Ion conductive layer and method for forming the same

Abstract

The present invention provides a solid ion-conducting layer that can include a foam matrix and an electrolyte material that includes a hygroscopic material. In one embodiment, the electrolyte material can include a halide-based material, a sulfide-based material, or any combination thereof. In another embodiment, the solid ion-conducting layer can include a total porosity of at least 30% by volume of the total volume of the solid ion-conducting layer.

Description

Technical Field

[0001] The following relates to ion-conducting layers and methods of forming the same, and in particular to solid ion-conducting layers and methods of forming the same.

[0002] Related technical notes

[0003] Compared to conventional lithium-ion batteries, solid-state lithium batteries are expected to offer higher energy density and faster charging times, as well as reduced safety concerns, by enabling lithium metal anodes. The use of solid-state electrolytes has been shown to help improve the performance of lithium metal anodes.

[0004] The industry continues to demand solid-state batteries with improved performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0005] The present disclosure may be better understood, and its numerous features and advantages made apparent to those skilled in the art by referencing the accompanying drawings.

[0006] Figure 1 Included is an illustration of a cross-section of an ion conducting layer according to one embodiment herein.

[0007] Figure 2 Included is a cross-sectional illustration of an ion conducting layer according to another embodiment herein.

[0008] Figure 3 Included is a cross-sectional illustration of an ion conducting layer according to another embodiment herein.

[0009] Figure 4 Included is a cross-sectional illustration of a multi-layer structure according to another embodiment herein.

[0010] Figure 5 Included is a cross-sectional illustration of a multi-layer structure according to another embodiment herein.

[0011] Figure 6 Included is a cross-sectional illustration of a multi-layer structure according to one embodiment herein.

[0012] Figure 7 Included is an illustration of a process according to one embodiment herein.

[0013] Figures 8A to 8D Included is a diagram of the process for forming the green layer.

[0014] Figure 9 Included is an illustration of a process according to another embodiment herein.

[0015] Those skilled in the art will appreciate that, for the sake of simplicity and clarity, the elements shown in the figures are not necessarily drawn to scale. For example, the dimensions of some elements in the figures may be exaggerated relative to other elements to help enhance understanding of the embodiments of the present invention. The same reference symbols are used in different figures to indicate similar or identical items. DETAILED DESCRIPTION

[0016] The following description in conjunction with the accompanying drawings is provided to assist in understanding the teachings disclosed herein. The following discussion will focus on specific implementations and examples of the teachings. This emphasis is provided to assist in describing the teachings and should not be construed as limiting the scope or applicability of the teachings.

[0017] As used herein, the terms "consisting of," "including," "comprising," "having," "having" or any other variations thereof are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of features is not necessarily limited to only those features but may include other features not expressly listed or inherent to such process, method, article, or apparatus. In addition, unless expressly stated otherwise, "or" refers to an inclusive or and not an exclusive or. For example, condition A or B may be satisfied by any 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), and both A and B are true (or exist).

[0018] The use of "a" or "an" to describe elements and components described herein is for convenience only and to give a general sense of the scope of the invention. Unless otherwise apparent, this description should be understood to include one or at least one and the singular also includes the plural, and vice versa.

[0019] 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 limiting.

[0020] The embodiments herein relate to a solid ion conductive layer comprising an ion conductive material. In an embodiment, the ion conductive material may be an electrolyte material. The electrolyte material may include a hygroscopic material. In certain cases, the electrolyte material may include a sulfide-based or halide-based electrolyte material having a bulk ion conductivity suitable for use in solid-state batteries (such as solid-state lithium-ion batteries). In certain embodiments, the solid ion conductive layer may include a porous structure (such as a foam matrix) comprising an electrolyte material. In an embodiment, the ion conductive layer may be a composite layer further comprising an electronically conductive material (such as an anode or cathode active material). In yet another embodiment, the ion conductive layer may be a component of an electrochemical device. For example, the ion conductive layer may be formed as a composite layer comprising an anode, a cathode, or any combination thereof. In certain embodiments, the electrochemical device may include a solid-state lithium-ion battery.

[0021] Embodiments further relate to methods for forming a solid ionically conductive layer. The methods can allow for the formation of porous structures comprising halide-based or sulfide-based electrolyte materials, which are typically hygroscopic. The methods can further allow for the formation of solid ionically conductive layers with controlled porosity and / or thickness, suitable for solid-state battery applications.

[0022] In one embodiment, the solid ion conductive layer can include a foam matrix containing an electrolyte material. In one aspect, the electrolyte material can be embedded in the foam matrix. In another aspect, the electrolyte material can include a hygroscopic material. Exemplary hygroscopic electrolyte materials can include halide-based materials, sulfide-based materials, or any combination thereof. In another aspect, the foam matrix can include a hygroscopic electrolyte material.

[0023] In one embodiment, the foam matrix may include a halide-based electrolyte material comprising a complex metal halide. In one aspect, the complex metal halide may be composed of M 3-δ (Me k+ ) f X 3-δ+k*f (Formula I) wherein -3≤δ<3; 0≤f≤1; k is the valence of Me; and 2≤k<6. In one particular aspect, the complex metal halide can be composed of M 3-δ Me k+ X 3-δ+k (Formula II) represents, wherein -0.95≤δ≤0.95.

[0024] M may include an alkali metal element, including Li, Na, Rb, Cs, K, or any combination thereof. Me may include a divalent element, a trivalent element, a tetravalent element, a pentavalent element, a hexavalent element, or any combination thereof. When Me is a combination of elements, k may be the average of the total valences of the elements. For example, when Me includes x moles of a trivalent element and y moles of a tetravalent element, k = (3x + 4y) / (x + y). In this case, Me includes equimolar amounts of the trivalent and tetravalent elements, and k = 3.5. In more specific cases, k may be 3, 4, or 5. X may include a halogen. In some cases, X may include an anionic group other than a halogen. Such anionic groups may include amides (–NH2), hydroxides (-OH), -BF4, -BH4 (borohydride), or combinations thereof. Anionic groups may be included as impurities or dopants. In certain cases, X may consist of one or more halogens or a combination of one or more halogens and anionic groups.

[0025] In certain instances, M may include Li. In one instance, M may include Li and another alkali metal element. In another example, M may consist of Li. In another example, M may consist of at least one of Li, Na, Cs, Rb, and K. In certain instances, M may consist of Li and at least one of Cs and Na.

[0026] Yet another example of Me may include alkaline earth metal elements (such as Mg, Ca, Sr and / or Ba), Group 12 elements (such as Zn), or any combination thereof. With respect to the groups of elements mentioned in the present disclosure, reference is made to the IUPAC Periodic Table of Elements published on December 1, 2018.

[0027] In another example, Me may include one or more trivalent elements. For example, Me may include Group 13 elements (such as In and / or Al), Group 3 elements, rare earth elements (such as Sc, Y) and / or lanthanides or any combination thereof. In yet another example, Me may include 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 specific example, Me may include rare earth elements, such as Y, Sc, La, Ce, Pr, Nd, Pm, Sm, Eu, Tm, Gd, Tb, Dy, Ho, Lu, or any combination thereof.

[0028] In one particular aspect, the halide-based material may include (Li 1-d Na d) Li2REX6 (Formula III), where RE is one or more rare earth elements, and 0 ≤ d < 1. Specific examples of RE may include Y, Gd, Er, or combinations thereof. For example, RE may consist of Y. In another specific case, RE may consist of Y and at least one other rare earth element.

[0029] In another specific aspect, the halide-based material may include Li3Y Z RE 1-Z X6 (Formula IV), where 0 < Z ≤ 1 and RE is one or more rare earth elements other than Y.

[0030] Specific examples of the halide-based electrolyte material may include Li3YBr6, Li3YCl6, Li3(Al, Ga, In)X6, (Li 0.5 , Na 0.5 )2LiYCl6, Li3YBr6, Li 2.5 Y 0.5 Zr 0.5 Cl6, Li3Y 0.95 Sm 0.05 Br3Cl3, Li3Y 0.9 Sm 0.1 Br3Cl3, Li3YBr3Cl3, Li3Y 0.9 Er 0.1 Br3Cl3, Li3Y 0.9 Lu 0.1 Br3Cl3, Li3Y 0.9 Tb 0.1 Br3Cl3, Li3Y 0.95 Bi 0.05 Br6, Li3Y 0.9 Dy 0.1 Br3Cl3, Li3Y 0.9 Eu 0.1 Br3Cl3, Li 3.1 Y 0.9 Ba 0.1 Br6, Li 2.8 Y 0.9 Ta 0.1 Br2Cl2I2, Li 3.2 Y 0.9 Sr 0.2 Br6, LiCsCl2, Li3YCl3Br3, etc. or any combination thereof.

[0031] In another specific aspect, the halide-based electrolyte material may include ammonium halides, such as NH4Cl, NH4Br, or combinations thereof. In a specific case, the ammonium halide may be a dopant or impurity present in the complex metal halide.

[0032] In another embodiment, the hygroscopic material may include lithium halide, lithium oxyhalide, lithium halide hydroxide, or a combination thereof having an antiperovskite crystal structure. For example, the hygroscopic material may include Li 3-x M x / 2 OA 1-z A' z , wherein A and A' are A-position halogens such as F, Cl, Br or I. Specific examples may include Li3OCl, Li3OBr, Li3O(Cl, Br) (e.g., Li3OCl 0.5 Br 0.5 ), Li2OHX (e.g., Li2OHCl and Li2OHBr), etc.

[0033] On the other hand, the electrolyte material may include a sulfide-based material. The sulfide-based material may include an amorphous phase, a crystalline phase, or any combination thereof. Specific examples of sulfide-based materials may include, but are not limited to, xLi2S-yP2S5 (LPS), such as 0.67Li2S-0.33P2S5, 80Li2S-20P2S5, 75Li2S-25P2S5, 70Li2S-30P2S5, etc., Li2S—X, where X represents at least one sulfide of SiS2, GeS2, and B2S3, such as 0.50Li2S–0.50GeS2, LiI-Li2S-SiS2, such as 0.40LiI–0.36Li2S–0. 24SiS2, etc., 0.05Li4SiO4–0.57Li2S–0.38SiS2, Li3PO4-Li2S-SiS2, such as 0.01Li3PO4–0.63Li2S–0.36SiS2, etc., LiI-Li2S-B2S3, such as 0.44LiI–0.30Li2S–0.26B2S3, etc., LiI-Li2S-P2S5, such as 0.45LiI–0.37Li2S–0.18P2S5, etc., a-Li3PS4, LGPS (e.g., Li 10 GeP2S 12 ), LPSCl (e.g., Li6PS5Cl), LPSBr (e.g., Li6PS5Br), LSPSCl (e.g., 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.

[0034] In another embodiment, the electrolyte material can have a specific bulk ionic conductivity, which can be beneficial for forming improved properties of the solid ionically conductive material. In one aspect, the electrolyte material can have a bulk ionic conductivity of at least 0.1 mS / cm, 0.5 mS / cm, 1 mS / cm, at least 1.5 mS / cm, or at least 2 mS / cm. In another aspect, the electrolyte material can have a bulk ionic conductivity of at most 50 mS / cm, at most 45 mS / cm, at most 40 mS / cm, at most 40 mS / cm, at most 40 mS / cm, at most 35 mS / cm, at most 30 mS / cm, at most 29 mS / cm, at most 25 mS / cm, at most 20 mS / cm, at most 15 mS / cm, at most 10 mS / cm, at most 5 mS / cm, at most 3 mS / cm, 2 mS / cm, or 1 mS / cm. Additionally, the electrolyte material can have a bulk ionic conductivity within a range including any of the minimum and maximum values noted herein. As described herein, bulk ionic conductivity is measured at 23°C.

[0035] In yet another embodiment, the solid ionically conductive layer can include a specific amount of electrolyte material that can be beneficial for improving the formation and characteristics and / or performance of the solid ionically conductive layer. In one aspect, the solid ionically conductive layer can include at least 5% by volume of the total volume of the solid ionically conductive layer, such as at least 7% by volume, at least 9% by volume, at least 10% by volume, at least 12% by volume, at least 15% by volume, at least 17% by volume, at least 19% by volume, at least 20% by volume, at least 25% by volume, at least 27% by volume, or at least 30% by volume of the total volume of the ionically conductive layer. On the other hand, the solid ion conducting layer can include up to 70% by volume of the total volume of the solid ion conducting layer, such as up to 68% by volume, up to 65% by volume, up to 60% by volume, up to 58% by volume, up to 55% by volume, up to 50% by volume, up to 48% by volume, up to 45% by volume, up to 42% by volume, up to 40% by volume, up to 38% by volume, up to 35% by volume, up to 30% by volume, up to 28% by volume, up to 25% by volume, up to 20% by volume, up to 15% by volume, up to 10% by volume or up to 5% by volume of the electrolyte material. On the other hand, the amount of electrolyte material can be within the range including any minimum and maximum percentages mentioned herein. For example, the solid ion conducting layer can include 20% to 40% by volume of the electrolyte material, based on the total volume of the solid ion conducting layer.

[0036] In one embodiment, the solid ion conductive layer may comprise an organic material that may be advantageous in improving the formation and performance of the solid ion conductive layer. For example, the organic material may be advantageous in forming a solid ion conductive layer having improved properties. The properties may include pore characteristics, thickness, ionic conductivity, wettability of the electrode active material, chemical and physical compatibility, flexibility, chemical stability, electrochemical stability, mechanical strength, elasticity, plasticity, softness, or any combination thereof. Exemplary pore characteristics may include porosity, average pore size, pore shape, pore orientation, aspect ratio, pore size distribution, surface area, or any combination thereof.

[0037] In one aspect, the organic material can have minimal or no reactivity with the electrolyte material during formation of the ionically conductive layer, under operating conditions for application of the solid ionically conductive layer, or both. For example, during formation of the solid ionically conductive material, the organic material can have little or no adverse effect on the composition, ionic conductivity, electronic conductivity, electrochemical stability, or both of the electrolyte material.

[0038] In one particular aspect, the organic material can have a specific reactivity value that can be beneficial to improving the formation and characteristics of the solid ion conductive layer. In one example, the organic material can have a reactivity value of at most 20% or less than 20%, such as at most 18%, at most 15%, at most 12% or at most 10%. In other examples, the organic material can have a reactivity value of less than 10%, such as 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%. In another example, the organic material can have a reactivity value of 0% or 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%. In addition, the reactivity value can be within the range of any minimum percentage and maximum percentage mentioned herein. For example, the organic material can have a reactivity value of up to 2%. In a specific embodiment, the organic material may have a reactivity value of less than 20% for a halide-based material including Li3YBr6 or a halide-based material including a crystalline structure similar to Li3YBr6 (such as a layered crystalline structure, or more specifically, a monoclinic crystalline structure). In another specific embodiment, the organic material may have a reactivity value of less than 10% for a halide-based material including Li3YCl6 or a halide-based material including a crystalline structure similar to Li3YCl6 (such as a hexagonal or trigonal crystalline structure).

[0039] The reactivity value can be determined as follows. The reactivity value of the organic material to the ion conductive material can be tested by mixing the solid ion conductive material with the organic material in a weight percentage of 10:90, and maintaining the mixture at no more than 100°C (such as 20°C to 60°C) in an inert atmosphere for at least 12 hours and up to 24 hours. X-ray diffraction analysis can be performed to detect changes in the XRD pattern, such as changes in characteristic peaks of the ion conductive material and changes in other peaks between before and after the test. For example, the change can include the disappearance of a characteristic peak, a change in the intensity of a characteristic peak, a change in the intensity of a characteristic peak of certain impurities or degradation or decomposition products of the solid ion conductive material, or any combination thereof.

[0040] The reactivity value of the organic material can be tested and determined as follows. The organic material and the ion conductive material can be mixed in a weight percentage of 70:30, wherein for the total weight of the ion conductive material and the organic material, each ion conductive material accounts for 30 weight percent and each polymer accounts for 70 weight percent in the mixture. In some cases, an inorganic catalyst of the organic material can be utilized to form a solid ion conductive layer, and a mixture of the catalyst and the organic material can be used instead of the organic material for testing the reactivity value of the mixture of the catalyst and the organic material. The mixture can be sealed in an airtight sample holder with a Kapton film window for performing XRD analysis. The entire test can be performed in a dry environment with a H2O content of <1ppm. XRD analysis can be performed from 25 to 80 degrees 2θ, with a step length of 7.5°C and a step time of 120 seconds, using an X-ray diffractometer.

[0041] The reactivity value of the organic material can be determined based on the XRD pattern of the dry solid material using the formula RV = [B / A] × 100%, where A represents the characteristic peak intensity of the solid ion conductive material and B represents the characteristic peak intensity of the representative decomposition product of the solid ion conductive material. The representative decomposition product can be binary, including lithium and the main anion atoms of the ion conductive material. For example, lithium halide can be a representative decomposition product of the halide-based material of the embodiments of this invention. Therefore, A can be the characteristic peak of the halide-based material, and B can be the characteristic peak of the lithium halide. Referring to Figure 18, A and B are shown in the XRD pattern for testing the reactivity value of the organic material with Li3YBr6 compared to the XRD pattern of the original Li3YBr6. The characteristic XRD peak of Li3YBr6 generally appears between 31 degrees 2θ and 32.2 degrees 2θ, and the characteristic peak of LiBr appears between 27.9 degrees 2θ and 28.5 degrees 2θ. The characteristic peak of Li3YCl6 is between 40.5 degrees 2θ and 41.5 degrees 2θ, and that of LiCl is between 34.5 degrees 2θ and 35.5 degrees 2θ. When the XRD pattern does not include the characteristic peak of a representative decomposition product of the ion-conductive material, and A is not 0, the reactivity value of the organic material can be determined to be 0. When the XRD pattern of the mixture of the organic material and the ion-conductive material does not include the characteristic peak of the ion-conductive material, the reactivity value of the organic material can be determined to be undefined.

[0042] In some cases, the XRD pattern of the original ion-conducting material may include characteristic peaks representative of decomposition products. For example, a halide-based material may include lithium halide as an impurity. In these cases, the XRD pattern of the original ion-conducting material may be referenced to determine the RI. O , where RI O =[b / a]×100%, where b represents the characteristic peak intensity of the decomposition product and a represents the characteristic peak intensity of the ion conductive material. The reactivity value (RV) of the organic material can be expressed by the formula RV=RI DS –RI O To determine, where RI DS =[B / A]×100%, B is the characteristic peak intensity of the decomposition product in the mixture, and A is the characteristic peak intensity of the ion conductive material in the mixture.

[0043] In one aspect, the organic material can have a specific moisture absorption rate (hereinafter referred to as "MAR") that can be beneficial for improving the formation and properties of the solid ion conductive layer. In one example, the organic material can have a MAR of at most 1.0 wt%, such as at most 0.8 wt%, at most 0.5 wt%, at most 0.3 wt%, or at most 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 yet another example, the organic material can have a MAR within a range including any minimum and maximum percentages mentioned herein. For example, the organic material can have a MAR of up to 0.3 wt%.

[0044] MAR can be tested and determined as follows. A specimen of organic material of a specific size can be placed in distilled water or exposed to moist air (i.e., 50% relative humidity) at 23°C or 100°C for 24 hours. The moisture absorption rate can be determined by the formula MAR = [(W AE -W BE ) / W BE ]×100% to determine, where W BE is the weight of the dry specimen, and W AE is the weight of the specimen before exposure to water or moist air. The specimen can be dried in an oven and then placed in a desiccator to cool. Weigh the specimen immediately after cooling to obtain W. BE Alternatively, the MAR may be determined according to ASTM D570 or ISO 62.

[0045] In one aspect, the organic material can have a hydrophobic portion, a lipophilic portion, or a combination thereof. In a specific aspect, the organic material can have a specific hydrophilic-lipophilic balance (hereinafter referred to as "HLB") value that can be beneficial for improving the formation and properties of the solid ion conductive layer. In one example, the organic material can have 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 3, at most 2.6, at most 2.2, at most 2, at most 1.5, at most 1, at most 0.5, or at most 0.1. In another example, the organic material can have an HLB value of 0 or higher, such as at least 0.001, at least 0.005, at least 0.01, at least 0.05, at least 0.0.08, or at least 0.1. In yet another example, the organic material can have an HLB value within a range including any of the minimum and maximum values mentioned herein. For example, the organic material can have an HLB value as high as 4.

[0046] The HLB value can be calculated using the Griffin mathematical method using the formula HLB = 20 × M h / M to determine, where M h is the molecular mass of the hydrophilic portion of the organic material, and M is the molecular mass of the entire organic material. To aid understanding, using an exemplary scale of HLB 0 to 20, an HLB value of 0 may correspond to a completely lipophilic / hydrophobic molecule, while a value of 20 may correspond to a completely hydrophilic / lipophobic molecule.

[0047] Exemplary hydrophilic groups may include N (tertiary amine), -COOH (carboxyl), -O- (ether), -OH (hydroxyl), -COO- (ester), C=O (carbonyl), or any combination thereof. Exemplary lipophilic groups may include -C≡N (nitrile), -CH3 (methyl), =CH2 (methylene), -CH2-, -CH=, -C6H5 (phenyl group), -F (fluoro group), -Cl (chloro group), or any combination thereof.

[0048] In one embodiment, the organic material can have a specific dielectric constant that can be beneficial to improving the formation, characteristics and / or performance of the solid ion conductive layer. In one aspect, the organic material can have a dielectric constant of at most 35, such as at most 33, at most 31, at most 29, at most 26, at most 23, at most 20, at most 19, at most 17, at most 15, at most 13, at most 12, at most 11, at most 10.5, at most 10, 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. On the other hand, the organic material can have a dielectric constant of at least 0.5, such as at least 1, at least 2, at least 3, at least 4 or at least 5. In addition, the organic material can be included in the dielectric constant within the scope of any minimum and maximum values mentioned herein.

[0049] 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 may include a solvent material having an HLB value of 0, a reactivity value of at most 20%, a dielectric constant of at most 35, or any combination thereof. In certain instances, the organic material may include 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 the organic solvent may include heptane, cyclohexane, dibromomethane, dichloromethane, 1,2-dichloroethane, or any combination thereof.

[0050] On the other hand, the organic material can include a binder material comprising a specific HLB value, a specific reactivity value, or any combination thereof. For example, the organic binder material can include an HLB value less than 10 and a reactivity value less than 20%. In another example, the organic binder material can include an HLB value less than 10 and a reactivity value less than 10%. More specific examples of organic binders can include hydrogenated nitrile rubber, styrene butadiene rubber, polyisobutylene, poly(vinylidene fluoride), poly(acrylonitrile), paraffin, polyethylene, polyvinyl chloride, poly(ethylene oxide), polyvinyl pyrrolidone, poly(methyl methacrylate), or any combination thereof.

[0051] In one aspect, the organic material can include a polymer, such as a thermosetting polymer, a thermoplastic polymer, or any combination thereof.

[0052] Examples of organic materials may include one or more of the following: paraffin wax, polyisobutylene, polyvinyl pyrrolidone, poly(methyl methacrylate), polyethylene glycol, camphene, urea, poly(acrylonitrile), polyethylene carbonate, polyvinyl chloride, poly(ethylene oxide), poly(propylene oxide), poly(vinylidene fluoride), poly(dimethylsiloxane), poly[bis(methoxyethoxyethanolate)-phosphazene], polypropylene glycol, polycaprolactone and poly(trimethylene carbonate), poly(methyl acrylate), poly(vinylidene fluoride)-co-hexafluoropropylene, poly(acrylonitrile-co-butadiene), poly(styrene-butadiene-styrene) and styrene-ethylene-butylene-styrene, styrene-butadiene rubber, hydrogenated nitrile rubber, high-density polyethylene, low-density polyethylene, poly(ethylene oxide), polystyrene and polyurethane, or any combination thereof.

[0053] In another example, the organic material may include one or more polymers selected from the group consisting of poly(propylene oxide), poly(vinylidene fluoride), poly(dimethylsiloxane), poly[bis(methoxyethoxyethanolate)-phosphazene], polypropylene glycol, polycaprolactone and poly(trimethylene carbonate), poly(methyl acrylate), poly(vinylidene fluoride)-co-hexafluoropropylene, poly(acrylonitrile-co-butadiene), poly(styrene-butadiene-styrene) and styrene-ethylene-butylene-styrene, hydrogenated nitrile rubber, high density polyethylene, low density polyethylene, poly(ethylene oxide), polystyrene, styrene-butadiene rubber and polyurethane.

[0054] In certain instances, the organic material can be composed of a polymer comprising polyurethane, epoxy resin, or a combination thereof. In another certain instance, the organic material can comprise a polymer comprising siloxane. In another certain instance, the solid ion conductive layer can comprise a polysiloxane. For example, the solid ion conductive layer can comprise an organosilicon-based polymer. In another example, the solid ion conductive layer can comprise a foam matrix comprising organosilicon.

[0055] In one embodiment, the ion conductive layer may include a specific amount of organic material that can be beneficial to improving the formation and performance of the ion conductive layer. For example, the ion conductive layer may include at least 1 volume %, such as at least 2 volume %, at least 3 volume %, at least 4 volume %, at least 5 volume %, at least 10 volume %, at least 15 volume %, at least 20 volume %, at least 25 volume %, at least 30 volume %, or at least 35 volume % of the organic material, based on the total volume of the ion conductive layer. In another example, the ion conductive layer may include at most 50 volume %, such as at most 48 volume %, at most 45 volume %, at most 40 volume %, at most 36 volume %, at most 30 volume %, at most 25 volume %, at most 20 volume %, at most 15 volume %, at most 10 volume %, at most 8 volume %, at most 7 volume %, at most 6 volume %, or at most 5 volume % of the organic material, based on the total volume of the ion conductive layer. In addition, the amount of organic material can be within a range including any minimum and maximum percentages mentioned herein. For example, the ion-conducting layer may comprise at least 5 volume % and at most 15 volume % of the organic material, based on the total volume of the ion-conducting layer.

[0056] In yet another embodiment, the ion conductive layer may include a specific ratio of electrolyte material content to organic material content. In one aspect, the ion conductive layer may include V E :V O The ratio of V O is the volume percentage of the organic material relative to the total volume of the solid ion conductive layer, and V E is the volume percentage of the electrolyte material relative to the total volume of the solid ion conductive layer. In one example, V E :V O The ratio of V can be at least 0.5, at least 1, at least 1.2, at least 1.5, at least 2, at least 2.5, or at least 3. In another embodiment, V E :V O The ratio of may be at most 15, at most 12, at most 10, 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. For example, V E :V O It can be at least 2.5 and at most 12. In yet another example, VE :V O The ratio can be within a range including any of the minimum and maximum values noted herein.

[0057] In certain embodiments, the solid ion conductive layer may comprise a polymer, which may be a reaction product of a foaming system. An exemplary foaming system may comprise an organic precursor, a cross-linking agent, and a foaming agent. In some cases, the foaming system may comprise a catalyst. In other cases, the foaming system may comprise a base resin, a plasticizer, and a foaming agent. In one aspect, each component of the foaming system may be hydrophobic. In another aspect, each component of the foaming system may have an HBL value, a MAR, a reactivity value, or any combination thereof, as mentioned in the embodiments herein.

[0058] In one embodiment, the solid ion conductive layer may include a polymer including siloxane. In a specific aspect, the solid ion conductive layer may include organosilicon. In specific cases, the solid ion conductive layer may include a foam matrix produced by a foaming system, the foam matrix including a polymer including organosilicon, a crosslinker, a catalyst and a foaming agent. Examples of organosilicon may include polydimethylsiloxane (PDMS), vinyl-terminated PDMS, hydride-functional siloxane, methylhydrogensiloxane-dimethylsiloxane copolymer or any combination thereof. In a specific example, the solid ion conductive material may include a catalyst for the organosilicon material. The catalyst may include an inorganic material, such as a metal. A specific example of the catalyst may include an inert metal. Another specific example of the catalyst may include platinum, a platinum complex or any combination thereof. In specific cases, the catalyst may be in a solvent material (such as xylene). In a specific embodiment, the catalyst may include a complex of platinum in xylene. In some cases, the solid ion conductive layer may include a crosslinker, such as PDMS-co-PHMS. The foaming agent may include monofunctional or difunctional silanol or benzyl alcohol. In certain instances, the solid ionically conductive layer can include a foam matrix produced by a foaming system including a silicone-containing polymer, a cross-linking agent, a catalyst, and a blowing agent.

[0059] In certain embodiments, the solid ion-conducting layer can include a polymer comprising siloxane in a specific amount that can facilitate improved formation and performance of the ion-conducting layer. For example, the ion-conducting layer can include at least 1% by weight of the total weight of the ion-conducting layer, such as at least 2% by weight, at least 5% by weight, at least 7% by weight, at least 9% by weight, at least 12% by weight, at least 15% by weight, at least 20% by weight, at least 25% by weight, at least 30% by weight, or at least 35% by weight of the polymer comprising siloxane, based on the total weight of the ion-conducting layer. In another example, the ion conductive layer can include up to 70 wt % of the total weight of the ion conductive layer, such as up to 60 wt %, up to 55 wt %, up to 50 wt %, up to 48 wt %, up to 45 wt %, up to 40 wt %, up to 35 wt %, up to 28 wt %, up to 25 wt %, up to 20 wt %, up to 15 wt %, up to 12 wt %, or up to 10 wt % of the total weight of the ion conductive layer. Furthermore, the amount of polymer comprising siloxane can be within a range including any of the minimum and maximum percentages mentioned herein.

[0060] In more specific cases, the solid ion conductive layer can contain a catalyst, such as Pt, in a specific amount of at least 10 ppm, at least 20 ppm, at least 30 ppm, or at least 50 ppm, based on the total weight of the foam matrix. In more specific cases, greater than 50 ppm or greater than 100 ppm, such as at least 150 ppm, at least 200 ppm, at least 250 ppm, at least 300 ppm, at least 350 ppm, at least 400 ppm, at least 500 ppm, or at least 600 ppm, based on the total weight of the foam matrix. Alternatively or additionally, the solid ionically conductive layer can contain a specific amount of catalyst, such as Pt, at most 1 wt % based on the total weight of the solid ionically conductive layer, such as at most 0.9 wt %, at most 0.7 wt %, at most 0.6 wt %, at most 0.5 wt %, at most 0.4 wt %, at most 0.3 wt %, at most 0.2 wt %, at most 0.1 wt %, at most 900 ppm, at most 800 ppm, at most 700 ppm, at most 600 ppm, at most 500 ppm, or at most 400 ppm based on the total weight of the foam matrix. Furthermore, the solid ionically conductive layer can contain an amount of catalyst, such as Pt, within a range including any minimum and maximum values mentioned herein.

[0061] In a particular aspect, the solid ion conductive layer can comprise polyvinyl chloride. More specifically, the foam matrix can be the reaction product of a foaming system comprising polyvinyl chloride, a plasticizer, and a foaming agent. In a particular embodiment, the plasticizer can comprise diisononyl phthalate (DINP), and the foaming agent can comprise azodicarbonamide.

[0062] In one particular aspect, the solid ion conductive layer can comprise a polyurethane which can be the reaction product of a foaming system comprising a hydrophobic polyol, a cross-linking agent having an HBL value of at most 4, and a blowing agent. Examples of cross-linking agents can include isocyanate 370, hexamethylene diisocyanate (HDI), isophorone diisocyanate, a hydrophobic polyisocyanate, diphenylmethane diisocyanate, or any combination thereof. Examples of blowing agents can include cyclopentane, pentane, isopentane, or any combination thereof. Examples of hydrophobic polyols can include VORAPEL® from Dow. TM D3201 and VORAPEL TM T5001 and from BASF 750 and 818 hydrophobic polyol.

[0063] In a particular embodiment, the solid ion conductive layer can include a specific content of polyurethane, which can be beneficial to improving the formation and performance of the ion conductive layer. For example, the ion conductive layer can include at least 1 volume % of the total volume of the ion conductive layer, such as at least 2 volume %, at least 5 volume %, at least 7 volume %, at least 10 volume %, at least 15 volume %, at least 20 volume %, at least 25 volume %, at least 28 volume %, at least 30 volume % or at least 35 volume % of the polyurethane. In another example, the ion conductive layer can include at most 30 volume % of the total volume of the ion conductive layer, such as at most 50 volume %, at most 48 volume %, at most 45 volume %, at most 42 volume %, at most 40 volume %, at most 38 volume % or at most 35 volume % of the polyurethane of the total volume of the ion conductive layer. In addition, the content of the polyurethane can be within the range of any minimum percentage and maximum percentage mentioned herein. For example, the ion conductive layer can include at least 5 volume % and at most 45 volume % of the total volume of the ion conductive layer.

[0064] In one particular aspect, the foam matrix may include V E :V PU A specific ratio, where V PU is the volume percentage of polyurethane relative to the total volume of the foam matrix, and V E is the volume percentage of the electrolyte material relative to the total volume of the foam matrix. In one example, V E :V PU The ratio of V can be at least 1.2, such as at least 1.5, at least 2, at least 2.2, at least 2.5, at least 2.7, at least 3, at least 3.3, or at least 3.5. In another embodiment, V E :V PUThe ratio of can be at most 15, at most 12, at most 10, at most 9.5, at most 9, at most 8.5, at most 8, at most 7.5, at most 7, at most 6.5, at most 6, at most 5.5, at most 5, at most 4.5, or at most 4, at most 3.5, at most 3, at most 2.5, or at most 2. For example, V E :V PU The ratio of V may be at least 2.5 and at most 12. In yet another example, V E :V PU The ratio can be within a range including any of the minimum and maximum values noted herein.

[0065] In another aspect, the solid ion conductive layer can comprise a polymer comprising an epoxy resin. In a specific aspect, the polymer can comprise an epoxy resin formed by a foaming reaction of a hydrophobic epoxy resin and a crosslinking agent. Examples of epoxy resins can include trihydroxyphenylethane, resorcinol diglycidyl ether, hydrogenated bisphenol-A diglycidyl ether, modified bisphenol-A diglycidyl ether, novolac epoxy resin, or any combination thereof. In another example, a polymer commercially available under the name Der TM In another example, epoxy resin from Vantico can be used. Casting system CY 221. Examples of crosslinking agents may include amines or thiols. A specific example of a hardener may be 1922A, 3-800 or 800. Exemplary blowing agents may include pentane.

[0066] In certain embodiments, the solid ion-conducting layer may include a specific amount of epoxy resin that can be beneficial for improving the formation and performance of the ion-conducting layer. For example, the ion-conducting layer may include at least 1% by volume of the total volume of the ion-conducting layer, such as at least 2% by volume, at least 3% by volume, at least 4% by volume, at least 5% by volume, at least 7% by volume, at least 10% by volume, at least 15% by volume, at least 20% by volume, at least 25% by volume, at least 30% by volume, or at least 35% by volume of the epoxy resin. In another example, the ion-conducting layer may include at most 50% by volume of the total volume of the ion-conducting layer, such as at most 48% by volume, at most 45% by volume, at most 40% by volume, at most 35% by volume, at most 28% by volume, at most 25% by volume, at most 20% by volume, at most 15% by volume, at most 12% by volume, at most 10% by volume, at most 8% by volume, or at most 5% by volume of the epoxy resin. Moreover, the epoxy resin can be present in an amount within a range including any of the minimum and maximum percentages noted herein.For example, the ion conductive layer can include at least 5 volume % and up to 45 volume % epoxy resin, based on the total volume of the ion conductive layer.

[0067] In one particular aspect, the foam matrix may include V E :V EP A specific ratio, where V EP is the volume percentage of epoxy resin relative to the total volume of the foam matrix, and V E is the volume percentage of the electrolyte material relative to the total volume of the foam matrix. In one example, V E :V EP The ratio of V can be at least 1.2, such as at least 1.5, at least 2, at least 2.2, at least 2.5, at least 2.7, at least 3, at least 3.3, or at least 3.5. In another embodiment, V E :V EP The ratio of may be at most 15, at most 12, at most 10, at most 9.5, at most 9, at most 8.5, at most 8, at most 7.5, at most 7, at most 6.5, at most 6, at most 5.5, at most 5, at most 4.5, or at most 4. In yet another example, V E :V EP The ratio of can be within a range including any of the minimum and maximum values mentioned herein. For example, V E :V EP It can be at least 2.5 and at most 12.

[0068] In one aspect, the organic material can be contained within a foam matrix. In yet another aspect, the electrolyte material can be dispersed within the organic material.

[0069] In one embodiment, the ion conductive layer may include a lithium salt dispersed in an organic material. The lithium salt may be beneficial for improving the ionic conductivity of the ion conductive layer. Examples of lithium salts may include, but are not limited to, LiPF6, LiClO4, LiBF4, LiAsF6, LiTf, LiSA, LiFSI, LiTFSI, LiBETI, LiCTFSI, LiBOB, LiTDI, LiPDI, LiDCTA, LiB(CN)4, LiPF6, LiBF4, LiSbF6, LiAsF6, LiSO3CF3, LiN(SO2CF3)2, LiN(SO2C2F5)2, LiN(SO2CF3)(SO2C4F9), LiC(SO2CF3)3, or combinations thereof.

[0070] In one embodiment, the ion conductive layer may include one or more pore characteristics, including but not limited to a specific average pore size, a specific pore size distribution (such as D 10 、D 50 and / or D 90), 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. It is expected that the one or more specific pore characteristics combined with one or more other characteristics of the ion conductive layer will improve the formation and performance of the ion conductive layer.

[0071] In one embodiment, the solid ion conductive layer may include a plurality of pores, including closed pores, open pores (e.g., interconnected pores), or any combination thereof. In another embodiment, the solid ion conductive layer may include a specific total porosity that may be beneficial for improving the formation and performance of the solid ion conductive layer. In one aspect, the solid ion conductive layer may include a total porosity of at least 20% by volume, such as at least 30% by volume, at least 40% by volume, at least 50% by volume, at least 60% by volume, at least 70% by volume, or at least 80% by volume of the total volume of the solid ion conductive layer. In another aspect, the solid ion conductive layer may include a total porosity of at most 95% by volume, such as at most 90% by volume, at most 85% by volume, at most 80% by volume, at most 75% by volume, at most 70% by volume, at most 65% by volume, at most 60% by volume, at most 55% by volume, or at most 50% by volume. In addition, the solid ion conductive layer may include a total porosity within a range including any minimum and maximum percentages mentioned herein.

[0072] In yet another embodiment, the solid ion conductive layer can include a specific average pore size that can be beneficial for improving the performance of the solid ion conductive layer. For example, the average pore size can be at most 50 microns, at most 45 microns, at most 40 microns, at most 35 microns, at most 30 microns, at most 25 microns, at most 20 microns, at most 17.5 microns, at most 15 microns, at most 12.5 microns, at most 10 microns, at most 7.5 microns, or at most 5 microns. In another embodiment, the average pore size can be at least 0.1 micron, at least 0.3 micron, at least 0.5 micron, at least 0.7 micron, at least 1 micron, at least 1.5 microns, at least 2 microns, at least 2.5 microns, at least 3 microns, at least 5 microns, at least 7.5 microns, at least 10 microns, at least 12.5 microns, at least 15 microns, at least 17.5 microns, at least 20 microns. In yet another embodiment, the average pore size can include any of the minimum and maximum values mentioned herein.

[0073] In another embodiment, the solid ion conductive layer may comprise at least 50% of the pores having a pore size within ±30% of the average pore size, or within ±25%, or within ±20%, or within ±15%, or within ±10%, or within ±5% of the average pore size. In another instance, at least 60% of the pores have a pore size within ±30% of the average pore size, or within ±25%, or within ±20%, or within ±15%, or within ±10%, or within ±5% of the average pore size. In yet another instance, at least 70%, such as at least 80%, or at least 90%, of the pores have a pore size within ±30% of the average pore size, or within ±25%, or within ±20%, or within ±15%, or within ±10%, or within ±5% of the average pore size.

[0074] In yet another embodiment, the solid ion conducting layer can comprise a specific porosity that can comprise open pores. In one aspect, at least 5% of the total porosity can be open, and at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, or at least 90% of the total porosity can be open. For example, a majority of the pores can comprise open porosity. For example, at least 60% of the total porosity can comprise open pores, such as at least 70%, at least 80%, or at least 90% of the total porosity can comprise open pores. In certain instances, 95% of the porosity or substantially all of the pores can be open pores. In another aspect, up to 95% of the total porosity can be open, and up to 90%, up to 85%, up to 80%, up to 75%, up to 70%, up to 65%, up to 50%, up to 45%, up to 40%, up to 35%, up to 30%, up to 25%, up to 20%, up to 15%, up to 10%, or up to 5% of the total porosity can be open. In addition, the solid ionically conductive layer can include open pores within a range including any of the minimum and maximum percentages mentioned herein. For example, open pores can constitute at least 50% to up to 95% of the total porosity of the solid ionically conductive layer. In another example, the foam matrix can include a similar amount of open pores as the solid ionically conductive layer. In a specific example, the foam matrix can consist essentially of open pores.

[0075] In one embodiment, the ion conductive layer may include closed pores. In one aspect, at least 0.5% of the total porosity may include closed pores. For example, at least 0.5%, at least 1%, at least 3%, at least 4%, or at least 5% of the total porosity may be closed. In another example, at most 10%, at most 8%, at most 6%, at most 4%, at most 3%, at most 2%, or at most 1% of the total porosity may include closed pores. In addition, the solid ion conductive layer may include closed pores within a range including any minimum percentage and maximum percentage mentioned herein. For example, closed pores may constitute at least 0.5% to 10% of the total porosity of the solid ion conductive layer. In another example, the foam matrix may include a similar amount of closed pores as the solid ion conductive layer. In a specific example, the foam matrix may be substantially free of closed pores. In a more specific example, the solid ion conductive layer may be composed of a foam matrix.

[0076] In one embodiment, the solid ion conducting layer may include a first type of porosity and a second type of porosity, wherein the first and second types of porosity may include different pore characteristics including average pore size, pore size distribution, pore orientation, pore content, or a combination thereof.

[0077] In one aspect, the first type porosity can include a first average pore size, and the second type porosity can include a second average pore size, wherein the first average pore size can be larger than the second average pore size. On the other hand, the first type porosity can include a first average pore size of at least 2 microns, at least 3 microns, at least 5 microns, at least 7 microns, at least 10 microns, at least 12 microns, at least 15 microns or at least 17 microns. On the other hand, the first type porosity can include a first average pore size of at most 50 microns, at most 45 microns, at most 40 microns, at most 35 microns, at most 30 microns, at most 25 microns, at most 20 microns, at most 17 microns, at most 15 microns, at most 12 microns, at most 10 microns, at most 7 microns or at most 5 microns. In addition, the first average pore size can be within the range of any minimum and maximum values mentioned herein. For example, the first type pore can have an average pore size of 3 microns to 10 microns.

[0078] In yet another aspect, the first type of porosity can include open porosity, closed porosity, or a combination thereof. In another aspect, the first type of porosity can include open pores. For example, the first porosity can constitute at least 60%, at least 80%, or at least 90% of the open pores of the solid ionically conductive layer. In a specific aspect, the first type of porosity can consist essentially of open pores.

[0079] In one embodiment, the solid ion conductive layer can include a specific amount of first type porosity that can be beneficial for improving the formation and function of the solid ion conductive layer. In one aspect, the first type porosity can constitute at least 1% by volume of the total volume of the ion conductive layer, at least 5% by volume, at least 10% by volume, at least 15% by volume, at least 20% by volume, at least 25% by volume, at least 30% by volume, at least 40% by volume, at least 50% by volume, at least 55% by volume, at least 60% by volume, at least 70% by volume, at least 80% by volume, or at least 90% by volume of the total volume of the ion conductive layer. In another aspect, the first type porosity can constitute at most 95% by volume of the total volume of the ion conductive layer, at most 90% by volume, at most 80% by volume, at most 70% by volume, at most 60% by volume, at most 50% by volume, at most 40% by volume, at most 30% by volume, at most 20% by volume, or at most 10% by volume of the total volume of the ion conductive layer. In one particular aspect, the solid ionically conductive layer can comprise a content of the first type of porosity within a range comprising any of the minimum and maximum percentages mentioned herein. For example, the first type of porosity can comprise 50% to 80% by volume of the total volume of the ionically conductive layer.

[0080] In one particular aspect, the first type of porosity can constitute at least 50% of the total porosity of the solid ion conductive layer, such as at least 60%, at least 70%, at least 80%, or at least 90% of the total porosity. In another aspect, the first type of porosity can constitute at most 95% of the total porosity of the solid ion conductive layer, such as at most 90%, at most 80%, or at most 70% of the total porosity. In yet another aspect, the total porosity can include the first porosity within a range including any minimum and maximum percentages mentioned herein. In more specific aspects, the first porosity can constitute the entire total porosity.

[0081] In one aspect, at least 50% of the pores of the first type of porosity have a pore size within ±30% of the first average pore size, or within ±25%, or within ±20%, or within ±15%, or within ±10%, or within ±5% of the first average pore size. In another instance, at least 60% of the pores of the first type of porosity have a pore size within ±30% of the first average pore size, or within ±25%, or within ±20%, or within ±15%, or within ±10%, or within ±5% of the first average pore size. In yet another instance, at least 70%, such as at least 80% or at least 90%, of the pores of the first type of porosity may have a pore size within ±30% of the first average pore size, or within ±25%, or within ±20%, or within ±15%, or within ±10%, or within ±5% of the first average pore size. The pore size distribution can be determined based on at least 100 pores randomly selected from one or more scanning electron microscopy images of one or more cross-sections of the ion-conducting layer using Image J 1.52a released on April 23, 2018, or a version with similar functionality.

[0082] In one aspect, the first type of porosity independently comprises an aspect ratio of length to width that is at least 1, 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. In another aspect, the first type of porosity can comprise an average aspect ratio that is 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. In yet another aspect, the average aspect ratio of the first type of porosity can be within a range including any of the minimum and maximum values mentioned herein. In yet another aspect, at least 50%, at least 60%, at least 70%, at least 80%, or at least 90% of the pores of the first type of porosity can comprise an aspect ratio of length to width that is at least 1 and at most 3.

[0083] In yet another aspect, the first type of porosity can include pores having a spherical shape. In another aspect, the first type of porosity can include horizontally oriented pores. As used herein, horizontal orientation is intended to describe pores having a longitudinal axis, with the length of the pore extending along the axis, along a plane defined by the x-axis and the y-axis, with the tape / membrane thickness along the z-axis. In certain instances, the first porosity can consist essentially of horizontally oriented pores.

[0084] In certain embodiments, the first type of porosity may consist essentially of pores formed by a foaming reaction. The foaming reaction will be described in detail later in this disclosure.

[0085] In one aspect, the solid ionically conductive layer can include a specific amount of the second type of porosity that can be beneficial for improving the formation and function of the solid ionically conductive layer. In one example, the solid ionically conductive layer can include up to 50% by volume of the total volume of the solid ionically conductive layer, such as up to 48% by volume, up to 45% by volume, up to 40% by volume, up to 37% by volume, up to 35% by volume, up to 30% by volume, up to 28% by volume, up to 25% by volume, up to 20% by volume, up to 18% by volume, up to 15% by volume, up to 12% by volume, up to 10% by volume, up to 8% by volume, or up to 5% by volume of the second type of porosity. In another example, the solid ion conductive layer can include at least 0.5 volume % of the total volume of the solid ion conductive layer, such as at least 1 volume %, at least 2 volume %, at least 3 volume %, at least 4 volume %, at least 5 volume %, at least 8 volume %, at least 10 volume %, at least 12 volume %, at least 15 volume %, at least 17 volume %, or at least 20 volume % of the total volume of the solid ion conductive layer. In yet another example, the solid ion conductive layer can include an amount of the second type of porosity within a range including any of the minimum and maximum values mentioned herein. For example, the solid ion conductive layer can include at least 1 volume % and at most 10 volume % of the second type of porosity of the total volume of the solid ion conductive layer. In a specific aspect, the solid ion conductive layer can be substantially free of the second type of porosity.

[0086] In yet another aspect, the second type of porosity can include open pores, closed pores, or a combination thereof. In a particular aspect, a majority of the pores of the second type of porosity can be open, and in a more specific aspect, the second type of porosity can consist essentially of open porosity.

[0087] In one embodiment, the solid ion conductive layer may include a second type of pores having a specific second average pore size, which may be beneficial to improving the formation and performance of the solid ion conductive layer. In one aspect, the second average pore size may be at most 1 micron, at most 0.8 micron, or at most 0.5 micron. In another aspect, the second average pore size may be at least 0.1 micron, at least 0.2 micron, at least 0.3 micron, or at least 0.5 micron. In a specific aspect, the second average pore size may be within a range including any minimum and maximum values mentioned herein. For example, the second average pore size may be at least 0.3 micron and at most 1 micron.

[0088] In one aspect, the second type of porosity can comprise an average aspect ratio of length to width that is at least 1, 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. In another aspect, the second type of porosity can comprise an average aspect ratio that is 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. In yet another aspect, the second type of porosity can comprise an average aspect ratio within a range including any of the minimum and maximum values mentioned herein. For example, the second type of porosity has an average aspect ratio of at least 1 to at most 5.

[0089] In yet another aspect, the second type of porosity can include spherical pores, irregularly shaped pores, hexahedral pores, elongated pores, tortuous pores, needle-shaped pores, pores having a 3-dimensional structure, or any combination thereof. In certain embodiments, the second type of porosity can include pores formed by the controlled removal of organic material as described in the embodiments herein. In more specific cases, the second type of porosity can consist essentially of pores formed by the controlled removal of organic material.

[0090] refer to Figure 1 , shows a cross-sectional view of an exemplary ion-conducting layer 100 including a foam matrix 101, the foam matrix including a matrix portion 110 comprising a material and an organic material. Foam matrix 101 further comprises a first type of porosity including pores 102 and a second type of porosity including pores 104. Pores 102 are substantially spherical. Pores 102 include spherical pores and pores having other shapes. In certain cases, ion-conducting layer 100 can be substantially free of the second type of porosity. As shown, solid ion-conducting layer 101 can include a thickness t extending in the z-axis direction.

[0091] refer to Figure 2 , an exemplary ion conductive layer 200 may include a foam matrix 201, which includes a matrix portion 210 including an electrolyte material and an organic material. Foam matrix 201 further includes a first type of porosity including pores 202 and a second type of porosity including pores 204. As shown, pores 202 are elongated in a horizontal direction perpendicular to the thickness t of the ion conductive layer. Pores 202 may have a longitudinal axis 220 extending along a plane defined by an x-axis and a y-axis. The orientation of pores 202 may be the direction of extension of longitudinal axis 220. As shown, pores 202 are horizontally oriented. Pores 202 include spherical pores and pores having other shapes. In certain cases, ion conductive layer 200 may be substantially free of the second type of porosity.

[0092] In one embodiment, the solid ion conductive layer may include a foam matrix composed of an electrolyte material and an organic material. In certain cases, the foam matrix may be composed of an electrolyte material and a polymer including polyurethane, epoxy resin, or a combination thereof.

[0093] In one embodiment, the solid ion conductive layer may have a specific thickness that may be advantageous for improving the formation and performance of the solid ion conductive layer. Any solid ion conductive layer mentioned in the embodiments herein may include a thickness such as Figures 1 to 2 In one aspect, the thickness t can be at most 1 mm, at most 800 microns, at most 600 microns, at most 500 microns, at most 400 microns, at most 300 microns, at most 200 microns, or at most 100 microns. In another instance, the thickness t can be at least 5 microns, at least 10 microns, at least 15 microns, at least 20 microns, at least 30 microns, or at least 40 microns. It will be understood that the solid ionically conductive layer can have a thickness t within a range including any minimum and maximum values mentioned therein. For example, the thickness t can be in the range of 20 microns to 300 microns.

[0094] In one embodiment, the solid ion conductive layer can be a composite layer comprising an electrolyte material and an electronically conductive material. The electronically conductive material can include an active electrode material. In another example, the electronically conductive material can include graphite, carbon fibers, carbon particles, carbon nanotubes, or a combination thereof. In certain cases, the ion conductive layer can have a coating comprising an electronically conductive material, such as a metal coating. In another embodiment, the anode can include a solid ion conductive layer and an active anode material disposed on the solid ion conductive layer.

[0095] In one embodiment, the solid ion conductive layer can include a specific ion conductivity that can be beneficial for improving the performance of the ion conductive layer. In one aspect, the solid ion conductive layer can have an ion conductivity suitable for solid-state batteries (such as solid-state lithium-ion batteries).

[0096] refer to Figure 3, shows a cross-sectional view of a solid ion conductive layer 300 comprising a foam matrix 301 containing pores 302. As shown, in certain cases, the ion conductive layer 300 can be a composite layer, such as a mixed ion and electron conductive layer. For example, the solid ion conductive layer 300 can include an electron conductive material 360 dispersed in the foam matrix 301. As shown, the electron conductive material 360 can be disposed in the pores 302. The electron conductive material can include an active electrode material, an electron conductive agent, or a combination thereof. In one embodiment, the solid ion conductive layer 300 can include an active anode material 360 disposed in the foam matrix 301. In certain cases, the active anode material can include lithium metal, lithium titanate, or graphite. The foam matrix 301 can include a matrix portion comprising an electrolyte material and an organic material (not shown). In an embodiment, the pores 302 can be a first type of porosity. The second type of porosity is not shown. In another embodiment, the solid ion conductive layer can consist essentially of the first type of porosity and the electrolyte material.

[0097] In certain embodiments, the anode may include Figure 3 The solid ion conducting layer 300 is shown. In another embodiment, the anode may include Figure 1 and Figure 2 1 or 2. The solid ion conductive layer 100 or 200 shown respectively. In certain cases, the anode can be a 3-dimensional structure. It is worth noting that the solid ion conductive layer described in the embodiments herein can be beneficial to improve the formation and performance of the anode. For example, when the anode as described in the embodiments herein is filled with Li metal, the anode can have a specific energy density of at least 650 mAh / g, at least 700 mAh / g, at least 750 mAh / g, at least 800 mAh / g, at least 850 mAh / g or at least 900 mAh / g.

[0098] In another embodiment, a solid ion conducting layer can be advantageous for improving the formation and performance of a solid state battery. In one aspect, a solid state battery can include a solid ion conducting layer, such as Figure 1 The layer 100 shown, Figure 2 200 as shown. Or Figure 3 300 shown. In one particular aspect, the solid-state battery can be a solid-state lithium-ion battery. In another particular aspect, the solid-state battery can include an anode comprising Figure 3 Composite layer 300 is shown.

[0099] In yet another aspect, the solid-state battery can have an energy density of at least 700Wh / L, at least 750Wh / L, at least 800Wh / L, or at least 850Wh / L. In another aspect, the solid-state battery can have an energy density of at least 250Wh / kg, at least 300Wh / kg, at least 350Wh / kg, or at least 400Wh / kg.

[0100] Energy density can be measured in coin cell tests by controlling the electrolyte / binder solid loading (g) on the anode and then measuring the charge / discharge capacity electrochemically. When all Li ions are placed at the cathode in the initial state, after charging, the Li metal weight at the anode can be calculated from the charge capacity (mAh) using the Li metal electrochemical capacity of 3860 mAh / g.

[0101] In another embodiment, the ion conductive layer may include an active cathode material. For example, the active electrode material 360 may be Figure 3 The active cathode material may include a lithium-containing oxide, a transition metal fluoride, a polyanion material, a fluorinated polyanion material, a transition metal sulfide, a transition metal oxyfluoride, a transition metal oxysulfide, a transition metal oxynitride, or any combination thereof. Specific exemplary cathode materials may include LiCoO2, LiFePO4, Li(NiCoAl)O2, LiMnPO4, LiMn2O4, LiNi 1 / 3 Co 1 / 3 Mn 1 / 3 O2 or any combination thereof.

[0102] Figure 4 4. The multilayer structure 400 includes a porous solid ion-conducting layer 401 including pores 402 and 404, which covers another ion-conducting layer 420. The ion-conducting layer 420 can be dense. For example, the ion-conducting layer 420 can have a porosity of at most 5% by volume of the total volume of the ion-conducting layer 420. The solid ion-conducting layer 401 can be similar to Figure 1 The ion conductive layer 100 or Figure 2 200 as shown, or including any of the features described in the embodiments herein. For example, ion conductive layer 401 may include a foam matrix 410 including a first type of porosity including pores 402 and a second type of porosity including pores 404. In one embodiment, the multilayer structure may form part of a solid-state battery. In an exemplary application, dense ion conductive layer 420 may be an electrolyte, and porous ion conductive layer 401 may be a scaffold or skeleton structure for an electrode layer.

[0103] Figure 5An illustration of a portion of a solid-state battery 500 comprising Figure 3 Ionically conductive layer 300 is shown covering layer 520. In certain instances, layer 520 can be an electrolyte. In another certain instance, ionically conductive layer 300 can include electronically conductive material 360 disposed in foam matrix 301.

[0104] refer to Figure 6 , showing a multilayer structure 600. The multilayer structure 600 may include an ion conductive layer 620 similar to Figure 5 520 or Figure 4 420. The porous solid ion conductive layers 601 and 610 may include pores 602 and 612, and are similar to those shown in FIG. Figure 1 、 Figure 2 and Figure 4 Any of the solid ion conductive layers 100, 200 or 401 shown respectively. Porous solid ion conductive layers 601 and 610 may include any of the features described with respect to the solid ion conductive layers of the embodiments herein. For example, each of ion conductive layers 601 and 610 may include a foam matrix including pores 602 and 612, respectively. In certain cases, ion conductive layers 601 and 610 may include pore characteristics that are different from each other, including porosity, average pore size, pore size standard deviation, pore orientation, aspect ratio, or a combination thereof. In more specific cases, pores 602 and 612 may form a gradient porosity having a varying pore size, pore content, aspect ratio, pore orientation, or any combination thereof. For example, the average pore size, pore content, or a combination thereof may increase in a direction extending away from ion conductive layer 620. In another example, as shown, pore 612 may have an average pore size larger than pore 602. In yet another example, ion conductive layer 611 can include a higher content of pores 612 compared to the content of pores 602 in ion conductive layer 601. In another case, multi-layer structure 600 can have additional layers.

[0105] refer to Figure 7 , an exemplary process 700 is shown. Process 700 may include forming a mixture at block 702, the mixture having a composition comprising an electrolyte material and a foaming agent, wherein the electrolyte material may include a hygroscopic material, such as a halide-based material, a sulfide-based material, or a combination thereof. The composition may further include an organic material precursor and a cross-linking agent. The composition may optionally include a binder material, a dispersant, a plasticizer, and / or a homogenizer. In some cases, the mixture may further include a lithium salt, an organic electrolyte material, and / or an electronically conductive material, such as a cathode material or an anode material.

[0106] The ingredients may be added in any suitable order for forming a homogeneous mixture, and mixing aids (eg, mixing agents) may be used to facilitate mixing.

[0107] The components of the composition may not react with hygroscopic materials. For example, each of the organic material precursor, crosslinking agent, blowing agent, and binder material may be hydrophobic. In another example, each of the organic material precursor, crosslinking agent, blowing agent, and binder material may have an HLB value, moisture absorption rate, reactivity value, or any combination thereof as described in the embodiments herein.

[0108] Exemplary organic material precursors may include resins, polymers, prepolymers, monomers, or combinations thereof. The organic material precursor may be formed into an organic material, such as a polymer. In the presence of a blowing agent and a cross-linking agent, the organic material precursor may also undergo a foaming reaction to form a foam matrix. A specific example of an organic material precursor may include an epoxy resin, a polyol, or a combination thereof.

[0109] Examples of foaming systems may include a hydrophobic polyol, a cross-linking agent, and a blowing agent, wherein the cross-linking agent includes isocyanate 370, hexamethylene diisocyanate (HDI), isophorone diisocyanate, a hydrophobic polyisocyanate, or any combination thereof, and the blowing agent is such as cyclopentane, pentane, isopentane, diphenylmethane diisocyanate, or any combination thereof.

[0110] Another example of a foaming system may include an epoxy resin, a crosslinker including an amine or a thiol, and a forming agent such as pentane.

[0111] In exemplary embodiments, the composition may include at least 50 wt % to at most 85 wt % of an electrolyte material, at least 2 wt % to at most 10 wt % of a blowing agent, at least 5 wt % to at most 20 wt % of an organic material precursor, and at least 5 wt % to at most 20 wt % of a cross-linking agent, based on the total weight of the composition.

[0112] Said composition can also comprise solvent, and this mixture can be formed into slurry or colloidal suspension.Solvent may not react with hygroscopic material.For example, solvent can have HLB value, moisture absorption rate, reactivity value or their arbitrary combination as mentioned in the embodiments of this paper.Exemplary solvent can comprise toluene, pentene, dimethylbenzene, hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, cycloundecane, cyclododecane, isobutyl isobutyrate, dimethyl carbonate, dimethyl sulfide etc.

[0113] In a particular embodiment, one or more binders can be mixed in the slurry to facilitate the formation and performance of the ion conductive layer. Exemplary binders can include one or more materials selected from the group consisting of paraffin wax, polyisobutylene, polyvinyl pyrrolidone, poly(methyl methacrylate), polyethylene glycol, camphene, urea, poly(acrylonitrile), polyethylene carbonate, polyvinyl chloride, poly(ethylene oxide), poly(propylene oxide), poly(vinylidene fluoride), poly(dimethylsiloxane), poly[bis(methoxyethoxyethanol salt)-phosphazene], polypropylene glycol, polycaprolactone and poly(trimethylene carbonate), poly(methyl acrylate), poly(vinylidene fluoride)-to-hexafluoropropylene, poly(acrylonitrile-to-butadiene), poly(styrene-butadiene-styrene) and styrene-ethylene-butylene-styrene, hydrogenated nitrile rubber, high density polyethylene, low density polyethylene, poly(ethylene oxide), polystyrene and polyurethane, or any combination thereof.

[0114] Process 700 may include forming a green layer at frame 704. In one example, forming a green layer may include processing the mixture by casting, coating, printing, binder injection, extrusion, compacting, calendering, pressing or any combination thereof. In particular, the green layer may be in the form of a band or film. The green layer may include any thickness mentioned in the embodiments herein. In particular, the embodiment forming the green ion conductive layer may include tape casting, such as blade coating or scraping. Tape casting may be performed under dry conditions (e.g., in a drying chamber or glove box). In another specific embodiment, the mixture may be extruded to form a film or band to form a green layer.

[0115] Process 700 may include forming an ionically conductive layer comprising a foam matrix and an electrolyte material at block 706. In one embodiment, process 700 may include performing a foaming reaction to form a foam matrix comprising an organic material formed from an organic material precursor. In certain instances, foaming may be performed within a film or tape. In another embodiment, process 700 may include forming a film or tape while simultaneously controlling the thickness and porosity of the film or tape. In particular, foaming may be performed while the thickness of the green layer is limited.

[0116] refer to Figures 8A to 8B , a green layer 810 is cast on a substrate 801 without limitation, and a foam layer 820 may have pores 822 and a thickness t1. Figure 8C and Figure 8D As shown, a similar green layer 830 can be formed into a foam layer 840 having pores 842 and a thickness t2 when the thickness of the green layer is limited, for example, by means of a fixture or mold 802. As shown, the pores 842 can have a different orientation than the pores 822. The thickness t2 can be less than t1.

[0117] In an exemplary embodiment, the foaming reaction can be performed at a temperature of at least 20°C to 100°C. In yet another example, extrusion and foaming can be performed continuously. In another example, foaming can be performed at a temperature higher than the extrusion temperature. In a specific example, extrusion and foaming can be performed in a single mold equipped with zoned temperature and thickness control.

[0118] refer to Figure 9 , shows an exemplary continuous process. Mixture 901 can be extruded at region 910 to form green layer 902. Green layer 902 can be heated at region 920 to perform a foaming reaction under thickness constraints to form foam green layer 903. Foam green layer 903 can then be cooled at region 940. In certain cases, this process can be performed in a mold.

[0119] In another embodiment, process 700 may include forming multiple green layers. For example, a first green layer may be formed, and a second green layer may be formed overlying the first green layer. The first green layer may include the mixture. The second green layer may include an electrolyte material, which may be the same as or different from the electrolyte material in the mixture of block 702. In an exemplary embodiment, tape casting may be used to form each green layer. In a specific embodiment, the green layers may 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 overlying the first and / or second green layers. In another example, multiple layers may be coextruded to form a multilayer structure.

[0120] In another case, one or more green layers can be dried to form one or more layers that are ultimately formed, such as a porous solid ion conductive layer, an electrolyte layer, or a multilayer structure comprising a combination thereof. Drying can be performed at room temperature, or performed with the application of heat. In yet another case, the mixture in the green layer can be cured at a temperature of 20°C to 160°C. In certain cases, the curing temperature can be higher than the foaming temperature. For example, epoxy resin can be cured at a temperature higher than the foaming temperature. After reading this disclosure, those skilled in the art will understand that the crosslinking temperature (e.g., the curing temperature of epoxy resin) can be controlled by selecting an organic material precursor (e.g., an epoxy compound) and a crosslinking agent. In yet another case, a multilayer structure comprising a first ion conductive layer covering a second ion conductive layer can be formed.

[0121] In a particular embodiment, heat can be applied to the first green layer to facilitate removal of the binder material. In particular cases, heating the first green layer can include removing one or more binder materials. In particular aspects, 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, polyisobutylene, polyvinyl pyrrolidone, poly (methyl methacrylate), polyethylene glycol, camphene, urea, poly (acrylonitrile), polyethylene carbonate, polyvinyl chloride, poly (ethylene oxide) or a combination thereof. In particular cases, heating can include a heating temperature and / or a heating time that can facilitate formation of a second type of porosity. Exemplary heating temperatures can include the evaporation temperature of the binder material. In another case, the heating temperature can include 30° C. to 200° C. In yet another case, the heating time can be 2 minutes to 120 minutes.

[0122] Many different aspects and embodiments are feasible. Some of those aspects and embodiments are described herein. 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 invention. Embodiments can be based on any one or more of the embodiments listed below.

[0123] Example

[0124] Example 1. A solid ionically conductive layer comprising a foam matrix containing an electrolyte material comprising a hygroscopic material.

[0125] Embodiment 2. The solid ion-conducting layer of embodiment 1, comprising a total porosity of at least 30 volume %, at least 40 volume %, at least 50 volume %, at least 60 volume %, at least 70 volume % or at least 80 volume % of the total volume of the solid ion-conducting layer.

[0126] Embodiment 3. A solid ion conducting layer according to embodiment 1 or 2, comprising a total porosity of at most 95 volume %, at most 90 volume %, at most 85 volume %, at most 80 volume %, at most 75 volume %, at most 70 volume %, at most 65%, at most 60%, at most 55% or at most 50%.

[0127] Embodiment 4. The solid ion conducting layer of any one of embodiments 1 to 3, comprising a thickness of at most 1 mm, at most 800 microns, at most 600 microns, at most 500 microns, at most 400 microns, at most 300 microns, at most 200 microns, or at most 100 microns.

[0128] Embodiment 5. The ionically conductive layer of any one of embodiments 1 to 4, comprising a thickness of at least 5 micrometers, at least 10 micrometers, at least 15 micrometers, at least 20 micrometers, at least 30 micrometers, or at least 40 micrometers.

[0129] Embodiment 6. The ionically conductive layer of any one of embodiments 1 to 5, wherein the electrolyte material comprises a bulk ionic conductivity 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.

[0130] Embodiment 7. An ionically conductive layer according to any one of embodiments 1 to 6, wherein the electrolyte material comprises a bulk ionic conductivity of at most 50 mS / cm, at most 45 mS / cm, at most 40 mS / cm, at most 35 mS / cm, at most 30 mS / cm, at most 29 mS / cm, at most 25 mS / cm, at most 20 mS / cm, at most 15 mS / cm, at most 10 mS / cm, at most 5 mS / cm, at most 3 mS / cm, at most 2 mS / cm, or at most 1 mS / cm.

[0131] Embodiment 8. The ionically conductive layer of any one of embodiments 1 to 7, comprising an organic material including a polymer, wherein the polymer does not react with the electrolyte material.

[0132] Embodiment 9. An ion-conducting layer according to any one of embodiments 1 to 8, comprising an organic material including a polymer, wherein the polymer has an HLB number of 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.

[0133] Embodiment 10. An ion-conducting layer according to any one of embodiments 1 to 9, comprising an organic material including a polymer, wherein the polymer has a moisture absorption rate of at most 1.0 wt%, such as at most 0.8 wt%, at most 0.5 wt%, at most 0.3 wt% or at most 0.1 wt%.

[0134] Embodiment 11. An ion-conducting layer according to any one of embodiments 1 to 10, comprising an organic material including a polymer, wherein the polymer has a reactivity value of at most 10%, such as 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%.

[0135] Embodiment 12. An ion-conducting layer according to any one of embodiments 1 to 11, comprising an organic material comprising paraffin, polyisobutylene, polyvinyl pyrrolidone, poly(methyl methacrylate), polyethylene glycol, camphene, urea, poly(acrylonitrile), polyethylene carbonate, polyvinyl chloride, poly(ethylene oxide), or any combination thereof.

[0136] Embodiment 13. An ion-conducting layer according to any one of embodiments 1 to 12, comprising an organic material selected from the group consisting of: poly(propylene oxide), poly(vinylidene fluoride), poly(dimethylsiloxane), poly[bis(methoxyethoxyethanolate)-phosphazene], polypropylene glycol, polycaprolactone and poly(trimethylene carbonate), poly(methyl acrylate), poly(vinylidene fluoride)-co-hexafluoropropylene, poly(acrylonitrile-co-butadiene), poly(styrene-butadiene-styrene) and styrene-ethylene-butylene-styrene, hydrogenated nitrile rubber, high-density polyethylene, low-density polyethylene, poly(ethylene oxide), polystyrene and polyurethane, or any combination thereof.

[0137] Embodiment 14. An ion-conducting layer according to any one of embodiments 1 to 13, comprising an organic material, wherein the content of the organic material is at most 50 volume %, at most 45 volume %, at most 40 volume %, at most 35 volume %, at most 30 volume %, at most 28 volume %, at most 25 volume %, at most 20 volume %, at most 15 volume %, at most 10 volume % or at most 5 volume % of the total volume of the solid ion-conducting layer.

[0138] Embodiment 15. An ion-conducting layer according to any one of embodiments 1 to 14, comprising an organic material, wherein the content of the organic material is at least 0.5 volume % of the total volume of the solid ion-conducting layer, at least 1 volume %, at least 2 volume %, at least 3 volume %, at least 4 volume %, at least 5 volume %, at least 6 volume %, at least 7 volume %, at least 8 volume %, at least 9 volume %, at least 10 volume %, at least 12 volume % or at least 15 volume % of the total volume of the solid ion-conducting layer.

[0139] Embodiment 16. The ion-conducting layer of any one of embodiments 1 to 15, wherein the foam matrix comprises V E :V O The ratio of V O is the volume percentage of the organic material relative to the total volume of the solid ion conductive layer, and V E is the volume percentage of the electrolyte material relative to the total volume of the solid ionically conductive layer, wherein the ratio is at least 0.5, at least 1, at least 1.5, at least 2, at least 2.5, or at least 3.

[0140] Embodiment 17. The ionically conductive layer of embodiment 16, wherein the ratio is at most 10, at most 9, at most 8, at most 7, at most 6, at most 5, at most 4, or at most 3.

[0141] Embodiment 18. The ionically conductive layer of any one of embodiments 1 to 17, comprising an organic material comprising a polymer comprising an epoxy, a polyurethane, a poly(ethylene oxide), or a combination thereof.

[0142] Embodiment 19. The ion-conducting layer of any one of embodiments 1 to 18, comprising at least 1 volume percent, at least 2 volume percent, at least 4 volume percent, at least 5 volume percent, at least 8 volume percent, at least 10 volume percent, at least 12 volume percent, at least 15 volume percent, at least 18 volume percent, at least 20 volume percent, at least 25 volume percent, at least 30 volume percent, or at least 35 volume percent of the total volume of the ion-conducting layer.

[0143] Embodiment 20. The ion-conducting layer of any one of embodiments 1 to 19, comprising up to 50 volume percent of the total volume of the ion-conducting layer, up to 45 volume percent, up to 42 volume percent, up to 40 volume percent, up to 38 volume percent, or up to 35 volume percent of the total volume of the ion-conducting layer.

[0144] Embodiment 21. An ionically conductive layer according to any one of embodiments 1 to 20, comprising at least 1 volume percent, at least 2 volume percent, at least 4 volume percent, at least 5 volume percent, at least 8 volume percent, at least 10 volume percent, at least 12 volume percent, at least 15 volume percent, at least 18 volume percent, at least 20 volume percent, at least 25 volume percent, at least 30 volume percent, or at least 35 volume percent of the total volume of the ionically conductive layer.

[0145] Embodiment 22. An ionically conductive layer according to any one of embodiments 1 to 21, comprising up to 50 volume % of the total volume of the ionically conductive layer, up to 45 volume %, up to 42 volume %, up to 40 volume %, up to 38 volume % or up to 35 volume % of the total volume of the ionically conductive layer.

[0146] Embodiment 23. The ionically conductive layer of any one of embodiments 1 to 22, wherein the electrolyte material is embedded in a foam matrix.

[0147] Embodiment 24. The ionically conductive layer of any one of embodiments 1 to 23, further comprising a lithium salt dispersed in the foam matrix, wherein the lithium salt comprises LiPF6, LiClO4, LiBF4, LiAsF6, LiTf, LiSA, LiFSI, LiTFSI, LiBETI, LiCTFSI, LiBOB, LiTDI, LiPDI, LiDCTA, LiB(CN)4, LiPF6, LiBF4, LiSbF6, LiAsF6, LiSO3CF3, LiN(SO2CF3)2, LiN(SO2C2F5)2, LiN(SO2CF3)(SO2C4F9), LiC(SO2CF3)3, or a combination thereof.

[0148] Embodiment 25. An ionically conductive layer according to any one of embodiments 1 to 24, comprising an average pore size of at most 50 microns, at most 45 microns, at most 40 microns, at most 35 microns, at most 30 microns, at most 25 microns, at most 20 microns, at most 17.5 microns, at most 15 microns, at most 12.5 microns, at most 10 microns, at most 7.5 microns, or at most 5 microns.

[0149] Embodiment 26. An ionically conductive layer according to any one of embodiments 1 to 25, comprising an average pore size of at least 0.1 micrometer, at least 0.3 micrometer, at least 0.5 micrometer, at least 0.7 micrometer, at least 1 micrometer, at least 1.5 micrometer, at least 2 micrometers, at least 2.5 micrometers, at least 3 micrometers, at least 5 micrometers, at least 7.5 micrometers, at least 10 micrometers, at least 12.5 micrometers, at least 15 micrometers, at least 17.5 micrometers, at least 20 micrometers, at least 22 micrometers, at least 25 micrometers, at least 30 micrometers, at least 33 micrometers, at least 35 micrometers, at least 38 micrometers, at least 40 micrometers, at least 42 micrometers, at least 45 micrometers, at least 47 micrometers, or at least 50 um.

[0150] Embodiment 27. The ionically conductive layer of any one of embodiments 1 to 26, comprising a total porosity comprising open pores, closed pores, or a combination thereof.

[0151] Embodiment 28. An ion-conducting layer according to embodiment 27, wherein at least 5% of the pores of the total porosity are open, and at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80% or at least 90% of the pores of the total porosity are open.

[0152] Embodiment 29. An ionically conductive layer according to embodiment 27 or 28, wherein at most 95% of the pores of the total porosity are open, at most 90%, at most 85%, at most 80%, at most 75%, at most 70%, at most 65%, at most 50%, at most 45%, at most 40%, at most 35%, at most 30%, at most 25%, at most 20%, at most 15%, at most 10% or at most 5% of the pores of the total porosity are open.

[0153] Embodiment 30. The ionically conductive layer of any one of embodiments 27-28, wherein the total porosity consists essentially of open pores.

[0154] Embodiment 31. The ionically conductive layer of any one of embodiments 27 to 29, wherein at least 0.5% of the pores of the total porosity are closed, at least 1%, at least 3%, at least 4%, or at least 5% of the pores of the total porosity are closed.

[0155] Embodiment 32. An ionically conductive layer according to embodiment 31, wherein at most 10% of the total porosity is closed, and at most 8%, at most 6%, at most 4%, at most 3%, at most 2% or at most 1% of the pores of the total porosity are closed.

[0156] Embodiment 33. An ion-conducting layer according to any one of embodiments 1 to 32, comprising a first type of porosity and a second type of porosity, wherein the first and second types of porosity comprise different pore characteristics, the pore characteristics comprising an average pore size, a pore size distribution, a pore orientation, a pore content, or a combination thereof.

[0157] Embodiment 34. The ionically conductive layer of Embodiment 33, wherein the first type of porosity comprises a first average pore size and the second type of porosity comprises a second average pore size, wherein the first average pore size is larger than the second average pore size.

[0158] Embodiment 35. The ionically conductive layer of Embodiment 33 or 34, wherein the first type of porosity comprises open porosity, closed porosity, or a combination thereof.

[0159] Embodiment 36. The ionically conductive layer of embodiment 35, wherein the first type of porosity consists of open pores.

[0160] Embodiment 37. An ion-conducting layer according to any one of Embodiments 33 to 36, wherein the first type of porosity constitutes at least 1 volume percent of the total volume of the ion-conducting layer, at least 5 volume percent, at least 10 volume percent, at least 15 volume percent, at least 20 volume percent, at least 25 volume percent, at least 30 volume percent, at least 40 volume percent, at least 50 volume percent, at least 55 volume percent, at least 60 volume percent, at least 70 volume percent, at least 80 volume percent, or at least 90 volume percent of the total volume of the ion-conducting layer.

[0161] Embodiment 38. An ion-conducting layer according to any one of Embodiments 33 to 37, wherein the first type of porosity constitutes at most 95 volume % of the total volume of the ion-conducting layer, at most 90 volume %, at most 80 volume %, at most 70 volume %, at most 60 volume %, at most 50 volume %, at most 40 volume %, at most 30 volume %, at most 20 volume % or at most 10 volume % of the total volume of the ion-conducting layer.

[0162] Embodiment 39. An ionically conductive layer according to any one of Embodiments 33 to 38, wherein the first type of porosity comprises a first average pore size of at least 2 microns, at least 3 microns, at least 5 microns, at least 7 microns, at least 10 microns, at least 12 microns, at least 15 microns, or at least 17 microns.

[0163] Embodiment 40. An ionically conductive layer according to any one of Embodiments 33 to 39, wherein the first type porosity comprises a first average pore size of at most 50 microns, at most 45 microns, at most 40 microns, at most 35 microns, at most 30 microns, at most 25 microns, at most 20 microns, at most 17 microns, at most 15 microns, at most 12 microns, at most 10 microns, at most 7 microns, or at most 5 microns.

[0164] Embodiment 41. The ionically conductive layer of any one of Embodiments 33 to 40, wherein the second type of porosity comprises open pores, closed pores, or a combination thereof.

[0165] Embodiment 42. The ionically conductive layer of Embodiment 41, wherein the second type of porosity consists essentially of open porosity.

[0166] Embodiment 43 The ionically conductive layer of any of Embodiments 33 to 42, wherein the second type of pores comprises a second average pore size of at most 1 micrometer, at most 0.8 micrometers, or at most 0.5 micrometers.

[0167] Embodiment 44. The ionically conductive layer of any of Embodiments 33 to 43, wherein the second type of pores comprises a second average pore size of at least 0.1 micrometers, at least 0.2 micrometers, at least 0.3 micrometers, or at least 0.5 micrometers.

[0168] Embodiment 45. An ion-conducting layer according to any one of Embodiments 33 to 44, wherein the second type of porosity constitutes at least 1 volume percent of the total volume of the ion-conducting layer, at least 2 volume percent, at least 3 volume percent, at least 4 volume percent, at least 5 volume percent, at least 6 volume percent, at least 7 volume percent, at least 8 volume percent, at least 9 volume percent, at least 10 volume percent, at least 12 volume percent, or at least 15 volume percent of the total volume of the ion-conducting layer.

[0169] Embodiment 46. An ion-conducting layer according to any one of Embodiments 33 to 45, wherein the second type of porosity constitutes at most 30 volume % of the total volume of the ion-conducting layer, at most 28 volume %, at most 25 volume %, at most 23 volume %, at most 20 volume %, at most 18 volume %, at most 15 volume %, at most 12 volume %, at most 10 volume %, at most 8 volume %, at most 7 volume %, at most 6 volume %, at most 5 volume %, at most 4 volume % or at most 3 volume % of the total volume of the ion-conducting layer.

[0170] Embodiment 47. An ion-conducting layer according to any one of Embodiments 27 to 46, wherein at least 50%, at least 60%, at least 70%, at least 80% or at least 90% of the pores of the total porosity have a pore size within ±30% of the average pore size, within ±25% of the average pore size, within ±20% of the average pore size, within ±15% of the average pore size, or within ±10% of the average pore size, within ±5% of the average pore size.

[0171] Embodiment 48. An ion-conducting layer according to any one of Embodiments 33 to 47, wherein at least 50%, at least 60%, at least 70%, at least 80% or at least 90% of the pores of the first type of porosity have a pore size within ±30% of the first average pore size, within ±25% of the first average pore size, within ±20% of the first average pore size, within ±15% of the first average pore size, within ±10% of the first average pore size, within ±5% of the first average pore size.

[0172] Embodiment 49. An ionically conductive layer according to any one of Embodiments 33 to 48, wherein the pores of the first and second types of porosity independently comprise a length:width aspect ratio of at least 1, 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.

[0173] Embodiment 50. The ion-conducting layer of embodiment 49, wherein the average aspect ratio is 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.

[0174] Embodiment 51. The ionically conductive layer of any one of Embodiments 33 to 50, wherein the first porosity comprises horizontally oriented pores.

[0175] Embodiment 52. The ionically conductive layer of any one of Embodiments 33 to 51, wherein the first porosity consists essentially of horizontally oriented pores.

[0176] Embodiment 53. The ionically conductive layer of any one of embodiments 1 to 52, wherein the foam matrix is composed of an electrolyte material and a polymer comprising polyurethane, epoxy resin, or a combination thereof.

[0177] Embodiment 54. The solid ionically conductive layer of any one of embodiments 1 to 53, wherein the electrolyte material comprises a halide-based material, a sulfide-based material, or a combination thereof.

[0178] Embodiment 55. The solid ion conducting layer of embodiment 54, wherein the halide-based material comprises M 3-δ (Me k+ ) f X 3-δ+k*f , wherein -3≤δ<3, 0≤f≤1, k is the valence of Me, 2≤k<6, M includes an alkali metal element, Me includes a metal element different from M, and X includes a halogen.

[0179] Embodiment 56. The solid ion conductive layer of embodiment 54, wherein the electrolyte material comprises a lithium halide, a lithium oxyhalide, a lithium halide hydroxide, or a combination thereof having an antiperovskite structure.

[0180] Example 57. The solid ion conductive layer according to Example 56, wherein the electrolyte material comprises Li3OCl, Li3OBr, Li3O(Cl, Br), Li3OCl 0.5 Br 0.5 , Li2OHX, Li2OHCl, Li2OHBr or a combination thereof.

[0181] Embodiment 58. A solid ion conductive layer according to embodiment 54, wherein the sulfide comprises xLi2S-yP2S5 (LPS), including 0.67Li2S-0.33P2S5, 80Li2S-20P2S5, 75Li2S-25P2S5 or 70Li2S-30P2S5, Li2S—X, wherein X represents at least one sulfide of SiS2, GeS2 and B2S3, including 0.50Li2S–0.50GeS2, LiI-Li2S-SiS2, including 0.40LiI–0 .36Li2S–0.24SiS2, 0.05Li4SiO4–0.57Li2S–0.38SiS2, Li3PO4-Li2S-SiS2, including 0.01Li3PO4–0.63Li2S–0.36SiS2, LiI-Li2S-B2S3, including 0.44LiI–0.30Li2S–0.26B2S3, LiI-Li2S-P2S5, including 0.45LiI–0.37Li2S–0.18P2S5, a-Li3PS4, Li 10 GeP2S 12 , Li6PS5Cl, Li6PS5Br, 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.

[0182] Embodiment 59. An ionically conductive layer according to any one of embodiments 1 to 58, comprising at least 5 volume % of the total volume of the ionically conductive layer, at least 7 volume %, at least 9 volume %, at least 10 volume %, at least 12 volume %, at least 15 volume %, at least 17 volume %, at least 19 volume %, at least 20 volume %, at least 25 volume %, at least 27 volume % or at least 30 volume % of the total volume of the ionically conductive layer.

[0183] Embodiment 60. An ionically conductive layer according to any one of embodiments 1 to 59, comprising up to 60 volume %, up to 58 volume %, up to 55 volume %, up to 50 volume %, up to 48 volume %, up to 45 volume %, up to 42 volume %, up to 40 volume %, up to 38 volume %, up to 35 volume %, up to 30 volume %, up to 28 volume %, up to 25 volume %, up to 20 volume %, up to 15 volume %, up to 10 volume % or up to 5 volume % of the total volume of the ionically conductive layer.

[0184] Embodiment 61. The ionically conductive layer of any one of Embodiments 1 to 60, further comprising lithium metal dispersed in the foam matrix.

[0185] Embodiment 62. An anode comprising the ionically conductive layer of embodiment 61, wherein when the anode is saturated with Li metal, the anode has a gravimetric energy density of at least 650 mAh / g, at least 700 mAh / g, at least 750 mAh / g, at least 800 mAh / g, at least 850 mAh / g, or at least 900 mAh / g.

[0186] Embodiment 63. A battery comprising the ionically conductive layer of any one of embodiments 1 to 60.

[0187] Embodiment 64. A battery comprising the anode according to embodiment 62.

[0188] Embodiment 65. A battery according to embodiment 63 or 64, comprising an energy density of at least 600 Wh / L, at least 650 Wh / L, at least 700 Wh / L, at least 750 Wh / L, at least 800 Wh / L, or at least 850 Wh / L.

[0189] Embodiment 66. A battery according to Embodiment 63 or 64 comprising an energy density of at least 250 Wh / kg, at least 300 Wh / kg, at least 350 Wh / kg, or at least 400 Wh / kg.

[0190] Example 67. A multilayer structure comprising

[0191] a first ion-conducting layer having a porosity of less than 5 volume percent of the total volume of the first ion-conducting layer; and

[0192] a second ion-conducting layer covering the first ion-conducting layer,

[0193] The second ion-conducting layer comprises at least one ion-conducting layer according to any one of embodiments 1 to 61.

[0194] Embodiment 68. The multilayer structure of embodiment 67, wherein the at least one ion conductive layer comprises a plurality of ion conductive layers, wherein the plurality of ion conductive layers comprise different pore characteristics comprising porosity, average pore size, or a combination thereof.

[0195] Embodiment 69. The multilayer structure of Embodiment 68, wherein the second ion-conducting layer comprises a graded porosity comprised of pores of the plurality of ion-conducting layers.

[0196] Embodiment 70 The multi-layer structure of Embodiment 68, wherein the second ionically conductive layer comprises an increasing average pore size, an increasing porosity, or a combination thereof in a direction extending away from the first ionically conductive layer.

[0197] Embodiment 71. A composition comprising a solid electrolyte material comprising a hygroscopic material and a foaming agent.

[0198] Embodiment 72. The composition of embodiment 71, further comprising an organic material precursor, wherein the organic material precursor is hydrophobic.

[0199] Embodiment 73. The composition of embodiment 71 further comprising an organic material precursor having an HLB value of at most 5, a reactivity value of at most 10%, a MAR of at most 1.0 wt %, or a combination thereof.

[0200] Embodiment 74. The composition of embodiment 72 or 73, wherein the organic material precursor comprises an epoxy resin, a polyol, or a combination thereof.

[0201] Embodiment 75. The composition of any one of embodiments 71 to 74, further comprising a crosslinker comprising an HLB value of at most 5, a reactivity value of at most 10%, a MAR of at most 1.0 wt %, or a combination thereof.

[0202] Embodiment 76. The composition of embodiment 75, wherein the crosslinker comprises isocyanate 370, hexamethylene diisocyanate (HDI), isophorone diisocyanate, a hydrophobic polyisocyanate, an amine, a thiol, or a combination thereof.

[0203] Embodiment 77. The composition of any one of embodiments 71 to 76, wherein the blowing agent comprises cyclopentane, pentane, isopentane, diphenylmethane diisocyanate.

[0204] Embodiment 78. The composition of any of Embodiments 71 to 77, comprising at least 50 wt% and at most 85 wt% electrolyte material, based on the total weight of the composition.

[0205] Embodiment 79. The composition of any one of Embodiments 71 to 78, wherein the electrolyte material comprises a halide-based material, a sulfide-based material, or a combination thereof.

[0206] Embodiment 80. The composition of any one of embodiments 71 to 79, comprising at least 2 wt% and at most 10 wt% of a blowing agent, based on the total weight of the composition.

[0207] Embodiment 81. The composition of any one of embodiments 71 to 80, comprising at least 5 wt% and at most 20 wt% of an organic material precursor, based on the total weight of the composition.

[0208] Embodiment 82. The composition of any one of embodiments 71 to 81 comprising at least 5 wt% and at most 20 wt% of a crosslinker, based on the total weight of the composition.

[0209] Embodiment 83. A slurry comprising the composition of any one of embodiments 71 to 82.

[0210] Embodiment 84. A colloidal suspension comprising the composition of any one of embodiments 71 to 82.

[0211] Example 85. A method comprising:

[0212] forming a mixture comprising an electrolyte material and a blowing agent, the electrolyte material comprising a hygroscopic material; and

[0213] A foam matrix is formed from the mixture.

[0214] Embodiment 86. The method of embodiment 85, wherein the mixture further comprises an organic material precursor and a cross-linking agent.

[0215] Embodiment 87. The method of embodiment 85 or 86, further comprising performing a foaming reaction that forms a foam matrix comprising an organic material formed from an organic material precursor.

[0216] Embodiment 88. The method of any one of embodiments 85 to 87, wherein each of the blowing agent and the crosslinking agent comprises an HLB value of at most 5, a reactivity value of at most 10%, a MAR of at most 1.0 wt %, or a combination thereof.

[0217] Embodiment 89. The method of any one of embodiments 85 to 88, wherein the organic material precursor is hydrophobic.

[0218] Embodiment 90. The method of any one of embodiments 85 to 89, wherein the organic material comprises an HLB value of at most 5, a reactivity value of at most 10%, a MAR of at most 1.0 wt %, or a combination thereof.

[0219] Embodiment 91. The method of any one of embodiments 85 to 90, wherein the organic material precursor comprises an epoxy resin, a polyol, or a combination thereof.

[0220] Embodiment 92. The method of any one of embodiments 85 to 91, wherein the crosslinking agent comprises isocyanate 370, hexamethylene diisocyanate (HDI), isophorone diisocyanate, a hydrophobic polyisocyanate, an amine, a thiol, or a combination thereof.

[0221] Embodiment 93. The method of any one of embodiments 85 to 92, wherein the blowing agent comprises cyclopentane, pentane, isopentane, diphenylmethane diisocyanate, or a combination thereof.

[0222] Embodiment 94. The method of any one of embodiments 85 to 93, further comprising forming a film or tape comprising the mixture, wherein foaming is performed in the film or tape.

[0223] Embodiment 95. The method of embodiment 94, wherein the film or tape is formed by extruding, calendaring, printing, or casting the mixture.

[0224] Embodiment 96. The method of Embodiment 94 or 95, wherein the film or tape is a first green layer, wherein the method further comprises forming a second green layer, wherein the second green layer overlies the first green layer.

[0225] Embodiment 97. The method of embodiment 96, wherein the first green layer is formed simultaneously with the formation of the second green layer.

[0226] Embodiment 98. The method of Embodiment 96, further comprising laminating the first and second green layers.

[0227] Embodiment 99. The method of any one of embodiments 85 to 98, wherein the foaming reaction is performed at a temperature of at least 40°C and at most 80°C.

[0228] Embodiment 100. The method of embodiment 99, wherein the foaming reaction is performed at a temperature above the formation temperature of the film or tape.

[0229] Embodiment 101. The method of any one of embodiments 85 to 100, further comprising limiting the thickness of the film or tape while performing the foaming reaction.

[0230] Embodiment 102. The method of any one of Embodiments 99 to 101, further comprising curing the mixture in the green layer to form a solid ionically conductive layer, wherein curing is performed at a temperature of 20°C to 150°C.

[0231] Embodiment 103. The method of any one of embodiments 96 to 102, further comprising forming a dense electrolyte layer (raw) armor component from the second green layer, the component comprising:

[0232] A subject, comprising:

[0233] A first portion comprising at least about 90% by weight of a calcium boride compound and having a density of at least about 80% of theoretical density, wherein the calcium boride compound comprises a non-stoichiometric amount of calcium boride (CaB x ) and stoichiometric calcium boride (CaB6).

[0234] Examples

[0235] Example 1

[0236] According to the examples herein, a mixture having the composition included in Table 1 can be used to form a porous solid ion-conducting layer. The cast tape can be heated to approximately 55°C, at which point the cyclopentane foaming reaction begins. Because the forming reaction is exothermic, the tape temperature further increases as the foaming reaction proceeds. At approximately 70°C, the isocyanate and VORAPEL crosslink, forming a porous polyurethane structure.

[0237] Table 1

[0238]

[0239]

[0240] Example 2

[0241] According to the embodiments herein, a mixture having the composition included in Table 2 can be used to form a porous solid ion conductive layer. Even if certain contents are within a certain range in Table 2, it should be understood that the contents of the components sum to 100%. The cast tape can be heated to about 40°C, at which temperature the foaming reaction of pentane begins. Since the forming reaction is exothermic, the tape temperature further increases as the foaming reaction proceeds. Hardening of the epoxy resin begins shortly after the porous epoxy resin frame is formed.

[0242] Table 2

[0243]

[0244] Example 3

[0245] According to the embodiments herein, a mixture having the composition included in Table 3 can be used to form a porous solid ion conductive layer. Casting system and 3800 can be mixed in a ratio of 10:18. Even if some contents are within a certain range in Table 3, it should be understood that the contents of the components sum to 100%. Foaming and crosslinking can be carried out in the cast tape according to the manufacturer's instructions.

[0246] Table 3

[0247]

[0248] Example 4

[0249] Each of the binder materials in Table 4 below was mixed with Li3YBr6 powder to form a solid ion conductive layer.

[0250] PVC powder and the plasticizer diisononyl phthalate (DINP) are premixed so that the mixture includes 40% by weight of PVC and 60% by weight of DINP, based on the total weight of the premix. The premix of PVC and DINP is then mixed with Li3YBr6 powder, where the Li3YBr6 powder accounts for 60% by weight of the total mixture of Li3YBr6 and the premix, and the premix of PVC and DINP accounts for 40% by weight of the total mixture. Azodicarbonamide (e.g., CelChem LLC Celgogen 780) is used as a blowing agent and is added to the mixture of PVC, DINP, and Li3YBr6. The mixture is cast into a sheet, which is heated at 150 to 200°C to allow the PVC to melt and cooled to form a Li3YBr6-PVC foam.

[0251] XRD analysis of a mixture of Li3YBr6 and DINP showed minimal decomposition of Li3YBr6 and low levels of lithium bromide formation. DINP has a reactivity value of less than 10%, and is believed to be chemically compatible with Li3YBr6. XRD analysis of a mixture of Li3YBr6 and PVC showed that PVC is chemically compatible with Li3YBr6.

[0252] Table 4

[0253] polymer matrix Compatibility with LYB Curing PVC (PVC + DINP plasticizer) yes yes <![CDATA[Silicone-epoxy resin and catalyst - B(C6F5)3]]> yes no Silicone and Catalyst-Sn no no Silicone HCR and Catalyst-Peroxide no no Silicone and Catalyst-Pt yes no Silicone and catalyst-Pt (high concentration) yes yes

[0254] The silicone-epoxy resin was premixed with the catalyst in a weight ratio of 99 wt% silicone to 1 wt% B(C6F5)3. The premix was then mixed with Li3YBr6 such that the premix comprised 70 wt% of the total of the premix and Li3YBr6 and Li3YBr6 comprised 30 wt% of the total. It was noted that the mixture of silicone-epoxy resin, catalyst B(C6F5)3, and Li3YBr6 powder did not fully cure under the curing conditions used for silicone-epoxy resin, 120°C for 30 minutes, and that the mixture did not fully cure as the amount of catalyst was increased.

[0255] A high consistency silicone rubber (HCR) (Nouryon Silicone Gum RB6-0902) and a catalyst peroxide were premixed with the catalyst in a weight ratio of 97 wt% silicone HCR to 3 wt% peroxide. The premix Li3YBr6 was then mixed so that the premix accounted for 70 wt% of the total of the premix and L3YBr6 and L3YBr6 accounted for 30 wt% of the total. It was also noted that the mixture of silicone HCR with catalyst peroxide (Nouryon Peroxide PD-50-S-PS) and Li3YBr6 powder did not fully cure, and the XRD pattern of the mixture of silicone HCR, peroxide and Li3YBr6 showed characteristic peaks of LiBr, which indicated decomposition of Li3YBr6.

[0256] A premix of silicone and Sn catalyst (Nusil RT Foam Silicone R-2370) was mixed with Li3YBr6. The mixture did not cure completely, and XRD analysis of the mixture indicated decomposition of the Li3YBr6.

[0257] A premix of silicone and Pt catalyst (Nusil RT Foam Silicone R-2360) was mixed with Li3YBr6 in a weight percentage of 50 wt% premix: 50 wt% Li3YBr6. XRD analysis of the mixture showed that the Li3YBr6 did not decompose and that the silicon and the Pt catalyst were chemically compatible. The Pt content in the premix was 50 ppm relative to the weight of the silicone. The mixture did not cure completely. Further analysis showed that impurities, ammonium bromide, in the Li3YBr6 powder may have affected the curing. An additional amount of Pt of 400 ppm to 5000 ppm was added to the previous mixture of silicon, Pt catalyst and Li3YBr6, and when the Pt content was increased to 600 ppm and above, the new mixture was able to cure at a temperature of 20°C to 70°C for 5 to 20 minutes.

[0258] Example 5

[0259] A two-part liquid silicone rubber (LSR) was used to form a solid ion-conducting layer comprising 65 wt% Li3YBr6 and 35 wt% of a foamed polysiloxane matrix. The following process was performed in a glove box.

[0260] For a two-part liquid silicone rubber (LSR), 45 wt% Li3YBr6 is uniformly dispersed in 55 wt% Part A. Part A includes vinyl silicone, catalyst Pt, and a blowing agent (silanol). 69 wt% Li3YB6 is uniformly dispersed in 31 wt% Part B. Part B includes vinyl silicone and a crosslinker (hydride silicone). The Li3YBr6-Part A premix and the Li3YBr6-Part B premix are combined. The final mixture is used to tape-cast films with a thickness of 50 to 300 μm. The film is heated and held at 60°C to 100°C for up to 10 minutes to allow foaming and curing to occur simultaneously. When Pt is present, the silanol (blowing agent in Part A) reacts with the hydride silicone (in Part B) to generate hydrogen gas for foaming. Simultaneously, the vinyl silicone (in both Part A and Part B) reacts with the hydride silicone (crosslinker in Part B) to form the silicone rubber. The membrane is then cooled, forming a solid ionically conductive layer comprising Li3YBr6 in the silicone foam.

[0261] Example 6

[0262] Table 5

[0263]

[0264] The foam sheet was formed from a platinum-based silicone foaming system comprising the components listed in Table 10 with a halide-based ion conductive material. The components were premixed and the premix was mixed with the halide-based ion conductive material in a weight ratio of 0.1 wt % to 99.9 wt %, 0.5 wt % to 99.5 wt %, 1 wt % to 99 wt %, 1.5 wt % to 98.5 wt %, 2 wt % to 98 wt %, 3 wt % to 98 wt %, 4 wt % to 96 wt %, 5 wt % to 95 wt %, 6 wt % to 94 wt %, 7 wt % to 93 wt %, 8 wt % to 92 wt %, 9 wt % to 91 wt %, and 10 wt % to 90 wt % to form an ion conductive layer.

[0265] The benefits, other advantages and solutions to problems have been described above with reference to specific embodiments. However, the benefits, advantages, solutions to problems and any features that may make any benefit, advantage or solution conceivable or more significant are not considered to be key, required or essential features of any or all claims. The materials mentioned herein that include one or more components may be interpreted as including at least one embodiment in which the material consists essentially of the one or more components specified. The term "consisting essentially of..." should be interpreted as including components that include those materials specified and excluding all other materials except for a small amount (e.g., impurity content) of the material that does not significantly change the properties of the material. In addition or alternatively, in certain non-limiting embodiments, any of the compositions specified herein may be substantially free of materials that are not explicitly disclosed. The embodiments herein include ranges of amounts of certain components within the materials, and it should be understood that the amounts of the components within a given material total 100%.

[0266] The description and illustrations of the embodiments described herein are intended to provide a general understanding of the structures of the various embodiments. The description and illustrations are not intended to be used as a detailed and comprehensive description of all elements and features of the apparatus and system using the structures or methods described herein. Individual embodiments may also be provided in a combined manner in a single embodiment, and conversely, the various features described in the context of a single embodiment for simplicity may also be provided individually or in any sub-combination. Further, reference to values expressed in ranges includes each value and all values within the range. Many other embodiments will be apparent to those skilled in the art only after reading this specification. Other embodiments may be utilized and obtained through this disclosure so that structural replacement, logical replacement, or other changes may be performed without departing from the scope of this disclosure. Therefore, this disclosure should be considered illustrative and not restrictive.

Claims

1. A solid ionically conductive layer comprising a foam matrix containing an electrolyte material, the electrolyte material comprising a halide-based material, the electrolyte material being mixed with an organic material, wherein the organic material comprises a polymeric material and the halide-based material is represented by formula M 3-δ (Me k+ ) f X 3-δ+k*f It represents, wherein -3≤δ<3, 0≤f≤1, k is the valence of Me, 2≤k<6, M includes an alkali metal element including Li, Me includes a metal element different from M, and X includes a halogen. 2 . The solid ion-conducting layer according to claim 1 , wherein the content of the organic material is at least 0.5% and at most 50% by volume of the total volume of the solid ion-conducting layer. The solid ion conducting layer of claim 1 , wherein the polymer comprises siloxane.

4. The solid ion conducting layer of claim 3 comprising platinum embedded within the foam matrix.

5. The solid ion conducting layer of claim 1, wherein the foam matrix comprises polydimethylsiloxane.

6. The solid ionically conductive layer of any one of claims 1 to 5, comprising at least 10 ppm and at most 1 wt% Pt, based on the total weight of the foam matrix.

7. The solid ion conducting layer of claim 1, wherein the polymer has an HLB number of at most 10, a reactivity value of at most 20%, or a combination thereof.

8. The solid ion conducting layer of any one of claims 1, 2, and 7, wherein the polymer comprises an epoxy resin, a polyurethane, poly(ethylene), poly(ethylene oxide), or a combination thereof.

9. The solid ion conducting layer of any one of claims 1, 2, and 7, wherein the foam matrix comprises polyvinyl chloride.

10. The solid ion conducting layer of any one of claims 1 to 5, comprising a total porosity of at least 30% and at most 95% by volume of the total volume of the solid ion conducting layer.

11. A solid ionically conductive layer according to any one of claims 1 to 5, wherein the foam matrix comprises a porosity of pores having an average pore size of at least 0.1 micrometers and at most 50 micrometers.

12. A solid ionically conducting layer according to any one of claims 1 to 5, wherein the electrolyte material comprises ammonium halide complexed with the halide-based material.

13. A solid ionically conducting layer according to any one of claims 1 to 5, wherein the electrolyte material comprises ammonium halide complexed with the halide-based material.

14. The solid ion conducting layer of any one of claims 1 to 4, wherein the polymer comprises vinyl terminated polydimethylsiloxane, hydride functional siloxane, methylhydrogensiloxane-dimethylsiloxane copolymer, or a combination thereof.

15. The solid ion conducting layer of any one of claims 1 to 5, further comprising lithium metal dispersed in the foam matrix.

16. A composite layer comprising the solid ion conductive layer according to any one of claims 1 to 5 and an electronic conductive material.

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