, at least 0.

[0025] vol%, at least 0.5 vol%, at least 1 vol %, or at least 1.5 vol% of ammonium halide. The content of ammonium halide can include any of the minimum and maximum ratios pointed out herein. In one aspect, the ion conductive layer can contain up to 20 vol% of ammonium halide, such as up to 18 vol%, 15 vol%, 10 vol%, 8 vol%, up to 5 vol%, up to 3 vol% %, up to 1 vol%, or up to 0.5 vol% with respect to the total volume of the solid ion conductive layer. In a further aspect, the ion conductive layer may contain at least 0.05 vol%, at least 0.1 vol%, at least 0. vol%, at least 0.5 vol%, at least 1 vol %, or at least 1.5 vol% of ammonium halide. The content of ammonium halide can include any of the minimum and maximum ratios pointed out herein. vol%, at least 0.5 vol%, at least 1 vol 2 %, or at least 1.5 vol% of ammonium halide. The content of ammonium halide can include any of the minimum and maximum ratios pointed out herein. %, or at least 1.5 vol% of ammonium halide. The content of ammonium halide can include any of the minimum and maximum ratios pointed out herein. The content of ammonium halide can include any of the minimum and maximum ratios pointed out herein. It is understood that it may also be the case.

[0026] In another example, the content of the ammonium halide is at most 10 wt%, for example at most 8 wt%, at most 5 wt%, at most 3 wt%, at most 1.5 wt%, at most 0.5 wt%, or at most 0.2 wt% with respect to the total weight of the ion conductive layer. In yet another example, the content of the ammonium halide is at least 0.01 wt% with respect to the total weight of the ion conductive layer, for example, at least 0 .1 wt%, at least 0.2 wt%, at least 0.3 wt%, or at least 0.5 wt%. Further, the content of the ammonium halide may include any of the minimum and maximum ratios pointed out herein.

[0027] In at least one non-limiting embodiment, the ion conductive layer may be essentially free of ammonium halide.

[0028] In another embodiment, the hygroscopic material can include lithium halide having an anti-perovskite crystal structure, lithium oxyhalide, lithium hydroxide halide, or a combination thereof. For example, the hygroscopic material is Li 3-x M x / 2 OA 1-z A’ z , where A and A’ are A-site halogens such as F, Cl, Br, or I. Specific examples are , Li 3 OCl, Li 3 OBr, Li 3 O(Cl,Br) (for example, Li 3 OCl 0.5 Br 0.5 ), Li 2 OHX (for example, Li​​​​​2 OHCl and Li 2 (such as OHBr) etc. can be mentioned It is possible.

[0029] In another embodiment, the ion conductive material can include a sulfide-based material. The sulfide-based material can include an amorphous phase, a crystalline phase, or any combination thereof. Specific examples of the sulfide-based material include xLi2S-yP2S5 (LPS), such as 0.67Li 2 S- 0.33P 2 S 5 、80Li 2 S-20P 2 S 5 、75Li 2 S-25P 2 S 5 、70L i 2 S-30P 2 S 5 etc., and can include Li 2 S-X, but are not limited thereto . Here, X represents at least one of the following sulfides: SiS 2 , GeS 2 , B 2 S 3 、 such as 0.50Li 2 S-0.50GeS 2 , LiI-Li 2 S-SiS 2 、such as 0. 40LiI-0.36Li 2 S-0.24SiS 2 etc., 0.05Li 4 SiO 4 -0. 57Li 2 S-0.38SiS 2 , Li 3 PO 4 -Li 2 S-SiS 2 , such as 0.01 Li 3 PO 4 -0.63Li 2S-0.36SiS 2 such as LiI-Li 2 S-B 2 S 3 , for example 0.44LiI-0.30Li 2 S-0.26B 2 S 3 such as LiI-Li 2 S -P 2 S 5 , for example 0.45LiI-0.37Li 2 S-0.18P 2 S 5 such as a-L i 3 PS 4 , LGPS (for example, Li 10 GeP 2 S 12 ), LPSCl (for example, Li 6 PS 5 Cl), LPSBr (for example, Li 6 PS 5 Br), LSPSCl (for example, Li 9.54 Si 1.74 P 1.44 S 11.7 Cl 0.3 ), Li 10.35 [Sn 0.27 Si 1.08 P 1.65 S 12 、or any combination thereof. Combination.

[0030] In a further embodiment, the solid ion conductive layer can contain a specific content of an ion conductive material that can promote the improved formation, properties and / or performance of the solid ion conductive layer. In one aspect, the solid ion conductive layer has at least 15 vol% of an ion conductive material based on the total weight of the solid ion conductive layer, for example at least 20 vol%, at least 25 vol%, at least 30 vol% based on the total volume of the ion conductive layer, at least The formation and characteristics and / or performance of the solid ion conductive layer can be promoted by including a specific content of an ion conductive material. Based on the total weight of the solid ion conductive layer, at least 15 vol% of an ion conductive material, for example, based on the total volume of the ion conductive layer at least 20 vol%, at least 25 vol%, at least 30 vol%, at least At least 35 vol%, at least 45 vol%, at least 50 vol%, at least 5 5 vol%, or at least 60 vol%. In another aspect, the solid ion conductive layer may contain, based on the total volume of the solid ion conductive layer, up to 95 vol% of the ion conductive material, for example, up to 90 vol%, up to 85 vol%, up to 80 vol%, up to 75 vo l%, up to 70 vol%, up to 65 vol%, up to 60 vol%, up to 55 vol%, or up to 50 vol%. In another aspect, the ion conductive material may be present in a content within a range including any of the minimum and maximum percentages indicated herein. In embodiments, the ion conductive layer can include an organic material that can facilitate the improved formation and improved performance of the solid ion conductive layer. For example, the organic material can promote the formation of a solid ion conductive layer having improved properties. The properties can

[0031] include pore characteristics, thickness, ionic conductivity, electronic conductivity, wettability of the electrode active material, compatibility, flexibility, chemical stability, electrochemical stability, or any combination thereof. In another example, the organic material may promote the formation of improved pore characteristics of the porous ion conductive layer. In one aspect, the organic material may include one or more binder materials, solvents, or a combination thereof. In embodiments, the solid ion conductive layer can include an organic material that is non-reactive with the ion conductive material. For example, the organic material is non-reactive with the ion conductive material during the process of forming the ion conductive layer, under the operating conditions to which the solid ion conductive layer is applied, or both. In embodiments, the solid ion conductive layer can include an organic material that is non-reactive with the ion conductive material. For example, the organic material is non-reactive with the ion conductive material during the process of forming the ion conductive layer, under the operating conditions to which the solid ion conductive layer is applied, or both. In another example, the organic material may promote the formation of improved pore characteristics of the porous ion conductive layer. In one aspect, the organic material may include one or more binder materials, solvents, or a combination thereof. In embodiments, the solid ion conductive layer can include an organic material that is non-reactive with the ion conductive material. For example, the organic material is non-reactive with the ion conductive material during the process of forming the ion conductive layer, under the operating conditions to which the solid ion conductive layer is applied, or both.

[0032] In embodiments, the solid ion conductive layer can include an organic material that is non-reactive with the ion conductive material. For example, the organic material is non-reactive with the ion conductive material during the process of forming the ion conductive layer, under the operating conditions to which the solid ion conductive layer is applied, or both. For example, the organic material is non-reactive with the ion conductive material during the process of forming the ion conductive layer, under the operating conditions to which the solid ion conductive layer is applied, or both. For example, the organic material is non-reactive with the ion conductive material during the process of forming the ion conductive layer, under the operating conditions to which the solid ion conductive layer is applied, or both. It can remain non-reactive with respect to the conductive material. In another example, in the process of forming a solid ion conductive material, the organic material can have little or no adverse effect on either the composition, the ion conductivity, or both of the ion conductive material. In the process of forming a solid ion conductive material, the organic material can have little or no adverse effect on either the composition, the ion conductivity, or both of the ion conductive material. It can remain non-reactive with respect to the conductive material. In another example, in the process of forming a solid ion conductive material, the organic material can have little or no adverse effect on either the composition, the ion conductivity, or both of the ion conductive material.

[0033] In certain embodiments, the organic material can have a specific reactivity value that promotes the improved formation and improved properties of the solid ion conductive layer. In one example, the organic material can have a reactivity value of up to 20%, such as up to 18%, up to 15%, up to 12%, or up to 10%. In a further example, the organic material can have a reactivity value of less than 10%, such as up to 9%, up to 8%, up to 7%, up to 6%, up to 5%, up to 4%, up to 3%, or up to 2%. In another example, the organic material can have a reactivity value greater than 0%, such as at least 0.01%, at least 0.1%, at least 0.2%, at least 0.3%, at least 0.5%, at least 0.8%, or at least 1%. Further, the reactivity value can be in a range that includes any of the minimum and maximum percentages described herein. For example, the organic material can have a reactivity value of up to 2%. In certain embodiments, the organic material has a reactivity value of less than 20% with respect to a halide-based material containing LiYBr, or a halide-based material having a crystal structure similar to that of LiYBr, such as a monoclinic crystal structure. In another specific embodiment, the organic material has a reactivity value of less than 20% with respect to a halide-based material containing LiYCl. In the process of forming a solid ion conductive material, the organic material can have little or no adverse effect on either the composition, the ion conductivity, or both of the ion conductive material. In the process of forming a solid ion conductive material, the organic material can have little or no adverse effect on either the composition, the ion conductivity, or both of the ion conductive material. In the process of forming a solid ion conductive material, the organic material can have little or no adverse effect on either the composition, the ion conductivity, or both of the ion conductive material. In the process of forming a solid ion conductive material, the organic material can have little or no adverse effect on either the composition, the ion conductivity, or both of the ion conductive material. In the process of forming a solid ion conductive material, the organic material can have little or no adverse effect on either the composition, the ion conductivity, or both of the ion conductive material. In the process of forming a solid ion conductive material, the organic material can have little or no adverse effect on either the composition, the ion conductivity, or both of the ion conductive material. In the process of forming a solid ion conductive material, the organic material can have little or no adverse effect on either the composition, the ion conductivity, or both of the ion conductive material. In the process of forming a solid ion conductive material, the organic material can have little or no adverse effect on either the composition, the ion conductivity, or both of the ion conductive material. In the process of forming a solid ion conductive material, the organic material can have little or no adverse effect on either the composition, the ion conductivity, or both of the ion conductive material. In the process of forming a solid ion conductive material, the organic material can have little or no adverse effect on either the composition, the ion conductivity, or both of the ion conductive material. In the process of forming a solid ion conductive material, the organic material can have little or no adverse effect on either the composition, the ion conductivity, or both of the ion conductive material. 3 LiYBr 6 In the process of forming a solid ion conductive material, the organic material can have little or no adverse effect on either the composition, the ion conductivity, or both of the ion conductive material. In the process of forming a solid ion conductive material, the organic material can have little or no adverse effect on either the composition, the ion conductivity, or both of the ion conductive material. 3 LiYBr 6 In the process of forming a solid ion conductive material, the organic material can have little or no adverse effect on either the composition, the ion conductivity, or both of the ion conductive material. In the process of forming a solid ion conductive material, the organic material can have little or no adverse effect on either the composition, the ion conductivity, or both of the ion conductive material. In the process of forming a solid ion conductive material, the organic material can have little or no adverse effect on either the composition, the ion conductivity, or both of the ion conductive material. 3 LiYCl 6A halide-based material containing, or Li 3 YCl 6 A crystal structure similar to For example, less than 10% for a halide-based material containing a hexagonal or trigonal crystal structure Can have a reactivity of

[0034] The reactivity value can be determined as follows. The reactivity value of an organic material with respect to an ion-conductive material Is obtained by mixing a solid ion-conductive material and an organic material in a weight percentage ratio of 10:90, And keeping the mixture in an inert atmosphere at 100 °C or lower, for example, at 20 °C to 60 °C for at least 12 hours, Up to a maximum of 24 hours. X-ray diffraction analysis is performed to detect changes in the characteristic peaks of the ion-conductive Material, as well as changes in other peaks before and after the test, such as changes in the XRD pattern For example, changes include disappearance of characteristic peaks, changes in the intensity of characteristic peaks Changes in the intensity of characteristic peaks of specific impurities or decomposition / deterioration products of the solid ion-conductive material, or combinations thereof, etc. Can be mentioned.

[0035] In particular, the reactivity value of an organic solvent can be determined by testing as follows. The solvent can be mixed with a solid Ion-conductive material in a weight percentage ratio of 90:10, where the solid Ion-conductive material is present in the mixture at 10 wt% with respect to the total weight of the mixture, and the solvent is present in the mixture At 90 wt% with respect to the total weight of the mixture. After mixing for at least 12 hours and up to 24 hours The remaining solvent can be dried or evaporated at a temperature up to 100 °C . After completely removing the solvent, the dried solid material is recovered and sealed in a gas Tight-sealed sample holder with a Kapton film window, and X-ray diffraction (XRD) analysis at 25 - 80 degrees 2θ is performed, It can be carried out with a step size of 7.5 degrees and a step time of 120 seconds. All tests can be performed in a dry environment with an H 2 O content of < 1 ppm.

[0036] The reactivity of the solvent material can be determined by the formula RV = [B / A] × 100% based on the XRD pattern of the dry solid material, where A represents the intensity of the characteristic peak of the solid ion-conductive material and B represents the intensity of the characteristic peak of the typical decomposition product of the solid ion-conductive material. The typical decomposition product may be a binary system containing lithium and the main anion atom of the ion-conductive material For example, lithium halide can be a typical decomposition product of the halide-based material according to the embodiments of the present specification Therefore, A can be the characteristic peak of the halide-based material, and B can be the characteristic peak of lithium halide Referring to FIG. 18, A and B are the reactivity values of the organic material having Li YBr 3 tested by comparing the XRD pattern with the original XRD pattern of Li 6 YBr The characteristic XRD peak of Li 3 YBr 6 usually appears between 2θ of 31 degrees and 32.2 degrees, and the characteristic peak of LiBr appears between 2θ of 27.9 to 28.5 degrees. The characteristic peak of Li 3 YCl 6 appears between 2θ of 40.5 degrees and 41.5 degrees, and LiCl appears between 2θ of 34.5 degrees and 35 .5 degrees. The XRD pattern of the dry solid material remaining after removing the solvent is the representative decomposition product of the ion 3 conductive material, for example, when a solvent test is performed on a halide-based material 6 characteristics between 2θ of 40.5 degrees and 41.5 degrees, and LiCl is between 2θ of 34.5 degrees and 35 .5 degrees. When the XRD pattern of the dry solid material remaining after removing the solvent is that of the representative decomposition product of the ion-conductive material, for example, when a solvent test is performed on a halide-based material and the XRD pattern of the dry solid material remaining after removing the solvent is that of the representative decomposition product of the ion-conductive material, for example, when a solvent test is performed on a halide-based material Without including the characteristic peak of lithium halide, when A is not 0, the reactivity value of the solvent is 0 and it can be determined. When the XRD pattern of the dry solid material does not include the characteristic peak of the ion conductive material, it can be determined as indeterminate. Also, when the ion conductive substance is completely decomposed after mixing with the solvent, the reactivity of the solvent can be regarded as indeterminate.

[0037] In some cases, the XRD pattern of the original ion conductive material may include the characteristic peaks of typical decomposition products. For example, the halide-based material may contain lithium halide as an impurity. In those cases, using the XRD pattern of the original ion conductive material, RI can be calculated, where RI O here RI O =[b / a]×100%, b represents the intensity of the characteristic peak of the decomposition product, and a represents the intensity of the characteristic peak of the ion conductive material. The reactivity value (RV) of the solvent is RV = RI - RI DS - RI O In the formula, RI DS =[B / A]×100 %, B represents the intensity of the characteristic peak of the decomposition product of the dry solid substance after solvent removal, and A represents the intensity of the characteristic peak of the ion conductive substance, and can be obtained.

[0038] The reactivity value of the soluble organic binder can be determined by testing as follows. A solvent with a reactivity value of 0 can be used in the test. The binder, ion conductive material, and solvent can be mixed at a weight ratio of 10:10:80. The binder is present at 10 wt% in the mixture with respect to the total weight of the mixture, the solvent is present at 80 wt% in the mixture with respect to the total weight of the mixture, and the ion conductive material is present at 10 wt% in the mixture with respect to the total weight of the mixture. At least 12 wt% of the binder, 10 wt% of the ion conductive material, and 80 wt% of the solvent are used. The mixture is heated at a temperature of at least 120 °C for at least 1 hour. After heating, the mixture is cooled to room temperature, and the XRD pattern of the resulting dry solid material is measured. If the XRD pattern of the dry solid material does not include the characteristic peak of the ion conductive material, it can be determined as indeterminate. Also, if the ion conductive substance is completely decomposed after mixing with the solvent, the reactivity of the solvent can be regarded as indeterminate. wt% of the binder, 10 wt% of the ion conductive material, and 80 wt% of the solvent are used. The mixture is heated at a temperature of at least 120 °C for at least 1 hour. After heating, the mixture is cooled to room temperature, and the XRD pattern of the resulting dry solid material is measured. If the XRD pattern of the dry solid material does not include the characteristic peak of the ion conductive material, it can be determined as indeterminate. Also, if the ion conductive substance is completely decomposed after mixing with the solvent, the reactivity of the solvent can be regarded as indeterminate. After mixing for up to 24 hours, the mixture is dried to remove the residual solvent at a temperature of 100 °C or lower. The dried solid mixture of the binder and the ion conductive material can be collected in an airtight sample holder with a Kapton film window for XRD measurement and sealed. The entire test can be carried out in a dry environment with an H O content of less than 1 ppm. XRD analysis can be performed using an X 2 ray diffractometer at 2θ from 25 to 80 degrees, with a step size of 7.5 °C and a step time of 120 seconds. The reactivity of the soluble binder can be determined in a similar manner using the same formula as described in the embodiments herein to determine the reactivity of the solvent.

[0039] The reactivity value of the insoluble organic binder can be determined by testing as follows. If the binder does not dissolve in a solvent having a reactivity value of 0, the ion conductive material and the insoluble binder are mixed in a 50:50 weight ratio such that each of the ion conductive material and the insoluble binder is present in the mixture at 50 wt% based on the total weight of the ion conductive material and the insoluble binder. This mixture can be heated to melt the binder into a liquid state.

[0040] After the binder is completely melted, mixing can be continued for at least 1 hour up to a maximum of 12 hours. After mixing, the mixture of the binder and the ion conductive material is cooled and solidified, and collected and sealed in an airtight sample holder with a Kapton film window for XRD analysis. The entire test can be carried out in a dry environment with an H O content of less than 1 ppm. XRD analysis is performed using an X ray diffractometer at 2θ of 25 to 80 degrees, with a step size of 7.5 °C and a step time of 1 second. The mixture of the binder and the ion conductive material is cooled and solidified, and collected and sealed in an airtight sample holder with a Kapton film window for XRD analysis. The entire test can be carried out in a dry environment with an H O content of less than 1 ppm. XRD analysis is performed using an X 2 ray diffractometer at 2θ of 25 to 80 degrees, with a step size of 7.5 °C and a step time of 1 second. It can be carried out at a 20 - second rate.

[0041] The reactivity value of the insoluble binder can be determined in a similar manner using the same formula as described in the embodiments of this specification for determining the reactivity value of the solvent. It can be determined in a similar way using the same formula as described in the embodiments of this specification for determining the reactivity value of the solvent.

[0042] In certain embodiments, the organic material can have a specific moisture absorption rate (hereinafter referred to as "MAR") that can facilitate the improved formation and improved properties of the solid ion - conductive layer. In one example, the organic material can have a MAR of up to 1.0 wt%, such as up to 0.8 wt%, up to 0.5 wt%, up to 0 .3 wt%, or up to 0.1 wt%. In another example, the organic material can have a MAR of 0 wt% or at least 0.01 wt% or at least 0.03 wt% . In a further example, the organic material can have a MAR within the range including any of the minimum and maximum percentages described herein. For example, the organic material can have a MAR of up to 0.3 wt%. The MAR can be determined by testing as follows. A test piece of the organic material having a predetermined dimension is placed in distilled water or exposed to humid air at 23 °C to 60 °C (i.e., relative humidity 5 0%) for 24 hours. The moisture absorption rate can be determined by the formula, MAR = [(W

[0043] - W AE ) / W AE - W BE ) / W BE × 100%, where W BE is the weight of the dried sample, and W AE is the weight of the sample before exposure to water or humid air. The sample can be dried in an oven and then placed in a desiccator to cool. Weigh the sample immediately after cooling to obtain W BE is obtained. Also, the MAR can be measured in accordance with ASTM D570 or ISO 62. It is also possible.

[0044] In one aspect, the organic material can have a hydrophobic portion, a lipophilic portion, or a combination thereof. In certain aspects, the organic material can have a specific hydrophilic-lipophilic balance (hereinafter referred to as "HLB") value that can facilitate the improved formation and properties of the solid ion conductive layer. In another specific aspect, organic solvents and organic binder materials having different HLB values can be used to form the ion conductive layer. In one example, the organic material has an HLB value of at most 10, such as at most 9.6, at most 9, at most 8.8, at most 8.2, at most 7.6, at most 7.3, at most 7, at most 6.6, at most 6, at most 5.6, at most 5, at most 4.8, at most 4 .2, at most 4, at most 3.8, at most 3.3, at most 2.6, at most 2.2 . In another example, the organic material can have an HLB value of 0 or more, such as at least 0.001, at least 0.005, at least 0.01, at least 0.05, at least 0.08, or at least 0. 1. In a specific example, the organic material can have an HLB value of 0. In a further example, the organic material can have an HLB value within a range including any of the minimum and maximum values described herein. For example, the organic material can have an HLB value of up to 4. In another example, the organic solvent can have an HLB value lower than that of the organic binder material. In a more specific embodiment, the solvent has an HLB value of 0. 1. In a specific example, the organic material can have an HLB value of 0. In a further example, the organic material can have an HLB value within a range including any of the minimum and maximum values described herein. For example, the organic material can have an HLB value of up to 4. In another example, the organic solvent can have an HLB value lower than that of the organic binder material. In a more specific embodiment, the solvent has an HLB value of 0. 1. In a specific example, the organic material can have an HLB value of 0. In a further example, the organic material can have an HLB value within a range including any of the minimum and maximum values described herein. For example, the organic material can have an HLB value of up to 4. In another example, the organic solvent can have an HLB value lower than that of the organic binder material. In a more specific embodiment, the solvent has an HLB value of 0. 1. In a specific example, the organic material can have an HLB value of 0. In a further example, the organic material can have an HLB value within a range including any of the minimum and maximum values described herein. For example, the organic material can have an HLB value of up to 4. In another example, the organic solvent can have an HLB value lower than that of the organic binder material. In a more specific embodiment, the solvent has an HLB value of 0. In a further example, the organic material can have an HLB value within a range including any of the minimum and maximum values described herein. For example, the organic material can have an HLB value of up to 4. In another example, the organic solvent can have an HLB value lower than that of the organic binder material. In a more specific embodiment, the solvent has an HLB value of 0. In a further example, the organic material can have an HLB value within a range including any of the minimum and maximum values described herein. For example, the organic material can have an HLB value of up to 4. In another example, the organic solvent can have an HLB value lower than that of the organic binder material. In a more specific embodiment, the solvent has an HLB value of 0. B value. In another example, the organic solvent can have an HLB value lower than that of the organic binder material. In a more specific embodiment, the solvent has an HLB value of 0. In a more specific embodiment, the solvent has an HLB value of 0. It can be had. In another more specific embodiment, the organic binder material can have an HLB value of 0 or greater than 0, for example up to 10 or less than 10. The HLB value can be determined according to Griffin's mathematical method using the formula, HLB = 20 × M

[0045] / M, where M h is the molecular mass of the hydrophilic part of the organic material and M is the molecular mass of the entire organic material. For the sake of understanding, using an exemplary scale of HLB from 0 to 20, an HLB value of 0 can correspond to a completely lipophilic / hydrophobic molecule and a value of 20 can correspond to a completely hydrophilic / h hydrophobic molecule. Exemplary hydrophilic groups can include N (tertiary amine), -COOH (carboxyl), -O -(ether), -OH (hydroxyl), -COO- (ester), C=O (carbonyl), or any combination thereof. Exemplary lipophilic groups can include -C≡ N (nitrile), -CH

[0046] (methyl), =CH (methylene), -CH -, -CH=, -C 3 (phenyl group), -F (fluoro group), -Cl (chloro group), or any combination of these 2 can be included. 2 -CH -C 6 H 5 (phenyl group), -F (fluoro group), -Cl (chloro group), or any combination of these can be included.

[0047] In an embodiment, the organic material can have a specific dielectric constant that can promote the improved formation, properties and / or performance of the solid ion conductive layer. In one aspect, the organic material can have a dielectric constant of up to 35, for example up to 33, up to 31, up to 29, up to 26, up to 23, up to 20 , up to 19, up to 17, up to 15, up to 13, up to 12, up to 11, up to 10, etc. dielectric can have a rate. In another aspect, the organic material is at least 1, at least 2, at least 3, at least 4, or at least 5, such as having a dielectric constant of at least 0.5 It may have. Further, the organic material may include a dielectric constant within the range including any of the minimum and maximum values pointed out herein.

[0048] In certain embodiments, the organic material may include a specific HLB value, a specific reactivity value, a specific dielectric constant, or any combination thereof. In one aspect, the organic material has an HLB value of 0, a reactivity value of at most 20%, a dielectric constant of at most 35, or any combination thereof, and may include a solvent material. In a specific embodiment, the organic material includes a solvent having an HLB value of 0, a reactivity value of less than 20%, and a dielectric constant of at most 12. More specific examples of organic solvents can include heptane, cyclohexane, dibromo methane, dichloromethane, 1,2-dichloroethane, or any combination thereof.

[0049] In a further aspect, the organic material may include a binder material including a specific HLB value, a specific reactivity value, or any combination thereof. For example, the organic binder material may include an HLB value of less than 10 and a reactivity value of less than 20%. In another example, the organic binder material may include an HLB value of less than 10 and a reactivity value of less than 10%. More specific examples of organic binders can include hydrogenated nitrile butadiene rubber, styrene butadiene rubber, polyisobutylene, poly(vinylidene fluoride), poly(acrylonitrile) , paraffin wax, polyethylene, polyvinyl chloride, poly(ethylene oxide), poly ​​​ Examples include vinylpyrrolidone, poly(methyl methacrylate), or any combination thereof. It can be.

[0050] In some embodiments, the organic material can include polymers such as thermosets, thermoplastics, or any combination thereof. It can include polymers such as poly(propylene oxide), polyvinyl chloride, poly(vinylidene fluoride), polyacrylonitrile, poly(dimethylsiloxane), poly[bis(methoxyethoxy)-phosphazene], polypropylene glycol, polyethylene carbonate, polycaprolactone, poly(trimethylene carbonate), paraffin wax, polyisobutylene, polyvinylpyrrolidone, hydrogenated nitrile butadiene rubber, styrene butadiene rubber, high density polyethylene, low density polyethylene, poly(ethylene oxide), polyurethane, polystyrene, poly(methyl acrylate), poly(vinylidene fluoride)-co-hexafluoropropylene, poly(acrylonitrile-co-butadiene), poly(styrene-butadiene-styrene), and styrene-ethylene-butylene-styrene.

[0051] Specific examples of organic materials can include at least one polymer selected from the group consisting of poly(propylene oxide), polyvinyl chloride, poly(vinylidene fluoride), polyacrylonitrile, poly(dimethylsiloxane), poly[bis(methoxyethoxy)-phosphazene], polypropylene glycol, polyethylene carbonate, polycaprolactone, poly(trimethylene carbonate), paraffin wax, polyisobutylene, polyvinylpyrrolidone, hydrogenated nitrile butadiene rubber, styrene butadiene rubber, high density polyethylene, low density polyethylene, poly(ethylene oxide), polyurethane, polystyrene, poly(methyl acrylate), poly(vinylidene fluoride)-co-hexafluoropropylene, poly(acrylonitrile-co-butadiene), poly(styrene-butadiene-styrene), and styrene-ethylene-butylene-styrene. In more specific examples, the organic material can be one or more polymers selected from the group consisting of poly(propylene oxide), polyvinyl chloride, poly(vinylidene fluoride), poly(methyl methacrylate), polyacrylonitrile, poly(dimethylsiloxane), poly[bis(methoxyethoxy)-phosphazene], polypropylene glycol, polyethylene carbonate, polycaprolactone, poly(trimethylene carbonate), paraffin wax, polyisobutylene. It can include polymers such as poly(propylene oxide), polyvinyl chloride, poly(vinylidene fluoride), poly(methyl methacrylate), polyacrylonitrile, poly(dimethylsiloxane), poly[bis(methoxyethoxy)-phosphazene], polypropylene glycol, polyethylene carbonate, polycaprolactone, poly(trimethylene carbonate), paraffin wax, polyisobutylene, polyvinylpyrrolidone, hydrogenated nitrile butadiene rubber, styrene butadiene rubber, high density polyethylene, low density polyethylene, poly(ethylene oxide), polyurethane, polystyrene, poly(methyl acrylate), poly(vinylidene fluoride)-co-hexafluoropropylene, poly(acrylonitrile-co-butadiene), poly(styrene-butadiene-styrene), and styrene-ethylene-butylene-styrene. It can include polymers such as poly(propylene oxide), polyvinyl chloride, poly(vinylidene fluoride), poly(methyl methacrylate), polyacrylonitrile, poly(dimethylsiloxane), poly[bis(methoxyethoxy)-phosphazene], polypropylene glycol, polyethylene carbonate, polycaprolactone, poly(trimethylene carbonate), paraffin wax, polyisobutylene, polyvinylpyrrolidone, hydrogenated nitrile butadiene rubber, styrene butadiene rubber, high density polyethylene, low density polyethylene, poly(ethylene oxide), polyurethane, polystyrene, poly(methyl acrylate), poly(vinylidene fluoride)-co-hexafluoropropylene, poly(acrylonitrile-co-butadiene), poly(styrene-butadiene-styrene), and styrene-ethylene-butylene-styrene. It can include polymers such as poly(propylene oxide), polyvinyl chloride, poly(vinylidene fluoride), poly(methyl methacrylate), polyacrylonitrile, poly(dimethylsiloxane), poly[bis(methoxyethoxy)-phosphazene], polypropylene glycol, polyethylene carbonate, polycaprolactone, poly(trimethylene carbonate), paraffin wax, polyisobutylene, polyvinylpyrrolidone, hydrogenated nitrile butadiene rubber, styrene butadiene rubber, high density polyethylene, low density polyethylene, poly(ethylene oxide), polyurethane, polystyrene, poly(methyl acrylate), poly(vinylidene fluoride)-co-hexafluoropropylene, poly(acrylonitrile-co-butadiene), poly(styrene-butadiene-styrene), and styrene-ethylene-butylene-styrene. It can include polymers such as poly(propylene oxide), polyvinyl chloride, poly(vinylidene fluoride), poly(methyl methacrylate), polyacrylonitrile, poly(dimethylsiloxane), poly[bis(methoxyethoxy)-phosphazene], polypropylene glycol, polyethylene carbonate, polycaprolactone, poly(trimethylene carbonate), paraffin wax, polyisobutylene, polyvinylpyrrolidone, hydrogenated nitrile butadiene rubber, styrene butadiene rubber, high density polyethylene, low density polyethylene, poly(ethylene oxide), polyurethane, polystyrene, poly(methyl acrylate), poly(vinylidene fluoride)-co-hexafluoropropylene, poly(acrylonitrile-co-butadiene), poly(styrene-butadiene-styrene), and styrene-ethylene-butylene-styrene. It can include polymers such as poly(propylene oxide), polyvinyl chloride, poly(vinylidene fluoride), poly(methyl methacrylate), polyacrylonitrile, poly(dimethylsiloxane), poly[bis(methoxyethoxy)-phosphazene], polypropylene glycol, polyethylene carbonate, polycaprolactone, poly(trimethylene carbonate), paraffin wax, polyisobutylene, polyvinylpyrrolidone, hydrogenated nitrile butadiene rubber, styrene butadiene rubber, high density polyethylene, low density polyethylene, poly(ethylene oxide), polyurethane, polystyrene, poly(methyl acrylate), poly(vinylidene fluoride)-co-hexafluoropropylene, poly(acrylonitrile-co-butadiene), poly(styrene-butadiene-styrene), and styrene-ethylene-butylene-styrene. It can include polymers such as poly(propylene oxide), polyvinyl chloride, poly(vinylidene fluoride), poly(methyl methacrylate), polyacrylonitrile, poly(dimethylsiloxane), poly[bis(methoxyethoxy)-phosphazene], polypropylene glycol, polyethylene carbonate, polycaprolactone, poly(trimethylene carbonate), paraffin wax, polyisobutylene, polyvinylpyrrolidone, hydrogenated nitrile butadiene rubber, styrene butadiene rubber, high density polyethylene, low density polyethylene, poly(ethylene oxide), polyurethane, polystyrene, poly(methyl acrylate), poly(vinylidene fluoride)-co-hexafluoropropylene, poly(acrylonitrile-co-butadiene), poly(styrene-butadiene-styrene), and styrene-ethylene-butylene-styrene. It can include polymers such as poly(propylene oxide), polyvinyl chloride, poly(vinylidene fluoride), poly(methyl methacrylate), polyacrylonitrile, poly(dimethylsiloxane), poly[bis(methoxyethoxy)-phosphazene], polypropylene glycol, polyethylene carbonate, polycaprolactone, poly(trimethylene carbonate), paraffin wax, polyisobutylene, polyvinylpyrrolidone, hydrogenated nitrile butadiene rubber, styrene butadiene rubber, high density polyethylene, low density polyethylene, poly(ethylene oxide), polyurethane, polystyrene, poly(methyl acrylate), poly(vinylidene fluoride)-co-hexafluoropropylene, poly(acrylonitrile-co-butadiene), poly(styrene-butadiene-styrene), and styrene-ethylene-butylene-styrene. It can include polymers such as poly(propylene oxide), polyvinyl chloride, poly(vinylidene fluoride), poly(methyl methacrylate), polyacrylonitrile, poly(dimethylsiloxane), poly[bis(methoxyethoxy)-phosphazene], polypropylene glycol, polyethylene carbonate, polycaprolactone, poly(trimethylene carbonate), paraffin wax, polyisobutylene, polyvinylpyrrolidone, hydrogenated nitrile butadiene rubber, styrene butadiene rubber, high density polyethylene, low density polyethylene, poly(ethylene oxide), polyurethane, polystyrene, poly(methyl acrylate), poly(vinylidene fluoride)-co-hexafluoropropylene, poly(acrylonitrile-co-butadiene), poly(styrene-butadiene-styrene), and styrene-ethylene-butylene-styrene. In more specific examples, the organic material can be one or more polymers selected from the group consisting of poly(propylene oxide), polyvinyl chloride, poly(vinylidene fluoride), poly(methyl methacrylate), polyacrylonitrile, poly(dimethylsiloxane), poly[bis(methoxyethoxy)-phosphazene], polypropylene glycol, polyethylene carbonate, polycaprolactone, poly(trimethylene carbonate), paraffin wax, polyisobutylene. It can include polymers such as poly(propylene oxide), polyvinyl chloride, poly(vinylidene fluoride), poly(methyl methacrylate), polyacrylonitrile, poly(dimethylsiloxane), poly[bis(methoxyethoxy)-phosphazene], polypropylene glycol, polyethylene carbonate, polycaprolactone, poly(trimethylene carbonate), paraffin wax, polyisobutylene, polyvinylpyrrolidone, hydrogenated nitrile butadiene rubber, styrene butadiene rubber, high density polyethylene, low density polyethylene, poly(ethylene oxide), polyurethane, polystyrene, poly(methyl acrylate), poly(vinylidene fluoride)-co-hexafluoropropylene, poly(acrylonitrile-co-butadiene), poly(styrene-butadiene-styrene), and styrene-ethylene-butylene-styrene. It can include polymers such as poly(propylene oxide), polyvinyl chloride, poly(vinylidene fluoride), poly(methyl methacrylate), polyacrylonitrile, poly(dimethylsiloxane), poly[bis(methoxyethoxy)-phosphazene], polypropylene glycol, polyethylene carbonate, polycaprolactone, poly(trimethylene carbonate), paraffin wax, polyisobutylene, polyvinylpyrrolidone, hydrogenated nitrile butadiene rubber, styrene butadiene rubber, high density polyethylene, low density polyethylene, poly(ethylene oxide), polyurethane, polystyrene, poly(methyl acrylate), poly(vinylidene fluoride)-co-hexafluoropropylene, poly(acrylonitrile-co-butadiene), poly(styrene-butadiene-styrene), and styrene-ethylene-butylene-styrene. It can include polymers such as poly(propylene oxide), polyvinyl chloride, poly(vinylidene fluoride), poly(methyl methacrylate), polyacrylonitrile, poly(dimethylsiloxane), poly[bis(methoxyethoxy)-phosphazene], polypropylene glycol, polyethylene carbonate, polycaprolactone, poly(trimethylene carbonate), paraffin wax, polyisobutylene, polyvinylpyrrolidone, hydrogenated nitrile butadiene rubber, styrene butadiene rubber, high density polyethylene, low density polyethylene, poly(ethylene oxide), polyurethane, polystyrene, poly(methyl acrylate), poly(vinylidene fluoride)-co-hexafluoropropylene, poly(acrylonitrile-co-butadiene), poly(styrene-butadiene-styrene), and styrene-ethylene-butylene-styrene. It can include polymers such as poly(propylene oxide), polyvinyl chloride, poly(vinylidene fluoride), poly(methyl methacrylate), polyacrylonitrile, poly(dimethylsiloxane), poly[bis(methoxyethoxy)-phosphazene], polypropylene glycol, polyethylene carbonate, polycaprolactone, poly(trimethylene carbonate), paraffin wax, polyisobutylene. N, polyvinylpyrrolidone, hydrogenated nitrile butadiene rubber, styrene butadiene rubber, high density polyethylene, low density polyethylene, poly(ethylene oxide), polyurethane. polystyrene, poly(methyl acrylate), poly(vinylidene fluoride)-co-hexaflu luoropropylene, poly(acrylonitrile-co-butadiene), poly(styrene-but adiene-styrene), styrene-ethylene-butylene-styrene, and the like.

[0052] In another specific example, the organic material can include a binder material containing silicone . Examples of silicone can include liquid silicone rubber. In a specific example, the organic material can include polydimethylsiloxane (PDMS), vinyl-terminated PDMS, hydride-functional siloxane, methylhydrogensiloxane-dimethylsiloxane copolymer, or any combination thereof. In a further embodiment, a catalyst can be used with the silicone material for forming the ion conductive layer. Specific examples of the catalyst can include platinum, platinum composite, or a combination thereof. In a specific embodiment, the catalyst can be in a solvent material such as xylene. In a specific embodiment, the catalyst can include a composite of platinum in xylene .

[0053] Referring to FIG. 1, a cross-sectional view of an exemplary ion conductive layer 100 including an organic material 104 such as a binder material and an ion conductive material 102 is illustrated. The conductive material 102 can be understood to include particles having a triangular cross-sectional shape as illustrated, or particles having different shapes. For example, the ion conductive particles can be spheres, cubes, and / or prisms . having a regular shape such as a rhythm, or an irregular shape, or any combination thereof is possible. In another example, the particles may have a cross-sectional shape including a circle, an ellipse, a polygon, or any combination thereof.

[0054] In an embodiment, the ion conductive layer can include a specific content of an organic material that can promote the improved formation and performance of the ion conductive layer. For example, the ion conductive layer can include at least 1 vol% of an organic material, such as at least 2 vol%, at least 5 vol%, at least 10 vol%, at least 15 v ol%, at least 20 vol%, at least 25 vol%, at least 30 vol%, at least 35 vol%, at least 40 vol%, at least 45 vol%, or at least 50 vol%, based on the total volume of the ion conductive layer. In another example, the ion conductive layer may include up to 50 vol% of an organic material, such as up to 48 vol%, up to 45 vol%, up to 40 vol%, up to 3 6 vol%, up to 30 vol%, up to 25 vol%, up to 20 vol%, up to 15 vol %, or up to 10 vol%, based on the total volume of the ion conductive layer. Further, the content of the organic material may be in a range including any of the minimum and maximum ratios specified herein. In at least one non-limiting embodiment, the ion conductive layer may be essentially free of an organic material. embodiment, the ion conductive layer may be essentially free of an organic material.

[0055] In an embodiment, the ion conductive layer can further include a lithium salt dispersed in the organic material. The lithium salt can promote the improvement of the ion conductivity of the ion conductive layer. Li ​​​​​An example of a lithium salt is LiPF 6 , LiClO 4 , LiBF 4 , LiAsF 6 , LiTf, LiSA, LiFSI, LiTFSI, L iBETI, LiCTFSI, LiBOB, LiTDI, LiPDI, LiDCTA, LiB(CN) 4 , LiSbF 6 , LiSO 3 CF 3 , LiN(SO 2 CF 3 ) 2 , LiN(SO 2 C 2 F 5 ) 2 , LiN(SO 2 CF 3 )(SO 2 C 4 F 9 ), LiC(SO 2 CF 3 ) 3 Or a combination of these In certain embodiments, the organic material can be, but is not limited to, one or more of: The polymer electrolyte material may be used as a carrier for one or more lithium salts. The electrolyte materials are poly(ethylene oxide), poly(propylene oxide), and polyvinyl chloride. , poly(vinylidene fluoride), poly(acrylonitrile), poly(dimethylsiloxane) , poly[bis(methoxyethoxy)-phosphazene], polyethylene carbonate, poly Propylene glycol, polycaprolactone, poly(trimethylene carbonate) or The lithium salt may be a polymer electrolyte material. It can form a chelate by complexing with one or more of the following entities: In embodiments, the solid ionically conductive layer is made of a solid ionically conductive material, such as a halide-based material. It may include a first phase formed by a material and a second phase including a polymer electrolyte material complexed with a lithium salt. phase.

[0056] Referring to FIG. 2, an exemplary cross-sectional view of an ion-conductive layer 200 including a lithium ion conductive material 202, an organic material 206, and ammonium halide particles 204 having different shapes such as cubes, octahedrons, and needles, rods, or any combination thereof, such as an elongated shape, is shown. In another example, the lithium ion conductive layer 200 may include ammonium halide particles having the same shape such as an elongated shape, or any combination of two shapes. In another example, the ammonium halide may have a spherical shape, another geometric shape, or a three-dimensional shape. In at least one embodiment, the solid ion conductive layer may not essentially contain ammonium halide. In an embodiment, the ion-conductive layer may include a dense layer. In one aspect, the ion-conductive layer may have a porosity of up to 10 vol% with respect to the total volume of the ion-conductive layer. For example, the ion-conductive layer may have a porosity of up to 9 vol%, up to 8 vol%, up to 7 vol%, up to 6 vol%, up to 5 vol% with respect to the total volume of the ion-conductive layer, up to 4 vol%, up to 3 vol%, up to 2 vol%, or up to 1 vol%. In another example, the ion-conductive layer may include a porosity of at least 0.05 vol% with respect to the total volume of the ion-conductive layer, such as at least 0.1 vol%, at least 0.5 vol%, or at least 1 vol%. Furthermore, the ion conductive layer may have a porosity of at least 0.05 vol% with respect to the total volume of the ion-conductive layer, such as at least 0.1 vol%, at least 0.5 vol%, or at least 1 vol%.

[0057] In an embodiment, the ion-conductive layer can include a dense layer. In one aspect, the ion-conductive layer can have a porosity of up to 10 vol% with respect to the total volume of the ion-conductive layer. For example, the ion-conductive layer can have a porosity of up to 9 vol%, up to 8 vol%, up to 7 vol%, up to 6 vol%, up to 5 vol %, up to 4 vol%, up to 3 vol%, up to 2 vol%, or up to 1 vol% with respect to the total volume of the ion-conductive layer. In another example, the ion-conductive layer can include a porosity of at least 0.05 vol% with respect to the total volume of the ion-conductive layer, such as at least 0.1 vol%, at least 0.5 vol%, or at least 1 vol% with respect to the total volume of the ion-conductive layer. Further, the ion conductive layer can have a porosity of at least 0.05 vol% with respect to the total volume of the ion-conductive layer, such as at least 0.1 vol%, The porosity of the conductive layer can be in the range including either the minimum and maximum percentages pointed out in this specification. In another aspect, the ion conductive layer can include a density exceeding 90% of the theoretical density. For example, the density can be at least 92% of the theoretical density, such as at least 94%, or at least 96%. In another example, the ion conductive layer can have a density of up to 99.99% of the theoretical density, such as up to 99% of the theoretical density. Further, the density of the ion conductive layer can be in the range including either the minimum and maximum percentages pointed out in this specification. In certain embodiments, the ion conductive layer can be a dense layer such as a separator in an electrochemical device, for example, an electrolyte.

[0058] FIG. 13 includes a SEM image of a cross-section of an exemplary high-density ion conductive layer according to an embodiment of this specification. The ion conductive layer includes a halide material 1303 and an organic binder material 130 1. In the illustrated example, the halide material can be represented by the general formula Li 3 YBr 6 and the organic binder material is hydrogenated nitrile butadiene rubber (also referred to as "HNBR" in this disclosure).

[0059] In an embodiment, the ion conductive layer can include a porous layer. In a further aspect, the ion conductive layer can include a specific porosity that can facilitate the improved formation and performance of the ion conductive layer. For example, the porosity can be at least 1 vol% with respect to the total volume of the porous layer, such as at least 2 vol%, at least 5 vol%, at least 10 vol%, at least 15 vol%, at least 20 vol%, at least It can be 30 vol%, at least 35 vol%. At least 40 vol% , at least 45 vol%, at least 50 vol%, at least 55 vol%, at least 60 vol%, at least 65 vol%, at least 70 vol%, at least 75 vol%, or at least 80 vol% is the total volume of the ion conductive layer. In another example , with respect to the total volume of the porous layer, the porosity is at most 7 5 vol%, at most 70 vol%, at most 65 vol%, at most 60 vol%, at most 55 vol%, at most 50 vol%, at most 45 vol%, at most 40 vol l%, at most 35 vol%, at most 30 vol%, at most 25 vol%, at most 20 vol%, at most 15 vol%, or at most 10 vol%. Further , the ion conductive layer can include a porosity within a range including any of the minimum and maximum ratios pointed out herein .

[0060] In one aspect, the ion conductive layer can include closed pores, open pores such as interconnected pores, or any combination thereof. For example, most of the pores can include open pores . For example, at least 60% of the pores can include at least 70% of the pores , at least 80%, or at least 90%, etc., of open pores. In a specific example, 95% or essentially all of the pores of the porosity can be open pores .

[0061] In another aspect, the ion conductive layer has at least 20 v ol% of open pores with respect to the total volume of the ion conductive layer, for example, at least 25 vol% with respect to the total volume of the ion conductive layer At least 28 vol%, at least 30 vol%, at least 35 vol%, at least 40 vol%, at least 45 vol%, at least 50 vol%, at least 55 v ol%, at least 60 vol%, at least 65 vol%, at least 70 vol%, at least 75 vol%, or at least 80 vol% etc. can be included. Another example is that the open pores are at most 90 vol% with respect to the total volume of the ion-conductive layer, for example, at most 75 vol%, at most 70 vol%, at most 65 vol%, at most 60 v ol%, at most 55 vol%, at most 50 vol%, at most 45 vol%, at most 40 vol%, at most 35 vol%, at most 30 vol%, at most 25 vol% , at most 20 vol%, at most 15 vol%, or at most 10 vol% content can be present. Further, the ion-conductive layer can include the content of pores within the range including either the minimum and maximum ratios pointed out in this specification.

[0062] In another aspect, the ion-conductive layer can include closed pores. For example, at least 60% of the porous can include at least 70%, at least 80%, or at least 90% etc. of closed pores. In a specific example, 95% or essentially all of the pores can be closed pores.

[0063] In a further aspect, the ion-conductive layer can include, with respect to the total volume of the ion-conductive layer, up to 5 0 vol% of closed pores, for example, up to 40 vol%, up to 30 vol%, up to 20 vo l%, up to 10 vol%, or up to 5 vol% of closed pores. In another example, the closed pores are at least 0.5 vol% with respect to the total volume of the ion-conductive layer, at least At least 1 vol%, at least 2 vol%, at least 3 vol%, at least 4 vo l% or may have a content of at least 5 vol%. Further, the ion conductive layer contains a content of closed pores in a range including either the minimum and maximum ratios pointed out in this specification. It can be.

[0064] In an embodiment, the ion conductive layer has a specific average pore diameter, D 10 , D 50 , and / or is D 90 such as a specific pore size distribution, a specific pore shape, a specific length, a specific width, a specific average aspect ratio, a specific pore distribution, a specific porosity, a specific open porosity, a specific closed porosity, or any combination thereof (but not limited to this) including one or more pore characteristics. One or more specific pore characteristics combined with one or more other characteristics of the ion conductive layer are expected to improve the formation and performance of the ion conductive layer.

[0065] In a specific embodiment, the ion conductive layer can be a porous layer. In an embodiment, the ion conductive layer can include pores having a specific shape that facilitates improved formation and performance of the ion conductive layer. In one aspect, the ion conductive layer can include elongated pores. For example, the pores can include meandering pores, needle-like pores, polygonal columnar pores, or any combination thereof. In a specific example, the pores can have an elongated shape and a polygonal cross-section. In another specific example, the pores can include needle-like pores, and at least a part of the needle -like pores can be connected. In another aspect, the ion conductive layer is , polyhedral pores such as spherical pores, cubic pores, octahedral pores, hexahedral pores, pores having a three-dimensional structure, or any combination thereof can be included. In a specific example, the ion conductive layer can include pores having an octahedral shape, a cubic shape, needle-like pores, rod-like pores, or any combination thereof. In a further aspect, the solid ion conductive layer can include pores having a specific average aspect ratio of length:width. In one example, the average aspect ratio is at least 1 or greater than 1, for example, at least 1.2, at least 1.5, at least 2, at least 2 .3, at least 2.5, at least 2.8, or at least 3, and in another example,

[0066] the average aspect ratio can be at most 30, at most 25, at most 22, at most 20, at most 15, at most 12, at most 10, at most 8, at most 5, or at most 4, and also, at most 4 is at most 5, at most 10, at most 5 5, at most 5, at most 4. Further, the pores can have an aspect ratio in the range including any of the minimum and maximum values pointed out in this specification. Referring to FIG. 3, an exemplary ion conductive layer 300 can include an ion conductive material 302, an organic material 304, and an ammonium halide 306. The ion conductive layer further includes pores 312, 314, 316, and 318. Pore 312 can be spherical. Pore 314 can be cubic. Pore 316 can be octahedral. Pore 318 can be elongated. As described in the embodiments of this specification, elongated pores are intended to refer to pores having an aspect ratio greater than 1. In one example, the ion conductive

[0067] layer 300 can include pores having an aspect ratio greater than 1. In one example, the ion conductive layer can include pores having an aspect ratio greater than 1. As described in the embodiments of this specification, elongated pores are intended to refer to pores having an aspect ratio greater than 1. In one example, the ion conductive layer can include pores having an aspect ratio greater than 1. As described in the embodiments of this specification, elongated pores are intended to refer to pores having an aspect ratio greater than 1. In one example, the ion conductive layer can include pores having an aspect ratio greater than 1. As described in the embodiments of this specification, elongated pores are intended to refer to pores having an aspect ratio greater than 1. In one example, the ion conductive layer can include pores having an aspect ratio greater than 1. As described in the embodiments of this specification, elongated pores are intended to refer to pores having an aspect ratio greater than 1. In one example, the ion conductive layer can include pores having an aspect ratio greater than 1. As described in the embodiments of this specification, elongated pores are intended to refer to pores having an aspect ratio greater than 1. In one example, the ion conductive The conductive layer 300 can have pores with shapes different from those of pores 312 to 318. In another example, the ion-conductive layer 300 can have pores with substantially the same shape, such as the shape of any one of pores 312 to 318. In another example, the ion-conductive layer 30 0 can include pores having the shape of any two or three of pores 312 to 318. In a further example, the ion-conductive layer 300 can essentially not include any of pores 312 to 318. In a specific example, the ion-conductive layer 300 can essentially not include the organic material 30 4. In another specific example, the ion-conductive layer can essentially not include the ammonium halide 306. In a further example, the ion-conductive material can include an ammonium halide-doped halide material.

[0068] FIG. 4A includes an illustration of a cross-section of an exemplary ion-conductive layer 40 0 that includes an ion-conductive material 402 and pores 404. As shown, within the bulk of the ion-conductive layer 400 the ion-conductive material 402 can be in the shape of flakes, and the elongated pores 404 can extend between the flakes 402. The pores 404 can have an elongated shape, and the elongated direction can extend horizontally, such as along the plane of the cross-section, vertically, such as toward the plane of the cross-section, and / or in a direction forming an acute or obtuse angle with the plane of the cross-section. In a specific example, the pores 404 can have a cylindrical shape with a polygonal cross-section. In another specific example, at least some of the pores 404 can extend three-dimensionally through at least a portion of the bulk of the ion-conductive layer 400 and be interconnected. In another specific example, the flakes 402 ​At least some of them can form an interconnected network, and at least some of the flakes are separated by elongated pores 404 extending through at least a part of the network. In a more specific example, the bulk of the ion-conductive layer 400 can include a network of interconnected flakes 402, and the elongated pores 404 can extend between the flakes 402. In another more specific example, the interconnected flakes 402 can be bonded to each other. In a particular embodiment, the ion-conductive layer 400 may be a scaffold or frame for forming a composite layer having ion conductivity and electronic conductivity. FIG. 4B includes an illustration of exemplary pores 404 in the ion-conductive layer 400. The pores 41 4 are defined by a plurality of flakes 412 and can have a cross-section in the shape of a polygon such as a triangle. As illustrated in FIG. 4B, the pores 404 can extend in a vertical direction. In a particular example, the pores 404 can extend in a direction substantially perpendicular to the major surface of the ion-conductive layer. Referring to FIG. 3, the major surface can be either the upper surface or the lower surface between which the thickness t extends.

[0069] FIG. 14 includes a SEM image of a part of the cross-section of an exemplary solid ion-conductive layer 1400 cast on a substrate 1410 according to another embodiment. The solid ion-conductive layer 1400 includes an organic binder material 1401, a solid ion-conductive material 1402 in the form of flakes or sheets, and pores including pores 1403 and 1404. The pores may be at least partially defined by the solid ion-conductive material 14 02. For example, the pores 1403 are organic binders

[0070] FIG. 14 includes a SEM image of a part of the cross-section of an exemplary solid ion-conductive layer 1400 cast on a substrate 1410 according to another embodiment. The solid ion-conductive layer 1400 includes an organic binder material 1401, a solid ion-conductive material 1402 in the form of flakes or sheets, and pores including pores 1403 and 1404. The pores may be at least partially defined by the solid ion-conductive material 14 02. For example, the pores 1403 are organic binders 02. For example, the pores 1403 are organic binders ​​​​It may be defined by an underlayer material 1401 and a solid ion conductive material 1402. Pores At least some other pores such as 1404 may be defined by the solid ion conductive material 1402.

[0071] In an embodiment, the ion conductive layer 400 may include elongated pores having an orientation in an elongation direction that forms a specific angle with one of the major surfaces. For example, within a maximum of ±30 degrees, a maximum of ±20 degrees, a maximum of ±10 degrees, or a maximum of ±5 degrees of the right angle formed between the elongation direction of the pores and the upper major surface or the lower major surface of the ion conductive layer, at least 30% or at least 40% or at least 50% or at least 60% or at least 70% of the pores are oriented.

[0072] In an embodiment, the elongated pores 404 can have a specific width, a specific length, or a combination thereof. In one aspect, the width of the elongated pores is at least 0.1 μm, at least 0.3 μm, at least 0.5 μm, at least 0.8 μm, at least 1 μm, at least 1.5 μm, or at least 2 μm. In another aspect, the width can be a maximum of 20 μm, a maximum of 15 μm, a maximum of 10 μm, a maximum of 8 μm, a maximum of 5 μm, a maximum of 4.5 μm, a maximum of 4 μm, a maximum of 3.5 μm, a maximum of 3 μm, or at least 2.5 μm. Furthermore, the width can be in a range including any of the minimum and maximum values indicated herein. Taking a triangular cross-section as an example, the width can be the maximum height of the triangle. For a square or rectangular cross-section, the width can be the length of the square or rectangle. For a cross-section of a polygon with four or more sides, the width can be the maximum diagonal distance of the polygon.

[0073] ​​​​​​​​ In a further aspect, the elongated pores can have a length of at least 0.5 μm, at least 0.8 μm , at least 1 μm, at least 2 μm, at least 5 μm, at least 8 μm, at least 10 μm, at least 15 μm, at least 20 μm, at least 30 μm, at least 40 μm, at least 50 μm or at least 60 μm. In another aspect, the length of the elongated pores can be up to 100 μm, for example, up to 90 μm, up to 80 μm, up to 70 μm, up to 60 μm, up to 50 μm, or up to 40 μm. Further, the elongated pores can have a length within a range including any of the minimum and maximum values pointed out herein. As pointed out herein, the width and length of the elongated pores are intended to be the average values of the width and length of at least 100 elongated pores, respectively. In another embodiment, the ion conductive layer can include pores having a particular undulation degree that can promote improved formation and performance of the ion conductive layer. In a particular aspect, the undulation degree (perpendicular to the major surface) of the porous tape is at most 1.2, or at most 1. 5, or at most 2, or at most 3. As used herein, the undulation degree, τ, can be defined by the following formula, where L is the average length of the geometric flow path through the porous layer and L is the thickness of the porous layer. The undulation degree can be determined using a three-dimensional shape measurement method. The three-dimensional shape is a focused ion

[0074] In another embodiment, the ion conductive layer can include pores having a particular undulation degree that can promote improved formation and performance of the ion conductive layer. In a particular aspect, the undulation degree (perpendicular to the major surface) of the porous tape is at most 1.2, or at most 1. 5, or at most 2, or at most 3. As used herein, the undulation degree, τ, can be defined by the following formula, where L is the average length of the geometric flow path through the porous layer and L is the thickness of the porous layer. The undulation degree can be determined using a three-dimensional shape measurement method. The three-dimensional shape is a focused ion t is the average length of the geometric flow path through the porous layer and L is the thickness of the porous layer.

Equation

[0075] The undulation degree can be determined using a three-dimensional shape measurement method. The three-dimensional shape is a focused ion Off-beam scanning electron microscope (FIB-SEM) method, micro-computed tomography —(micro-CT), nano-computed tomography (nano-CT). It can be obtained. L t The average length of the geometric flow path through the porous layer can be obtained by measuring the length of the center line of the through holes in the representative area and averaging them. The waviness can also be determined using the effective binary diffusivity. The effective binary diffusivities of substances A and B passing through the porous layer:

[0076] It can be investigated by measuring the gas diffusivity. Substances A and B passing through the porous layer Effective binary diffusivities:

Equation

Equation

Equation

Equation

[0077] In embodiments, the ion conductive layer is formed of a material that facilitates improved formation and performance of the ion conductive layer. In one embodiment, the flakes 404 may have a particular thickness that can be easily adjusted. The flakes 404 may be at least 0.1 μm, at least 0.3 μm, at least 0. 5 μm, at least 0.8 μm, at least 1 μm, at least 2 μm, at least 4 μm In another embodiment, the flake 404 may have a thickness of at least 5 μm. is max. 20μm, max. 18μm, max. 15μm, max. 12μm, max. 10μm, max. 9μm It is possible for the thickness to be up to 8 μm, up to 6 μm, or up to 5 μm. Additionally, the flakes 404 may be in a range that includes any of the minimum and maximum values ​​noted herein. As used herein, thickness can include at least 20 sheets of paper. It is intended to refer to the average thickness of the lake.

[0078] Referring to FIG. 5, an exemplary ion-conducting layer 500 includes an ion-conducting material 502, an organic The material 504 may include an ammonium halide 508 and holes 506 .

[0079] In an embodiment, the ion-conducting layer has a particular average pore size D 50 may include. For example, the ion conductive layer may be at least 50 nm, at least 80 nm, at least 10 0nm, at least 200nm, at least 300nm, at least 400nm, at least D of at least 500 nm, at least 600 nm, at least 700 nm 50 Can contain At least 800 nm, at least 900 nm, at least 1 micron, at least At least 2 microns, at least 3 microns, at least 5 microns, at least 10 microns , at least 30 microns, at least 50 microns, at least 100 microns, and also must be at least 200 microns. In another example, the ion conductive layer has a maximum of 300 microns, for example, a maximum of 200 microns, a maximum of 150 microns, a maximum of 100 microns , a maximum of 80 microns, a maximum of 70 microns, at most 65 microns, for example at most 60 microns, at most 55 microns, at most 50 microns, at most 40 microns, at most 30 microns, at most 10 microns, at most 5 microns, at most 3 microns, or at most 1 micron of D 50 may be included. Further, the ion conductive layer may include D in a range including any of the minimum and maximum values pointed out herein . In an exemplary 50 specific embodiment, D may be in the range of 100 nm to 50 microns 50 . In another specific example, D may be in the range of 0.5 microns to 5 microns. For pores having a substantially spherical shape, the pore size may refer to the diameter of the pore in the cross-section 50 . In the case of pores having a non-spherical shape, the pore size may refer to the maximum dimension such as the length of the pore in the cross-section .

[0080] In the present disclosure, the average pore diameter can be measured using ASTM standard E112 Standard Test Methods for Determi ning Average Grain Size. The cross-sectional image of the body was observed at a magnification of 60 times with a Hitachi microscope . The macro for determining the pore length includes drawing 6 lines at equal intervals on the image and determining the regions that intersect the pores among those lines . Based on this It follows the technique of measuring the crystal size. The region of the line intersecting the pores is measured. This process was repeated for seven different images of the adhered polishing body part. After analyzing all the images, the values were averaged to calculate the average pore diameter. Furthermore, it will be understood that reference to the average pore diameter can also refer to the average pore diameter.

[0081] Briefly looking at FIG. 3, as shown, the pores 312 are substantially spherical obtained. In a particular example, the pores 312 can result from the removal of the organic material in the process of forming the solid ion conductive layer. In another particular example, the pores 314 - 318 illustrated in FIG. 3, and the pores 404 illustrated in the figure, are the same as the pores 314 - 318 illustrated in FIG. 3 and the pores 404 illustrated in the figure. 4A and 4B may result from the removal of ammonium halide in the process of forming the ion conductive layer. In another embodiment, the pores resulting from the sublimation of ammonium halide may have a spherical shape, an irregular shape, or another shape.

[0082] In an embodiment, the solid ion conductive layer can include a first type of porosity and a second type of porosity, and the first and second types of porosity can include one or more different pore characteristics including pore shape, pore size, pore size distribution, pore structure, aspect ratio, or any combination thereof. In a particular aspect, the first type of porosity can include pores having a non - spherical shape. In another particular aspect, the first type of porosity can include pores resulting from the removal of ammonium halide. For example, the first type of pores can include the pores 404 illustrated in the figure. 4A and 4B, ​ Holes 314, 316, the holes 318 illustrated in FIG. 3, or combinations thereof. In certain embodiments the first type of pores can consist essentially of the pores 404 illustrated in the figures. 4 A and 4B. In another aspect, the second type of porosity can include spherical pores such as the pores 312 illustrated in FIG. 3 . In another aspect, the second type of porosity can include pores formed by removal of an organic material.

[0083] In embodiments, the solid ion conducting layer can include a specific content of the first type of porosity that can facilitate improved formation and function of the solid ion conducting layer. In one aspect, the first type of porosity can constitute at least 10 vol%, at least 15 vol%, at least 20 vol%, at least 25 vo l%, at least 30 vol%, at least 40 vol%, at least 50 vol%, at least 55 vol%, at least 60 vol%, at least 70 vol%, at least 80 vol%, or at least 90 vol% of the total volume of the ion conducting layer. In a further aspect, the first type of porosity can occupy, at most, 95 vol%, at most 90 vol%, at most 80 vol%, at most 70 vol%, at most 60 vol% , at most 50 vol%, at most 40 vol%, at most 30 vol%, or at most 20 vol% of the total volume of the ion conducting layer. In certain aspects, the solid ion conducting layer can include the content of the first type of voids within a range including any of the minimum and maximum percentages described herein.

[0084] In a further aspect, the first type of porosity can include open pores, closed pores, or a combination thereof. In another specific aspect, the first type of porous material can consist essentially of open pores. In another aspect, the first type of porous material can have an average pore diameter that includes any value pointed out in the

[0085] embodiments herein with respect to the average pore diameter. In another example, the solid ion conductive layer can consist essentially of a second type of porosity that includes pore 312, pores having an irregular shape, or both. In a specific example, the second type of porosity can consist essentially of spherical pores, pores having an irregular shape, or a combination thereof. Referring

[0086] to FIGS. 4 and 5, solid ion conductive layers 400 and 500 each include spherical pores 406 and 506, respectively.

[0087] In a further aspect, the second type of pores can include open pores, closed pores,

[0087] or a combination thereof. In one example, most of the second type of porosity of the pores can include open pores, and more particularly, the second type of porosity including interconnected pores including elongated pores connected to pores having another shape such as it is possible.

[0088] In an embodiment, the solid ion conductive layer can include a first phase including an ion conductive material and an organic a second phase including a material. The first phase can extend continuously for at least a part of the solid ion conductive layer. In a specific example, the first phase can extend through the thickness of the solid ion conductive layer. In a specific embodiment, the solid ion conductive layer can include a plurality of first phases extending for at least a part of the solid ion conductive layer, and at least a part of the plurality of first phases can be separated from each other. In another embodiment, the solid ion conductive layer can include a heterogeneous phase including a phase including an ion conductive material and a phase including an organic material. including.

[0089] In an embodiment, the multilayer structure can include a plurality of ion conductive layers, and at least some of the plurality of ion conductive layers can include any of the features described in the embodiments herein. In an embodiment, the plurality of ion conductive layers can include the same or different features. For example, the plurality of ion conductive layers can be different from each other by at least one feature including the type and / or content of the ion conductive material, density, porosity, type and / or content of the organic material, or any combination thereof. In another example, the plurality of ion conductive layers can include the same lithium ion conductive material but have different densities or porosities. In a specific example, the multilayer structure can include a first high-density ion conductive layer and a second porous ion conductive layer. In a specific example, the porous ion conductive layer has a three-dimensional structure ​ It can be fabricated.

[0090] FIG. 6 includes a cross-sectional view of an exemplary multilayer structure 600 according to a particular embodiment and includes a dense ion conductive layer 610 and a porous ion conductive layer 620 having a three-dimensional structure. The layer 610 can include a lithium halide conductive material, or in a particular example, a lithium conductive material represented by Formula 1. Any ion conductive material 612. The layer 620 can include the same or different ion conductive materials 622 and pores 626. In another example, the sublayer 620 can include ammonium halide, an organic material, or a combination thereof. In a particular example, the layer 620 may include ammonium halide in the content pointed out in the embodiments herein. In an exemplary application, the dense layer 610 can be an electrolyte, and the porous layer 6 20 can be a scaffold or backbone structure for the electrode layer of a solid lithium battery. In embodiments, the ion conductive layer can be a composite layer having mixed ion conductivity and electron conductivity. In one aspect, the composite layer can include an electron conductive material. In one example, the electron conductive material can include an active electrode material, an electron conductive additive, or a combination thereof. In a particular example, the electrode material can include an active cathode material. Exemplary cathode materials can include lithium-containing oxides, transition metal fluorides, polyanion materials, fluorinated polyanion materials, transition metal sulfides, transition metal oxyfluorides, transition metal oxysulfides, transition metal oxynitrides, or any combination thereof. A particular exemplary positive electrode material is LiCoO

[0091] In embodiments, the ion conductive layer can be a composite layer having mixed ion conductivity and electron conductivity. In one aspect, the composite layer can include an electron conductive material. In one example, the electron conductive material can include an active electrode material, an electron conductive additive, or a combination thereof. In a particular example, the electrode material can include an active cathode material. Exemplary cathode materials can include lithium-containing oxides, transition metal fluorides, polyanion materials, fluorinated polyanion materials, transition metal sulfides, transition metal oxyfluorides, transition metal oxysulfides, transition metal oxynitrides, or any combination thereof. transition metal oxysulfides, transition metal oxynitrides, or any combination of these. A particular exemplary positive electrode material is LiCoO 2 , LiFePO 4, Li(NiCoAl)O 2 , LiCoO 2 , LiMnPO 4 , LiMn 2 O 4 , LiNi 1 / 3 Co 1 / 3 Mn 1 / 3 O 2 , or any combination thereof may be included. In another specific example, the composite layer may include a metal coating disposed on the ion-conductive layer. The metal coating may include an active anode material such as lithium or a lithium alloy, graphene, carbon nanotubes, or any combination thereof.

[0092] In a particular embodiment, the multilayer structure may include a first ion-conductive layer and a second composite layer having mixed ion and electron conductivity. Referring to FIG. 7, an exemplary multilayer structure 700 may include an ion-conductive layer 710 including an ion-conductive material 712 and a composite layer 720 including an ion-conductive material 722 and an electron-conductive material 730. Exemplary electron-conductive materials may include lithium-containing transition metal oxides such as LiCoO , LiMnO , or combinations thereof. 2 , LiMn 2 O 4 , or lithium -containing transition metal oxides. In another specific example, the electron-conductive material may include a lithium metal or a lithium-containing alloy. In one example, layer 720 may include an ammonium halide, an organic material, or a combination thereof.

[0093] Layer 720 may overlap and be in direct contact with the underlying layer 710. The ion-conductive materials 712 and 722 may be the same or different.

[0094] In a particular implementation, layer 710 may be an electrolyte, and layer 720 may be a composite positive electrode layer containing an ion-conductive material and an active positive electrode material, or a composite negative electrode layer containing an ion-conductive material and a negative electrode material. The multilayer structure 700 may be part of an electrochemical device such as a solid lithium battery.

[0095] In an embodiment, the ion-conductive layer can have a particular thickness that facilitates improved formation and performance of the ion-conductive layer. Referring to FIGS. 1-7, the ion-conductive layer can include a thickness t. Referring to FIGS. 7, the ion-conductive layer can include a thickness t. In one example, the thickness "t" can be up to 1 mm, such as up to 800 microns, up to 600 microns, up to 400 microns, up to 200 microns, or up to 100 microns. In another example, the thickness "t" can be at least 1 micron, for example, at least 5 microns, or at least 10 microns. It is understood that the ion-conductive layer can have a thickness "t" within a range that includes any of the minimum and maximum values set forth therein.

[0096] As shown in FIGS. 6 and 7, layers 610 and 710 can have a thickness "t1", and sub-layers 620 and 720 can have a thickness "t2". The thicknesses "t1" and " t2" can include any of the thickness values pointed out in the embodiments herein in relation to the thickness "t" of the ion-conductive layer. In one aspect, the thickness "t2" can be at least the thickness " t1". For example, the thickness "t2" can be at least 5 microns and up to 1 mm. In another aspect, the thickness "t1" can be from 5 microns to 100 microns. ​​​​​​​​​​It may be within the range. In a further aspect, the thickness "t2" can be different from "t1". In yet another aspect, the thickness "t2" can be at most the thickness "t1".

[0097] In an embodiment, the ion-conductive material can include a specific ionic conductivity that can promote the performance improvement of the ion-conductive layer. In one aspect, the ionic conductivity can be at least 0.1 mS / cm, for example, at least 0.3 mS / cm, at least 0.5 mS / c m, at least 1 mS / cm, at least 1.2 mS / cm, at least 1.5 mS / c m, at least 1.7 mS / cm, or at least 1.9 mS / cm. In another aspect, the ionic conductivity can be at most 50 mS / cm, at most 40 mS / cm, at most 35 mS / cm, at most 30 mS / cm, at most 20 mS / cm, at most 1 5 mS / cm, at most 10 mS / cm, at most 8 mS / cm, at most mS / cm 6 mS / cm at most 5 mS / cm, at most 3 mS / cm, at most 2.8 mS / cm, at most 2.5 mS / cm, at most 2. 2 mS / cm, or at most 2 mS / cm. Furthermore, the ionic conductivity can be in a range including any of the minimum and maximum values described herein. The lithium ion conductivity described in the embodiments herein can be determined at room temperature (i.e., 20 °C to 25 °C) in the range of activation energies of 0.2 eV and 0.5 eV.

[0098] Referring to FIG. 8, the process of forming the ion-conductive layer 800 begins at block 802. ​It can be started to form a mixture containing a lithium ion conductive material. In one aspect, the mi xture can also contain a solvent, a binder, and optionally a dispersant, a plasticizer, a homogenizing agent, and / or a pore-forming material. The components of the mixture may not react with the ion conductive material.

[0099] In some embodiments, the mixture may further contain a lithium salt, an organic ion conductive material, and / or an electronic conductive material such as an active cathode material or an active anode material. By mixing the lithium ion conductive material and the electronic conductive material, the reaction sites for lithium ion charge transfer and electron conduction can be improved, and the interfacial resistance and cyclicity of the ion conductive layer (e.g., the cathode and / or the anode) can be promoted.

[0100] The components may be added in any suitable order to form a homogeneous mixture, and a mixing aid such as a mixer may be used to facilitate mixing.

[0101] In an embodiment, the ion conductive material can be mixed with a solvent to form a suspension or a slurry. In a particular aspect, the solvent can have an HLB value, a reactivity value, or a combination thereof as pointed out in the embodiments of the present specification. Exemplary solvents can include toluene, pentene, xylene, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclododecane, cycloundecane, dimethyl sulfide, dibromomethane, dichloromethane, o-chlorotoluene, o-dichlorobenzene, or any combination thereof.

[0102] ​​​​​​​​​​​​​ To promote the improved formation and performance of the ion conductive layer, one or more binders can be mixed into the slurry. The binder can have an HLB value, a reactivity value, a MAR, or a combination thereof, as described in the embodiments of this specification. . Exemplary binders include paraffin wax, polypropylene carbonate, polyisobutylene, polyvinylpyrrolidone, poly(methyl methacrylate), polyethylene glycol, hydrogenated nitrile butadiene rubber, styrene butadiene rubber, high density polyethylene, low density polyethylene, polyurethane, poly(propylene oxide), vinyl chloride, poly(vinylidene fluoride), and can be one or more materials selected from the group consisting of. Poly(acrylonitrile), poly(dimethylsiloxane), poly[bis(methoxyethoxy)phosphazene], poly(ethylene carbonate), polypropylene glycol, polycaprolactone, poly(ethylene oxide), trimethylene carbonate, polystyrene, poly(methyl acrylate), poly(vinylidene fluoride)-co-hexafluoropropylene, poly(acrylonitrile-co-butadiene), poly(styrene-butadiene-styrene), styrene-ethylene-butylene-styrene, and the like. Optional components may be added to the mixture. In an embodiment, the mixture may be formed into a colloidal suspension.

[0103] In some embodiments, a pore forming material may be included in the mixture. In an embodiment, the pore forming material can include an organic material, an inorganic material, or a combination thereof. In certain embodiments, the pore forming material is NH 4 Br, NH 4 Cl, NH 4 I, NH4 F, or combinations thereof, etc., can include ammonium halides. In an embodiment , the ammonium halide can be sublimated to form pores in the ion-conductive layer. In certain embodiments, the pore-forming material can include an ammonium halide. In one aspect, the ammonium halide particles can have a shape similar to the shape of the pores described in the embodiments herein. In another aspect, the ammonium halide can be compounded with an ion-conductive material to form pores having specific pore characteristics.

[0104] In another embodiment, a pore-forming material other than ammonium halide can be used. In certain embodiments, evaporation of the pore-forming material can be performed to form pores. Conventionally, pore-forming agents such as carbon black, graphite, poly(methyl methacrylate) (PMMA), starch, and tellurium are burned in an oxidative environment to form pores. When an organic pore-forming agent is burned off, water vapor may be released, and the water vapor may cause deterioration of a hygroscopic ion-conductive material such as a halide-based material. Therefore, it may be a process not suitable for hygroscopic ion-conductive materials. Due to deterioration, compounds and / or molecules with low ionic conductivity may be formed. For example, deterioration of a halide-based material by water vapor forms hydrates of the halide-based material, simple metal halides, metal oxohalides, and compounds with low ionic conductivity such as H and may adversely affect the ionic conductivity of the hygroscopic ion-conductive material. Further, the halide-based material reacts with O 2 2 ​​​​​​​​​, there is a tendency to form metal oxides or halogens with poor or almost no ionic conductivity. There is.

[0105] In some cases, due to the evaporation of the organic pore-forming material, derivatives such as hydrocarbons, char, graphite, or combinations thereof may be generated and remain in the porous ionic conductive layer. Such organic pore-forming agents may not be preferred for forming a porous ionic conductive layer that does not contain their derivatives. There are cases.

[0106] In an embodiment, the mixture can contain at least 1 wt% to a maximum of 6 0 wt% of an organic material, based on the total weight of the mixture. In another embodiment, the mixture is based on the total weight of the mixture It can contain at least 1 wt% to a maximum of 60 wt% of ammonium halide. In another embodiment, the mixture can contain at least 20 wt % to a maximum of 90 wt% of an ionic conductive material, based on the total weight of the mixture. In yet another embodiment, the mixture can contain at least 2 wt% to a maximum of 60 wt% of a solvent, based on the total weight of the mixture. There are cases.

[0107] Process 800 may continue to block 804. In the example, forming the green layer can include treating the mixture by casting, coating, printing, binder jetting, extrusion, compression, calendaring, pressing, or any combination thereof. . In a specific example, the green layer can be in the form of a tape or film. The green layer can include any thickness pointed out in the embodiments of this specification. In a specific embodiment In the case of forming a green ionic conductive layer, it can be a doctor blade or a knife coater. It can include tape casting such as ting. Tape casting can be carried out in a dry state, for example, in a dry room or a glove box. In another specific embodiment, the green layer can be formed by extruding a mixture to form a film or a tape. In a specific embodiment, tape casting can be carried out in such a way that the green layer can have an improved thickness having any value pointed out in the embodiments of the present specification. The improved thickness of the ion conductive layer can help improve the ionic current resistance. In another specific embodiment, the green layer can be formed by extruding a mixture to form a film or a tape. In a specific embodiment, tape casting can be carried out in such a way that the green layer can have an improved thickness having any value pointed out in the embodiments of the present specification. The improved thickness of the ion conductive layer can help improve the ionic current resistance. The improved thickness of the ion conductive layer can help improve the ionic current resistance. The improved thickness of the ion conductive layer can help improve the ionic current resistance.

[0108] In another aspect, forming the green ion conductive layer may include forming a plurality of green underlying layers. For example, a first green layer can be formed, and a second green layer can be formed on the first green layer. The first green layer can include a mixture. The second green layer can include an ion conductive material that may be the same as or different from the ion conductive material in the mixture of block 802. In an exemplary implementation, tape casting may be used to form each green layer. In a specific embodiment, the green layers can be formed separately and then laminated. Alternatively, tape casting may be performed to form the green layers simultaneously. In a specific embodiment, roll-to-roll deposition may be performed to simultaneously cast a stack of green layers. In another example, additional green layers may be formed on the first green layer and / or the second green layer. In another example, a plurality of layers can be co-extruded to form a multilayer structure. In another aspect, forming the green ion conductive layer may include forming a plurality of green underlying layers. For example, a first green layer can be formed, and a second green layer can be formed on the first green layer. The first green layer can include a mixture. The second green layer can include an ion conductive material that may be the same as or different from the ion conductive material in the mixture of block 802. The second green layer can include an ion conductive material that may be the same as or different from the ion conductive material in the mixture of block 802. In an exemplary implementation, tape casting may be used to form each green layer. In a specific embodiment, the green layers can be formed separately and then laminated. Alternatively, tape casting may be performed to form the green layers simultaneously. In a specific embodiment, roll-to-roll deposition may be performed to simultaneously cast a stack of green layers. In another example, additional green layers may be formed on the first green layer and / or the second green layer. In another example, a plurality of layers can be co-extruded to form a multilayer structure.

[0109] Following block 806, process 800 can form an ion-conductive layer. . In embodiments, forming the ion-conductive layer from the green layer can include drying the green layer. The drying may be performed at room temperature or with the application of heat. In some embodiments, the dried layer can be a dense solid ion-conductive layer.

[0110] In another embodiment, forming the ion-conductive layer can include heating the green layer. In some examples, the heating may be performed up to the dried layer. In further examples, heating the green layer may promote the crystallization and / or connectivity of the lithium-ion conductive material.

[0111] In one aspect, heating the green layer can include removing one or more binder materials. In certain aspects, the heating can include evaporating one or more binder materials. Such binder materials can include one or more materials selected from the group consisting of paraffin wax, polypropylene carbonate, polyisobutylene, polyvinylpyrrolidone, poly(methyl acrylate), polyethylene glycol, poly(ethylene oxide), polyvinyl chloride, poly(acrylonitrile), polyethylene carbonate, or combinations thereof. In further examples, the removal of the binder material can be performed without generating water molecules such as water. In specific examples, the heating can include a heating temperature and / or heating time that facilitates the formation of a porous ion-conductive layer having one or more specific pore structure characteristics. Exemplary heating temperatures are provided in block It can include the evaporation temperature of the indium material. In another example, the heating temperature can include 30°C to 400 °C. In a further example, the heating time can include 2 minutes to 24 hours. After the removal of the binder material, a porous ion-conductive layer may be formed.

[0112] In another aspect, the heating of the green layer can be carried out at a temperature that promotes the formation of a dense ion-conductive layer. In some embodiments, the heating can be performed to remove the binder material and at the same time soften the ion-conductive material so that a dense ion-conductive layer can be formed under a relatively low pressure. Specifically, when heating the green layer, it is also possible to apply pressure to the green layer. For example, the evaporation of the binder material can be carried out simultaneously with applying pressure to the green layer. In another example, the pressure can be 0.1 MPa to 100 MPa. can be 0.1 MPa to 100 MPa. 0.1 MPa to 100 MPa.

[0113] In another aspect, heating the green layer may include sublimating ammonium halide. In some embodiments, the green layer may be heated at a temperature that can promote the sublimation of ammonium halide and the formation of a porous ion-conductive material. For example , the sublimation of NH 4 Br can be carried out in advance by heating the green layer to 396°C or higher. The sublimation of NH 4 Cl can be carried out by heating the green layer to 338°C or higher. can be carried out by heating the green layer to 338°C or higher.

[0114] In another aspect, the heating of the green layer may be performed to evaporate the binder material and sublime the pore-forming material to form a porous ion-conductive layer. As another example, polyisobutylene Styrene can be heated to 260 °C under nitrogen and evaporated.

[0115] In certain embodiments, heating of the green layer can be performed in a controlled manner so that intermediate products that can react with the lithium ion conductive material are not formed. For example, the heating temperature can be controlled so as not to burn out one or more binders so as to help prevent the formation of H O. In another aspect, heating can be carried out so as to help avoid the formation of a hydrated phase of the ion conductive material that allows the formation of pores and defines the pores. For example, 2 at least at least 90 wt%, or at least 9 5 wt%, or at least 99 wt% of the total weight of the ion conductive material has no hydrated phase. In another example, at most 10 wt%, or at most 5 wt % or at most 1 wt% of the ion conductive material can contain a hydrated phase, based on the total weight of the ion conductive material. Further, the ion conductive material can contain a hydrated phase in a content that includes any of the minimum and maximum percentages pointed out herein. In a particular example, the ion conductive material can be essentially free of a hydrated phase. % or at most 1 wt% of the ion conductive material can contain a hydrated phase, based on the total weight of the ion conductive material. Further, the ion conductive material can contain a hydrated phase in a content that includes any of the minimum and maximum percentages pointed out herein. In a particular example, the ion conductive material can be essentially free of a hydrated phase. can contain a hydrated phase in a content that includes any of the minimum and maximum percentages pointed out herein. In a particular example, the ion conductive material can be essentially free of a hydrated phase. In certain examples, the ion conductive material can be essentially free of a hydrated phase.

[0116] FIG. 9 includes an explanatory view of a cross-sectional view of an electrochemical unit 900 including an electrolyte 902 disposed between an anode 904 and a cathode 906. In an embodiment, the electrolyte 902 can include an ion conductive layer as pointed out in the embodiments herein. The anode 904 can be a porous layer including a lithium-containing anode material. In a particular example, the anode 904 can be composed of lithium. The cathode 906 can be a porous layer including a cathode material. In an exemplary embodiment the cathode 906 can be a porous layer including a cathode material. In an exemplary embodiment the anode 904 can be composed of lithium. The cathode 906 can be a porous layer including a cathode material. In an exemplary embodiment the anode 904 can be composed of lithium. The cathode 906 can be a porous layer including a cathode material. In an exemplary embodiment ​​, the electrolyte 902, the anode 904, and the cathode 906 are separately formed by tape casting and laminated through a pressing process such as uniaxial pressing to form the electrochemical unit 900. In another exemplary embodiment, a green multilayer structure including the electrolyte 902, the anode 904, and the cathode 906 may be formed by using simultaneous multilayer roll-to-roll technology. In another embodiment, at least one or two or each of the electrolyte 902, the anode 904, and the cathode 906 can include the ion conductive layer pointed out in the embodiments of this specification.

[0117] FIG. 10 includes a cross-sectional view of the electrochemical unit 1000 including the multilayer structure 700 illustrated in FIG. 7 and the anode 1004. The layer 710 may be the electrolyte of the electrochemical unit 1000, and the layer 720 may be the cathode. In an exemplary embodiment, the components of the electrochemical unit are separately formed by tape casting or the like and laminated to form the final electrochemical unit. In other embodiments, simultaneous casting of green layers may be utilized to form the green unit.

[0118] FIG. 11 includes a cross-sectional explanatory view of the multilayer structure 1100 including the ion conductive layer 600 illustrated in FIG. 6 and the cathode 1106. The layers of the multilayer structure may be separately formed and laminated to form the multilayer structure. Alternatively, the green multilayer structure may be formed by simultaneously casting a stack of green layers, drying and / or heating.

[0119] In an exemplary embodiment, the anode material forms the electrochemical unit 1200 including the three-dimensional structured anode 1204, the electrolyte 610, and the cathode 1206 as shown in FIG. 12. The anode 1204 can be disposed on the layer 620 to form a conductive layer. 214 may be included.

[0120] In an embodiment, the solid ionically conductive layer has an ionic conductivity of at least 0.05 mS / c. m, at least 0.08mS / cm, at least 0.10mS / cm, at least 0.1 5mS / cm, at least 0.18mS / cm, at least 0.2mS / cm, at least At least 0.25mS / cm, at least 0.28mS / cm, at least 0.3mS / cm, At least 0.34mS / cm, at least 0.38mS / cm, at least 0.4mS / cm, at least 0.5 mS / cm, or at least 0.6 mS / cm. In another embodiment, the solid ionically conductive layer has a conductivity of at most 25 mS / cm, at most 22 mS / cm, at most 20 mS / cm, at most 18 mS / cm At most 16mS / cm, at most 13mS / cm, at most 10mS / cm, At most 9mS / cm, at most 7mS / cm, at most 6mS / cm, at most 5mS / cm, at most 3mS / cm, at most 2mS / cm, or at most 1mS / cm Furthermore, the solid ionically conductive layer may have any of the minimum and maximum values ​​noted herein. The ionic conductivity may include a range including

[0121] The ionic conductivity of the ion-conductive layer can be measured as follows. A 15 mm sample was punched out from the layer and inserted into a stainless steel plunger to measure the conductivity. The sample can be placed in a Teflon die equipped with a pressure gauge. The resistance between the samples can be measured by impedance measurement. Subsequently, the sample can be taken out and its thickness can be measured. The conductivity can be calculated by the following formula.

Equation

[0122] Many different aspects and embodiments are possible. Some of those aspects and embodiments are described in this specification. After reading this specification, those skilled in the art will understand that those aspects and embodiments are merely illustrative and do not limit the scope of the present invention. The embodiments may conform to any one or more of the embodiments listed below. That's okay.

[0123] Embodiment Embodiment 1. A solid ion conductive layer comprising: An ion conductive material containing a hygroscopic material; A porosity of at least 10 vol% with respect to the total volume of the ion conductive layer; and The content of residual NH 4 X (where X includes halogen). Embodiment 2. A solid ion conductive layer comprising an ion conductive material containing a hygroscopic material and at least one elongated pore extending between a plurality of thin flakes within the bulk of the solid ion conductive layer, wherein the plurality of thin flakes contain a hygroscopic material. Embodiment 3. A solid ion conductive layer comprising a first phase continuously extending over at least a part of the solid ion conductive layer, the first phase containing an ion conductive material containing a hygroscopic material, and a second phase containing an organic material having an HLB value of at most 10, a reactivity value of at most 20, a moisture absorption rate of at most 1 wt%, or any combination thereof. LB value of at most 10, a reactivity value of at most 20, a moisture absorption rate of at most 1 wt%, or any combination thereof. A solid ion conductive layer characterized by comprising a second phase containing an organic material. A method comprising forming a green layer containing a mixture, wherein the mixture is: An ion-conductive material having a content of at least 50 wt% based on the total weight of the mixture, wherein the ion-conductive material contains a hygroscopic material; and at least one of a binder material or NH4X (where X includes halogen and the binder material has: an HLB value of at most 10, a reaction value of at most 20%, a water absorption rate of at most 1 wt%; or any combination thereof), a method characterized by this. Embodiment 5. The solid ion-conductive layer according to any one of Embodiments 1 to 3, including a thickness of up to 1 mm, up to 800 microns, up to 600 microns, up to 400 microns, up to 200 microns, or up to 100 microns. Embodiment 6. The solid ion-conductive layer according to any one of Embodiments 1 to 3, including a thickness of up to 100 microns. Embodiment 7. The solid ion-conductive layer according to any one of Items 1 to 3 of the embodiment, including a thickness of at least 1 micron, at least 5 microns, or at least 10 microns. Embodiment 8. The ion-conductive material is at least 50 vol% based on the total volume of the solid ion-conductive layer and at most 90 vol% based on the total volume of the solid ion-conductive layer. The solid ion-conductive layer according to any one of Embodiments 1 to 3. Embodiment 9. The solid ion-conductive layer according to any one of Embodiments 1 to 3, including elongated pores having a width of at least 0.1 μm, at least 0.3 μm, at least 0.5 μm, at least 0.8 μm, at least 1 μm, at least 1.5 μm, or at least 2 μm. Embodiment 10. The width is at most 20 μm, at most 15 μm, at most 10 μm, at most 8 μm, at most 5 μm, at most 4.5 μm, at most 4 μm, at most 3.5 μm, at most 3 μm, or at least 2 ​ The solid ion conductive layer of Embodiment 9, which can be 0.5 μm.

[0124] Embodiment 11. The elongated pores can have a length of at least 0.5 μm, at least 0.8 μm, at least 1 μm, at least 2 μm, at least 5 μm, at least 8 μm, at least 10 μm, at least 15 μm, at least 20 μm, at least 30 μm, at least 40 μm, at least 50 μm, or at least 60 μm, the solid ion conductive layer of Embodiment 9 or 10. Embodiment 12. The length can be at most 100 μm, for example at most 90 μm, at most 80 μm, at most 70 μm, at most 60 μm, at most 50 μm, or at most 40 μm, the solid ion conductive layer of Embodiment 11. Embodiment 13. The bulk of the solid ion conductive layer contains a network of interconnected flakes, wherein the flakes contain a hygroscopic material and have elongated pores extending through at least a part of the network, the solid ion conductive layer according to any one of Embodiments 1 to 3. Embodiment 14. The flakes contain a thickness of at least 0.1 μm, at least 0.3 μm, at least 0.5 μm, at least 0.8 μm, at least 1 μm, at least 2 μm, at least 4 μm, or at least 5 μm, the solid ion conductive layer of Embodiment 13. Embodiment 15. The flakes contain a thickness of at most 20 μm, at most 18 μm, at most 15 μm, at most 12 μ m, at most 10 μm, at most 9 μm, at most 8 μm, at most 6 μm, or at most 5 μm, the solid ion conductive layer of Embodiment 13 or 14. Embodiment 16. At least 30%, or at least 40%, or at least 50% of the elongated pores form an extension direction that forms an angle of 90 ± 30 degrees with the main surface of the ion conductive layer The solid ion conductive layer according to any one of Embodiments 13 to 15, having Embodiment 17. The elongated pores include a waviness of at most 1.2, or at most 1.5, or at most 2, or at most 3, and the solid ion conduction according to any one of Embodiments 13 to 15 layer. Embodiment 18. The pores include meandering pores, needle-shaped pores, rod-shaped pores, spherical pores, cubic pores, octahedral pores, three-dimensional pores, or any combination thereof, and at least a part of the pores are connected to each other The solid ion conductive layer according to any one of Embodiments 1 to 17. Embodiment 19. At least 50 nm, at least 100 nm, at least 200 nm, at least 300 nm, at least 400 nm, at least 500 nm, at least 60 0 nm, at least 700 nm, at least 800 nm, at least 900 nm, at least 1 micron, at least 2 microns, at least 3 microns, at least 5 microns The solid ion conductive layer according to any one of Embodiments 1 to 3 and 18, including an average pore diameter of at least 10 microns or at least 30 microns. Embodiment 20. The average pore diameter is at most 80 microns, at most 70 microns, at most 65 microns For example, at most 60 microns, at most 55 microns, at most 50 microns, at most 45 microns, at most 40 microns, at most 30 microns, at most 20 microns, or at most 15 microns The solid ion conductive layer of Embodiment 19.

[0125] Embodiment 21. Hydrogenated nitrile butadiene rubber, high density polyethylene, low density polyethylene rene, polyurethane, polystyrene, poly(propylene oxide), poly(vinylidene fluoride) ride), poly(dimethylsiloxane), poly[bis(methoxyethoxide)-phospho Phases, polypropylene glycol, polycaprolactone, and poly(trimethylene carbonate), poly(methyl acrylate), poly(vinylidene fluoride)-co- hexafluoropropylene, poly(acrylonitrile-co-butadiene), and styrene -ethylene-butylene-styrene or combinations thereof, including polymers, any one of solid ion conductive layers from Embodiment Forms 1 to 20. Embodiment 22. At least 5 vol%, at least 10 vol%, at least 20 vol%, at least 30 vol%, at least 50 v ol%, at least 60 vol%, or at least 70 vol% porosity, including the solid ion conductive layer according to any one of Embodiment Forms 1 to 21. Embodiment 23. With respect to the total volume of the solid ion conductive layer, a maximum of 80 vol%, a maximum of 70 v ol%, a maximum of 60 vol%, a maximum of 50 vol%, a maximum of 40 vol%, or a maximum of 30 vo l% porosity, including the solid ion conductive layer according to any one of Embodiments 1 to 22. Embodiment 24. Further including a polymer electrolyte material, the solid ion conductive layer according to any one of Embodiments 1 to 23. Embodiment 25. The polymer electrolyte material is poly(ethylene oxide), poly(propylene o xide), polyvinyl chloride, poly(vinylidene fluoride), poly(acrylonitrile), p oly(dimethylsiloxane), poly[bis(methoxyethoxy)-phosphazene], polyethylene carbonate, polypropylene glycol, polycaprolactone and poly(trimethylene carbonate), including the solid ion conductive layer according to Embodiment 24. Embodiment 26. LiPF 6 , LiClO 4 , LiBF4, LiAsF6 , LiTf, LiSA, LiFSI, LiTFSI, LiBETI, LiCTFSI, LiBOB, LiTDI, LiPDI, LiDCTA, LiB(CN) 4 , LiSbF 6 , LiSO 3 CF 3 , LiN(SO 2 CF 3 ) 2 , LiN(SO 2 C 2 F 5 ) 2 , LiN(SO 2 CF 3 )(SO 2 C 4 F 9 ), LiC(SO 2 CF 3 ) 3 , or a lithium salt containing a combination thereof, further comprising the solid ion conductive layer of Embodiment 24 or 25. The solid ion conductive layer of Embodiment 27, further comprising an active electrode material. Embodiment 27. The solid ion conductive layer according to any one of Embodiments 1 to 26, further comprising an active electrode material. . Embodiment 28. The active electrode material includes an active positive electrode material, and the active positive electrode material is LiCoO 2 , LiFePO 4 , LiMnPO 4 , LiMn 2 O 4 , LiNi 1 / 3 Co 1 / 3 Mn 1 / 3 O 2 , or an oxide containing a combination thereof, the solid ion conductive layer of Embodiment 27, wherein the active electrode material includes an active positive electrode material. . Embodiment 29. The first phase extends through the thickness of the solid ion conductive layer, the solid ion conductive layer according to Embodiment 3 . Embodiment 30. On the solid ion conductive layer according to any one of Embodiments 1 to 29, A multilayer structure including an electrode layer.

[0126] Embodiment 31. A multilayer structure including: A solid electrolyte layer including an ion-conductive material containing a halide-based material; and an ion-conductive layer according to any one of Embodiments 1 to 29. Embodiment 32. An electrochemical unit including a solid ion-conductive layer according to any one of Embodiments 1 to 29. Embodiment 33. The solid ion-conductive layer according to Embodiment 3, including a porosity of at most 10 vol% with respect to the total volume of the solid ion-conductive layer. Embodiment 34. The method according to Embodiment 4, wherein the green layer is in the form of a tape. Embodiment 35. The method according to Embodiment 4 or 31, further including forming a solid ion-conductive layer from the green layer at a temperature of 20°C to 400°C. Embodiment 36. The method according to any one of Embodiments 4, 34, and 35, further including drying the green layer to form the solid ion-conductive layer. Embodiment 37. The method according to any one of Embodiments 4 and 34 to 36, further including sublimating ammonium halide to induce porosity for forming the solid ion-conductive layer, the porosity including pores such as open pores, closed pores, or a combination thereof. Embodiment 38. The method according to any one of Embodiments 4 and 34 to 37, further including evaporating at least one binder to induce porosity for forming the solid ion-conductive layer, the porosity including pores such as open pores, closed pores, or a combination thereof. Embodiment 39. The method according to any one of Embodiments 4 and 34 to 38, wherein the green layer is a first green layer. The method according to item 1, wherein the method further comprises forming a second green layer on the first green layer. The method further comprising. Embodiment 40. The method according to embodiment 3, wherein the formation of the first green layer and the formation of the second green layer are performed simultaneously. The method according to item 9.

[0127] Embodiment 41. The method according to embodiment 39, comprising laminating the first green layer and the second green layer. The method according to item 12. Embodiment 42. The method according to any one of embodiments 39 to 41, comprising forming a dense layer from the second green layer. The method according to any one of items 16. Embodiment 43. The solid ion conductive layer or method according to any one of embodiments 3 to 42, wherein the polymer has an HLB value of at most 10, at most 9, at most 8, at most 7, at most 6, at most 5, at most 4.6, at most 4.2, at most 4, at most 3.5, at most 3, at most 2.5, at most 2, at most 1, at most 0.5, or at most 0.1. The solid ion conductive layer or method according to any one of items 24. Embodiment 44. The solid ion conductive layer or method according to any one of embodiments 3 to 42, wherein the polymer has a water absorption rate of at most 1.0 wt%, for example at most 0.8 wt%, at most 0.5 wt%, at most 0.3 wt%, or at most 0.1 wt%. The solid ion conductive layer or method according to any one of items 30. Embodiment 45. The solid ion conductive layer or method according to any one of embodiments 3 to 42, wherein the polymer has a reactivity of at most 20%, at most 18%, at most 16%, at most 14%, at most 12%, at most 10%, for example at most 9%, at most 8%, at most 7%, at most 6%, at most 5%, at most 4%, at most 3%, or at most 2%. The solid ion conductive layer or method according to any one of items 38. Embodiment 46. The binder is paraffin wax, polypropylene carbonate, poly isobutylene, polyvinylpyrrolidone, poly(methyl methacrylate), polyethylene glycol col, hydrogenated nitrile butadiene rubber, high density polyethylene, low density polyethylene, Poly(ethylene oxide), polyvinyl chloride, poly(acrylonitrile), polyethylene Carbonate, polyurethane, polystyrene, polypropylene oxide, polyvinylidene Fluoride, polydimethylsiloxane, poly[bis(methoxyethoxyethoxy)-phospha Zene], polypropylene glycol, polycaprolactone. And poly(trimethylene Carbonate), poly(methyl acrylate), poly(vinylidene fluoride)-co-hexa Fluoropropylene, poly(acrylonitrile-co-butadiene), poly(styrene Butadiene-styrene), styrene-ethylene-butylene-styrene, etc. selected from the group consisting of The solid ion conductive layer or method according to embodiment 3 or 4 comprising a polymer selected Embodiment 47. A composition comprising a hygroscopic material and a solid ion conductive material comprising at least one of an organic material and an ammonium halide, wherein the organic material has at most 10 H LB value, at most 20% reactivity value, at most 1.0 wt% MAR, or a combination thereof A composition having Embodiment 48. The organic material is paraffin wax, polypropylene carbonate, poly Isobutylene, polyvinylpyrrolidone, polyethylene glycol, hydrogenated nitrile butadiene Rubber, high density polyethylene, low density polyethylene, poly(ethylene oxide), poly Vinyl chloride, poly(acrylonitrile), polyethylene carbonate, polyurethane, po Lystyrene, poly(propylene oxide), poly(vinylidene fluoride), poly(dimethyl Siloxane), poly[bis(methoxyethoxyethoxide)-phosphazene], polypro Pylene glycol, polycaprolactone and poly(trimethylene carbonate). Poly ​(Methyl acrylate), poly(vinylidene fluoride)-co-hexafluoropropylene, poly(acrylonitrile-co-butadiene), poly(styrene-butadiene-styrene) , a polymer selected from the group consisting of poly(methyl methacrylate), styrene-ethylene-butylene-styrene, etc. A composition of embodiment 47 comprising a polymer so selected. Embodiment 49. A composition according to any one of embodiments 47 and 48, and a solvent having an HLB value of 0 , a reactivity value of up to 20%, or a combination thereof, comprising a slurry. Embodiment 50. The composition of embodiment 49, wherein the solvent is toluene, pentene, xylene, pentane, hexane, hepta ne, octane, nonane, decane, undecane, dodecane, cyclopentane, cyclohexane ne, cycloheptane, cyclooctane, cyclodecane, cycloundecane, cyclododecane , dimethyl sulfide, dibromomethane, dichloromethane, o-chlorotoluene, o-dichloro benzene, or a combination thereof.

[0128] Embodiment 51. A composition or slurry according to any one of embodiments 47 to 50, comprising at least 1 wt% to a maximum of 60 wt% organic material based on the total weight of the composition. Embodiment 52. A composition or slurry according to any one of embodiments 47 to 51, comprising at least 1 wt% to a maximum of 60 wt% ammonium halide based on the total weight of the composition. Embodiment 53. A composition or slurry according to any one of embodiments 47 to 52, comprising at least 20 wt% to a maximum of 90 wt% ionic conductive material based on the total weight of the composition. Embodiment 54. A composition or slurry according to any one of embodiments 47 to 53, comprising at least 2 wt% to a maximum of 60 wt% solvent based on the total weight of the composition. Embodiment 54. A composition or slurry according to any one of embodiments 47 to 53, comprising at least 2 wt% to a maximum of 60 wt% solvent The slurry according to any one of Embodiments 49 to 53, inclusive. Embodiment 55. The slurry according to any one of Embodiments 49 to 53, wherein the slurry is a colloidal suspension. Embodiment 56. The solid ion conductive layer, method, slurry, or composition according to any one of Embodiments 1 to 3, wherein the hygroscopic material contains a halide-based material, a sulfide-based material, oxyhalogenated lithium, lithium hydroxide halide, or a combination thereof. Embodiment 57. The solid ion conductive layer, method, slurry, or composition according to Embodiment 56, wherein the halide-based material can be represented by M 3-δ (Me k+ ) f X 3-δ+k*f where -3 ≦ δ < 3, 0 ≦ f < 1, k is the valence of Me, 2 ≦ k < 6, M contains an alkali metal element, Me contains a metal element different from M, and X contains a halogen. Embodiment 58. The solid ion conductive layer, method, or composition according to Embodiment 56, wherein the ion conductive material consists of Li 3 OCl, Li3OBr, Li3O(Cl, Br), Li3OCl0.5Br0.5, Li2OFX, Li 2 OHCl, Li 2 OHB r, or a combination thereof. Embodiment 59. The solid ion conductive layer, method, slurry, or composition according to Embodiment 56, wherein the sulfide contains the following: xLi2S - yP2S5 (LPS), for example, 0.67Li2S - 0.33P2S5, 80Li2S - 20P2S5, 75Li2S - 25P2S5, or 70Li2S - 30P2S5, Li2S - X, where X represents at least one of the following sulfides: SiS2, GeS2, and B2S3, for example, 0.50Li2S - 0.50GeS2, LiI - Li2S - ​ SiS2, for example, 0.40LiI - 0.36Li2S - 0.24SiS2, 0.05Li4SiO4 - 0.57Li2S - 0.38SiS2, Li3PO4 - L i2S - SiS2, for example, 0.01Li3PO4 - 0.63Li2S - 0.36SiS2, LiI - Li2S - B2S3, for example, 0.44LiI - 0 .30Li2S - 0.26B2S3, LiI - Li2S - P2S5, for example, 0.45LiI - 0.37Li2S - 0.18P2S5, a - Li3PS4, Li 10GeP2S12, Li6PS5Cl, Li6PS5Br, Li9.54Si1.74P1.44S11.7Cl0.3, Li10.35[Sn0.27Si1.08 P1.65S12 or any combination thereof. Embodiment 60. The ion - conductive material has an ionic conductivity in bulk of at least 0.1 mS / cm, at least 0.5 mS / cm, at least 1 mS / cm, at least 1.5 mS / cm, or at least 2 mS / cm, in the solid - ion - conductive layer, method, slurry, or composition according to any one of Embodiments 1 to 59.

[0129] Embodiment 61. The ion - conductive material has an ionic conductivity in bulk of at most 50 mS / cm, at most 40 mS / cm, at most 35 mS / cm, at most 30 mS / cm, at most 20 mS / cm, at most 15 mS / cm, at most 10 mS / cm, at most 8 mS / cm, at most 6 mS / cm, at most 5 mS / cm, at most 3 mS / cm, at most 2.8 mS / cm, at most 2.5 mS / cm,, at most 2.2 mS / cm,, at most 2 mS / cm, in the solid - ion - conductive layer, method, slurry, or composition according to any one of Embodiments 1 to 60. A tape comprising the composition or slurry according to any one of Embodiments 47 to 55 , tape.

[0130] Example Example 1 The slurry can be formed to have the composition shown in Table 1. This slurry can be used to form a dense ion conductive layer as described in the embodiments of this specification .

Table 1

[0131] Example 2 Exemplary ion conductive materials can be formed to have the compositions shown in Table 2 below according to the embodiments of this specification .

Table 2

[0132] Example 3 Exemplary porous ion conductive materials can be formed using the compositions shown in Table 3 below, and NH X can be removed to induce porosity as described in the embodiments of this specification 4 .

Table 3

[0133] Example 4 According to the embodiments of this specification, the cathode composite layer can be formed using the compositions shown in Table 4 .

Table 4

[0134] Example 5 Each organic solvent material contained in Table 5 below was mixed with Li 3 YBr 6 powder, and the reactivity value of the solvent was tested by the method described in the embodiments of this specification. The HLB value and the dielectric constant of the solvent determined in the embodiments of this specification are also included.

Table 5

[0135] FIG. 15 is an illustration including the XRD pattern of Li 3 YBr 6 powder and the XRD pattern of Li after testing the reaction values of xylene and dichloromethane as described in the embodiments of this specification. The similar XRD patterns indicate that xylene or dichloromethane does not cause the decomposition of Li 3 YBr 6 3 YBr 6

[0136] FIG. 16 is an explanatory diagram including the XRD pattern of Li 3 YBr 6 powder and the XRD pattern of Li after testing the reactivity of 1,4-dioxane, dimethyl carbonate, N,N-dimethylformamide, diethyl ether, and acetonitrile as described in the embodiments of this specification. The appearance of the LiBr peak and the decrease in the intensity of the characteristic peak of Li 3 YBr 6 indicate significant decomposition of Li 3 YBr 6 3 YBr 6

[0137] Example 6 ​​​​​​​​​ Each binder material included in Table 6 below was mixed with Li 3 YBr 6 powder, and the reactivity value of the binder was tested by the method described in the embodiments of this specification. The HLB value and dielectric constant of the binder are also included. [Table 6]

[0138] When PVA and PC were mixed with the powder of Li 3 YBr 6 , significant decomposition of Li 3 YBr 6 was caused. XRD analysis could not be performed.

[0139] Figure 17 includes an illustration showing the XRD pattern of Li 3 YBr 6 powder and the XRD pattern of Li after testing the reactivity values of poly(acrylonitrile), hydrogenated nitrile butadiene rubber, styrene butadiene rubber, poly(methyl methacrylate), and polyvinylpyrrolidone. From the similar XRD patterns, it can be seen that the binder materials except polyvinylpyrrolidone do not cause the decomposition of Li 3 YBr 6 . Further, as shown in Figure 18, the decomposition of Li YBr powder by polyvinylpyrrolidone is not significant, and the reactivity value of poly 3 YBr 6 vinylpyrrolidone was determined to be 11%. 3 YBr 6

[0140] Example 7 Furthermore, using a chemically compatible binder, tests were conducted on the formation of a solid ion conductive layer by tape casting. ​​​​​​

[0141] Polyisobutylene, styrene-butadiene rubber, hydrogenated nitrile buta diene rubber, and poly(ethylene-vinyl acetate), which are binder materials, were pre-dissolved in toluene, a chemically compatible solvent material, and Li was mixed with YBr 3 powder. All samples were stored and handled in a dry inert 6 environment. To facilitate mixing, a vibratory mill jar and media were used. When operating the vibratory mill apparatus at a frequency of 30 Hz for 20 minutes, the mill jar was sealed. After pulverization, the pulverized jar was returned to the glove box and prepared for further sample handling.

[0142] Li 3 When YBr 6 powder was mixed with pre-dissolved PEVA, it was confirmed that no dispersion or slurry was formed.

[0143] Dispersions formed when pre-dissolved PIB, SBR, and HNBR were mixed with Li 3 YBr 6 powder. The composition of the mixture is included in Table 7. Tape casting of the mixture was performed on thin aluminum foil using a doctor blade. The tape was dried without applying heat so that no cracks occurred.

Table 7

[0144] The ion conductive layer formed with SBR as the binder contains relatively more pores compared to the layers formed with HNBR or PIB, and SBR has an adhesion to Li 3 YBr 6 powder ​​​​Or it was confirmed by cross-sectional analysis using a scanning electron microscope (SEM) that the wettability was low or might be low. It was confirmed.

[0145] The ionic conductivity of the tape was measured as follows and included in Fig. 19. A 15-mm sample was punched out from a dried tape cast and placed in a Teflon (registered trademark) die equipped with a stainless-steel plunger to measure the conductivity. This sample was compressed at a pressure of 10 MPa and the resistance value between the samples was measured by impedance measurement. After the test, the sample was taken out and its thickness was measured. The conductivity was calculated by the following formula.

Equation

[0146] The compressibility of the binder was determined by the change in the thickness of the tape before and after testing the conductivity of the tape and is included in Table 8. The compressibility can be obtained by the formula, C = [(T Press - T B ) / T A B × 100%, where C * represents the compressibility of the binder material, T Press represents the thickness of the tape before the ionic conductivity test, and T B represents the thickness of the tape after the ionic conductivity test. A

Table 8

[0147] Example 8 Each binder material in Table 9 below was mixed with Li 3 YBr 6 powder for forming a solid ionic conductive layer and mixed.

[0148] PVC powder and diisononyl phthalate (DINP) as a plasticizer were mixed so that the mixture contained 40 wt% PVC and 60 wt% DINP based on the total weight of the mixture. Next, the mixture of PVC and DINP was mixed with Li YBr 3 powder. Here, the Li 6 YBr 3 powder 6 was 60 wt% based on the total of the mixture, and the mixture of PVC and DINP was 40 wt% . It was found that when the Li YBr 3 powder was mixed with PVC and DINP, the viscosity of the mixture increased significantly 6 . In the XRD analysis of the mixture of Li YBr 3 and DINP, it was suggested that the decomposition of Li 6 YBr 3 was low and the formation of lithium bromide (LiBr) was low. The reactivity value of DINP was less than 10%, suggesting that it was chemically compatible with Li 6 YBr . In the XRD analysis of the mixture of Li 3 YBr 6 and PVC, it was suggested that PVC was chemically compatible 3 with Li 6 YBr 3 . 6

Table 9

[0149] Silicone - epoxy was premixed with a catalyst in a weight ratio of silicone 99 wt%: B(C 6 F 5 ) 3 . Next, this premix and Li YBr 3 were mixed such that the premix was 70 wt% 6 , Li YBr 3 was 30 wt% 6 ​​Mix to 30 wt% and make a premix with Li 3 YBr 6 in total to make a mixture that is 30 wt%. Note that the mixture of silicone epoxy and catalyst B (C ... 6 F 5 ) 3 and Li 3 YBr 6 The powder mixture cannot be fully cured at 120 °C, which is the curing condition of silicone epoxy, for 30 minutes. It was found that increasing the amount of catalyst does not allow for full curing. ...

[0150] Silicone high consistency rubber (HCR) (Nouryon Silicone Gum RB6 - 0902) and the peroxide which is a catalyst were premixed at a weight ratio of silicone HCR 97 wt%: peroxide 3 wt%. Next, this premix and Li ... 3 YBr 6 were mixed so that the premix was 70 wt% and L3Y Br6 was 30 wt%, and the total of the premix and Li 3 YBr 6 was mixed so that L3Y Br6 was 30 wt%. Also, the mixed powder of silicone HCR, the peroxide which is a catalyst (Nouryon Peroxide PD - 50 - S - PS) and Li ... 3 YBr 6 could not be fully cured, and the XRD pattern of the mixture of silicone HCR, peroxide and Li ... 3 YBr 6 showed characteristic peaks of LiBr, suggesting the decomposition of Li ... 3 YBr 6 ...

[0151] A premix of silicon and the catalyst Sn (Nusil RT Foam Silicone R - 2370) with Li 3 YBr 6was mixed. This mixture did not fully cure, and from the XRD analysis of the mixture, the decomposition of Li 3 YBr 6 was found to be suggested.

[0152] A preliminary mixture of silicon and Pt catalyst (Nusil RT foam silicon R-236 0) and Li 3 YBr 6 were mixed at a weight ratio of 50 wt% of the preliminary mixture: 50 wt% of Li 3 Y Br 6 . From the XRD analysis of this mixture, there was no decomposition of Li 3 YBr 6 , and it was found that silicon and the Pt catalyst were chemically compatible. The Pt content in this mixture was 50 ppm relative to the weight of silicon. This mixture could not be fully cured. Further analysis showed that ammonium bromide, an impurity contained in the powder of Li 3 YBr 6 , might affect the curing. When 400 - 5000 ppm of Pt was additionally added to the mixture of silicon, Pt catalyst, and Li 3 YBr 6 to make the Pt amount 600 ppm or more, it could be cured at a temperature from 2 0 °C to 70 °C.

[0153] Example 9

Table 10

[0154] The solid ion conductive layer is formed using a binder material containing the components listed in Table 10 and a halide ion conductive material. The binder material consists of a binder and a halide ion conductive The weight ratio with the conductive material is 0.1 wt%:99.9 wt%, 0.5 wt%:99.5 wt% , 1 wt%:99 wt%, 1.5 wt%:98.5 wt%, 2 wt%:98 wt%, 3 w t%:97 wt%, 4 wt%:96 wt%, 5 wt%:95 wt%, 6 wt%:94 wt %, 7 wt%:93 wt%, 8 wt%:92 wt%, 9 wt%:91 wt%, 10 wt% :90 wt% and are mixed to form an ion conductive layer.

[0155] This disclosure represents a departure from the art. The ion conductive layers of the embodiments herein can have improved thickness, specific pore characteristics, and composition, and by combining some or all of these with other features, improved performance of the ion conductive layer can be promoted. The ion conductive layer is expected to have improved ion current resistance and / or lithium ion conductivity. The processes described in the embodiments herein can enable improved control over the thickness, porosity, pore characteristics, and composition of the ion conductive layer. The processes may be particularly suitable for forming an ion conductive layer comprising a lithium ion conductive material comprising a halide. Control of heating in combination with the use of specific binders and pore forming materials and other process features can enable improved formation of an ion conductive layer comprising a lithium ion conductive material comprising a halide. The ion conductive layer is suitable for use in solid lithium batteries and can be expected to promote performance improvement of solid lithium batteries. Advantages, other advantages, and solutions to problems have been described above with respect to specific embodiments.

[0156]

[0157] ​​​​​​​​However, advantages, advantages, solutions to problems, and any features (s) that may cause or make more prominent any advantages, advantages, or solutions should not be construed as important, essential, or essential features of any or all of the claims. As used herein, references to a material containing one or more components can be construed to include at least one embodiment in which the material consists essentially of the one or more identified components. The term "consisting essentially of" includes a composition containing these identified materials and excludes all other materials except for minor contents (e.g., impurity contents) that do not significantly change the properties of the materials and will be so construed. Further, or alternatively, in certain non-limiting embodiments, any of the compositions specified herein may potentially consist essentially of materials not explicitly disclosed. Embodiments herein include ranges of contents of specific components within a material, and it will be understood that the contents of the components within a given material total 100%.

[0158] The specification and illustrations of the embodiments described herein are intended to provide a general understanding of the structures of the various embodiments. The specification and illustrations are not intended to function as an exhaustive and inclusive description of all elements and features of an apparatus and system using the structures or methods described herein. Separate embodiments may also be provided in combination in a single embodiment, and conversely, for the sake of brevity, the various features described in the context of a single embodiment may also be provided separately or in any sub-combination. Further, references to values within a range include each and every value within that range. Other Many embodiments may become apparent to those skilled in the art only after reading this specification. Other embodiments may be used and derived from this disclosure so that structural substitutions, logical substitutions, or other changes can be made without departing from the scope of this disclosure. Therefore this disclosure is considered to be illustrative rather than restrictive.

Claims

1. Formula M ３－δ (Me ｋ＋ ) ｆ X ３－δ＋ｋ＊ｆ represented by, -3 ≤ δ < 3, 0 ≤ f ≤ 1, k is the valence of Me, 2 ≤ k < 6, M contains an alkali metal element including Li, Me contains In, Al, a rare earth element, Zr, Hf, Nb, Ta, Zn, an alkaline earth element, or a combination thereof, X consists of one or more halogens, or a combination of one or more halogens and one or more anion groups selected from -NH 2, -OH, -BF 4, and -BH 4, a solid ion conductive material containing a halide-based material, wherein the halide-based material contains at least two metal elements, a solid ion conductive material, and An organic material containing poly(vinylidene fluoride), polyisobutylene, or a combination thereof, wherein the solid ion conductive material is at least 50 vol% based on the total volume of the layer, a layer.

2. The layer according to claim 1, wherein the organic material contains polyisobutylene.

3. The layer according to claim 1 or 2, wherein the organic material is at most 10 vol% based on the total volume of the layer.

4. The layer according to any one of claims 1 to 3, containing at most 10 vol% porosity based on the total volume of the layer.

5. The layer according to any one of claims 1 to 4, wherein X contains at least one of Cl and Br.

6. The layer according to any one of claims 1 to 5, wherein Me contains a rare earth element, In, Al, Zr, or a combination thereof.

7. The layer according to any one of claims 1 to 6, further containing an organic material including a maximum HLB value of 10, a maximum reactivity value of 20%, a maximum dielectric constant of 12, or a combination thereof.

8. A multilayer structure including an electrode covering the layer according to any one of claims 1 to 7.

9. Formula M ３－δ (Me ｋ＋ ) ｆ X ３－δ＋ｋ＊ｆ represented by, -3 ≤ δ < 3, 0 ≤ f ≤ 1, k is the valence of Me, 2 ≤ k < 6, M contains an alkali metal element including Li, Me contains In, Al, a rare earth element, Zr, Hf, Nb, Ta, Zn, an alkaline earth element, or a combination thereof, X consists of one or more halogens or a combination of one or more halogens and one or more anion groups selected from -NH 2, -OH, -BF 4, and -BH 4, a solid ion conductive material containing a halide-based material, wherein the halide-based material contains at least two metal elements, a solid ion conductive material A cathode material, including an organic material containing a polymer including poly(vinylidene fluoride), polyvinyl chloride, poly(vinylidene fluoride-co-hexafluoropropylene), or a combination thereof, wherein the material of the polymer is at most 10 vol% based on the total volume of the layer, a layer.

10. The layer according to claim 9, wherein the polymer has an HLB value of 0 and a dielectric constant of 12 or less.

11. A multilayer structure including an electrolyte layer covering the layer according to any one of claims 9 to 10, wherein the electrolyte layer contains a solid electrolyte material.

12. The layer according to any one of claims 9 to 10, wherein the cathode material contains one or more of lithium-containing oxides, transition metal fluorides, polyanion materials, fluorinated polyanion materials, transition metal sulfides, transition metal oxyfluorides, transition metal oxysulfides, and transition metal oxynitrides.

13. Formula M ３－δ (Me ｋ＋ ) ｆ X ３－δ＋ｋ＊ｆ represented by, -3 ≤ δ < 3, 0 ≤ f ≤ 1, k is the valence of Me, 2 ≤ k < 6, M contains an alkali metal element including Li, Me contains In, Al, a rare earth element, Zr, Hf, Nb, Ta, Zn, an alkaline earth element, or a combination thereof, X consists of one or more halogens, or a combination of one or more halogens and one or more anion groups selected from -NH 2, -OH, -BF 4, and -BH 4, a solid ion conductive material containing a halide-based material A composition including an organic material containing poly(vinylidene fluoride), polyvinyl chloride, poly(vinylidene fluoride-co-hexafluoropropylene), polyisobutylene, or a combination thereof, wherein the solid ion conductive material is at least 50 vol% based on the total volume of the composition.

14. The composition according to claim 13, wherein the organic material contains polyisobutylene.

15. The composition according to claim 13 or 14, further comprising an electron conductive material.

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