A secondary hybrid solid-state battery and methods of making thereof

Abstract

Disclosed is a separator comprising: a substrate having a first surface and an opposite second surface; and a first ceramic layer disposed on at least the first surface of the substrate, wherein the separator exhibits an ionic conductivity of about 0.01 mS / cm to about 100 mS / cm when inserted in an electrolyte and wherein the separator is used in a rechargeable battery. Also disclosed are methods of making the same. Also disclosed herein are batteries comprising the same.

Description

A SECONDARY HYBRID SOLID-STATE BATTERY AND METHODS OF MAKING THEREOFCROSS-REFERENCE TO THE RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Provisional Application No. 63 / 498,076, filed on April 25, 2023, and of U.S. Provisional Application No.63 / 515,875, filed on July 27, 2023, the contents of which are hereby incorporated in its entirety.TECHNICAL FIELD

[0002] This application relates generally to secondary hybrid solid-state batteries and methods of making the same.BACKGROUND

[0003] The urgent need for clean and renewable power and the rapid development of electric vehicles (EV) and portable electronic devices drive the strong demand for high-energy-density batteries. Lithium metal batteries (LMB) have come into the spotlight due to the specific capacity of the Li metal anode (3860 mAh g~1), which is about 10 times greater than that of the graphite anode (370 mAh g~1) employed by currently commercialized Li-ion batteries (LIBs). The origin of rechargeable lithium metal batteries dates to the 1970s. However, the safety of lithium anode is still problematic. One challenge is the uncontrollable formation of mossy and dendritic lithium metal on the anode during the charging of the cell. Li dendrites drastically reduce the lifespan of a battery and cause low Coulombic efficiency. Additionally, dendrites can lead to an internal short circuit which can cause a catastrophic failure resulting in a battery fire or explosion.

[0004] Current lithium-ion technology uses flammable organic liquid electrolytes, which are highly unstable with lithium metal. These safety issues are mitigated in current lithium-ion technology by implementing an intercalation host anode, such as graphitic carbon. However, at high charge rates where it becomes favorable for lithium ions to be deposited on the surface of the graphite rather than intercalate into thestructure, lithium dendrite formation ensues, and the aforementioned safety risks are present. To overcome these challenges, there has been tremendous work on exploring solid-state electrolytes and liquid-state electrolyte formations and implementing lithium metal alloy architectures to prevent Li dendrite formation and enhance battery safety. However, incorporating new materials and concepts into existing lithium-ion batteries has yet to yield any significant improvement that overcomes the economic barrier of commercial scale-up and implementation.

[0005] Separator modification has been found to be an effective approach to improve the safety of conventional LIBs by enhancing the thermal stability of the separators, which are commonly made of polypropylene (PP) and polyethylene (PE). Coating layers usually comprise inorganic ceramic materials (i.e., AI2O3, SiC , and ZrC ).However, these inorganic ceramic fillers commonly used for separator coating for LIBs, such as AI2O3 and TiO2, are not Li-ion conductive.

[0006] Thus, new approaches to provide effective separators that address these needs are needed. Electrochemical cells utilizing these new separators are also needed. These needs and other needs are at least partially satisfied by the present disclosure.SUMMARY

[0007] The present disclosure is directed to a separator comprising: a substrate having a first surface and an opposite second surface; and a first ceramic layer disposed on at least the first surface of the substrate, wherein the separator exhibits an ionic conductivity of about 0.01 mS / cm to about 100 mS / cm when inserted in an electrolyte and wherein the separator is used in a rechargeable battery.

[0008] Also disclosed are aspects where a second ceramic layer is disposed at the second surface of the substrate.

[0009] In still further aspects, the first ceramic layer comprises a first homogeneous blend comprising a first ceramic material and a first binder. Yet, in other aspects, if the second ceramic layer is present, the second ceramic layer comprises a second homogeneous blend comprising a second ceramic material and a second binder. Insome exemplary and unlimiting aspects, the first and / or second ceramic material can comprise Li7 xLasZr2 xTaxOi2, Li?La3Zr20i2 Lii+XAlxTi2-x(PO4)3 (LATP), Lii+x+yAlxTi2-xSi3 yOi2, LiioGeP2Si2, Lii4Zn(GeO4)4, LiTi2(PO4)3, Li?La3Zr20i2, Lio.sLao.sTiOs, l_i2S-P2S5, Li2S-GeS2, Li2S-SiS2, Li2S-SnS2 Li3.sPO2.8Nx, LiePSsX, U3YX6, (wherein X is F, Cl, Br, or I), LiGe2(PO4)3, Lii+xAlxGe2-x(PO4)3, or any combination thereof. In still further exemplary and unlimiting aspects, the first and / or second binder is polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), carboxymethylcellulose (CMC), styrene-butadiene rubber (SBR), polyacrylic acid (PAA), polyvinyl alcohol (PVA), polyvinyl butyral (PVB), polyvinylpyrrolidone (PVP), ethyl cellulose (EC), copolymers thereof, or any combination thereof.

[0010] In still further aspects, the separator disclosed herein comprises the first and / or second ceramic layers that are substantially free of lithium, potassium, sodium, or a combination thereof. In still further aspects, the first and / or second ceramic layer is substantially non-conductive for ions of lithium, potassium, sodium, or a combination thereof. In yet still further aspects, the ceramic layers are substantially crystalline.

[0011] In yet still further exemplary and unlimiting aspects, the ceramic layers do not conduct alkali-ions through a bulk of a crystalline lattice. In such exemplary and unlimiting aspects, the first and / or second ceramic material comprises Cei-xGdxOy, wherein x is greater or equal to 0 and less than 1 , and wherein y is selected to account for the valency of each element and overall neutrality.

[0012] In yet further aspects, the separator has a total thickness of less than about 35 microns.

[0013] In still further aspects, the separator exhibits a lithium transference number equal to or greater than about 0.76 in the presence of an electrolyte (or when exposed to an electrolyte). In yet still further exemplary and unlimiting aspects, the separator exhibits a lithium transference number equal to or greater than about 0.89 in the presence of an electrolyte (or when exposed to an electrolyte).

[0014] In yet still further aspects, disclosed herein is a rechargeable battery comprising: any of the disclosed herein separators; an anode material; a cathode material; and an electrolyte.

[0015] Also disclosed is a method of making any of the disclosed herein separators, wherein the method comprises: depositing a first homogeneous mixture of a first ceramic material and a first binder at a first surface of a substrate and drying the separator to form a first uniform ceramic layer. Still further, the method can further comprise depositing a second homogeneous mixture of a second ceramic material and a second binder on a second surface of the substrate that is opposite to the first surface.

[0016] Also disclosed herein is a rechargeable battery comprising: a Li anode material; a cathode material; and an electrolyte, wherein the electrolyte comprises about 1 M to about 4 M of lithium bis(fluorosulfonyl)imide and about 0.05 M to about 0.5 M of lithium difluoro(oxalato)borate dissolved in a mixture of solvents comprising about 40 vol% to about 90 vol% of DME, about 10 vol% to about 60 vol% of DOL, and about 0.05 wt% to about 5 wt% of DMI.

[0017] Additional advantages will be set forth in part in the description which follows, and in part will be obvious from the description or can be learned by practice of the aspects described below. The advantages described below will be realized and attained by means of the chemical compositions, methods, and combinations thereof, particularly pointed out in the appended claims. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and is not restrictive of the invention, as claimed.BRIEF DESCRIPTION OF DRAWINGS

[0018] FIGURE 1 depicts a graph showing the conductivity of Ta-doped Li7-xLasZr2- xTaxOi2 (0<x < 1 .0) at room temperature, as described in Y. Li et al., J. Mater. Chem., 2012, 22, 15357-15361 , incorporated herein in its entirety.

[0019] FIGURES 2A-2B depict a schematic illustration of the single-side coated separator (FIG. 2A) and the double-coated separator (FIG.2B).

[0020] FIGURES 3A-3B depict a schematic illustration of an exemplary hybrid lithium cell in one aspect, wherein the cathode is NMC81 1 ; single side coated separator; and a lithium foil as the anode (FIG. 3A), and an exemplary hybrid lithium cell in a different aspect, wherein the cathode is NMC622; double side coated separator; and a lithium foil as the anode (FIG. 3B). These NMC compositions can be substituted with alternative lithium cathode materials.

[0021] FIGURES 4A-4B depict scanning electron microscopy (SEM) images of the surface of LLZTO / PEO coating on a PE (Entek) 9 pm separator with different magnifications.

[0022] FIGURE 5 depicts a graph showing the galvanostatic cycling stability of exemplary Li / Li symmetric cells with a commercial PE (Entek) separator and LLZTO / PEO coated separator in one aspect; the applied current density to the cell is 0.5 mAcm-2.

[0023] FIGURE 6 depicts a graph showing the evolution of current with polarization time under a polarization voltage of 10 mV and Nyquist plots of the impedance of exemplary cells with commercial PE (Entek) separator before and after DC polarization at room temperature - this series of measurements were performed to calculate the Li+transference number of the separator with a commercial liquid electrolyte.

[0024] FIGURE 7 depicts a graph showing the evolution of current with polarization time under a polarization voltage of 10 mV and Nyquist plots of the impedance of exemplary cells with coated separator before and after DC polarization at room temperature - this series of measurements was performed to calculate the Li+transference number of the separator with a commercial liquid electrolyte.

[0025] FIGURE 8 depicts a graph of the comparison of average discharge potential during galvanostatic cycling of an exemplary LFP / Li cell with a single coated separatororiented towards the lithium metal anode and an exemplary LFP / Li cell with a commercial PE (Entek) separator.

[0026] FIGURE 9 depicts a graph of the galvanostatic cycling curves of an exemplary NMC81 1 / Li cell with a commercial PE (Entek) separator.

[0027] FIGURE 10 depicts a graph of the galvanostatic cycling curves of an exemplary NMC81 1 / Li cell with a coated PE (Entek) separator.

[0028] FIGURE 11 depicts a graph of the capacity versus cycle number for exemplary NMC81 1 / Li cells (cathode active material mass loading is 2.6 mAh erm2) with the commercial and coated separators. The cycling rate is C / 10 for the first three cycles and C / 5 for the subsequent cycles.

[0029] FIGURE 12 depicts a graph of capacity versus cycle number for an exemplary LFP / Li pouch cell implementing the coated separator.

[0030] FIGURE 13 depicts a graph of capacity versus cycle number for an exemplary NMC622 / Li pouch cell using a coated separator.

[0031] FIGURE 14 depicts the cycling performance of exemplary liquid electrolyte lithium batteries consisting of a LiFePC cathode, a lithium metal anode, and an uncoated commercial separator.

[0032] FIGURES 15A-15B depict a schematic illustration of two types of single-side coated separators with a 5 pm coating layer containing a mixture of micro / nanosized gadolinium doped ceria (GDC) ceramic and ethyl cellulose (EC) binder (FIG. 15A) and an 8pm coating layer containing only nanosized GDC ceramic and EC binder (FIG.15B).

[0033] FIGURES 16A-16B depict scanning electron microscopy (SEM) images of the surface of nanosized GDC / EC coating on a polyethylene (PE) (Entek) 9 pm separator with different magnifications.

[0034] FIGURES 17A-17B depict scanning electron microscopy (SEM) images of micro / nanosized GDC ceramic powder with different magnifications.

[0035] FIGURE 18 depicts digital photographs of an uncoated 9 pm PE (Entek) separator and nanosized GDC / EC single-side coated separator (9pm Entek) after dropping 10 pL liquid electrolyte (LiFSI-DME-TTE, 1 :1.2:3 by mol).

[0036] FIGURES 19A-19C depict an illustration of an exemplary hybrid lithium cell in one aspect, wherein the cathode is NMC81 1 ; single-side coated separator with a 5 pm micro / nanosized GDC / EC coating layer; and a lithium foil as the anode (FIG. 19A), and an exemplary hybrid lithium cell in another aspect, wherein the cathode is NMC622; single-side coated separator with an 8 pm nanosized GDC / EC coating layer; and a lithium foil as the anode (FIG. 19B), and an exemplary hybrid lithium cell in different aspect, wherein the cathode is LFP; single-side coated separator with an 8 pm nanosized GDC / EC coating layer; and a lithium foil as the anode (FIG. 19C). These NMC compositions can be substituted with alternative lithium cathode materials. The base separators are 9pm Entek PE.

[0037] FIGURE 20 depicts the galvanostatic cycling stability of exemplary Li / Li symmetric cells with an uncoated 9 pm PE (Entek) separator, nanosized GDC / EC coated separator (9pm Entek) in one aspect, and micro / nanosized GDC / EC coated separator in another aspect; the applied current density to the cell is 0.5 mAcnr2.

[0038] FIGURE 21 shows linear sweep voltammetry (LSV) curves of Al foil / separator / Li pouch cells with an uncoated 9 pm PE (Entek) separator and a nanosized GDC / EC single-side coated separator (9pm Entek) measured at the scan rate of 10 mV s-1.

[0039] FIGURE 22 shows the evolution of current with polarization time under a polarization voltage of 10 mV and Nyquist plots of the impedance of exemplary cells with commercial PE (9pm Entek) separator before and after DC polarization at room temperature - this series of measurements were performed to calculate the Li+transference number of the separator with a commercial liquid electrolyte.

[0040] FIGURE 23 shows the evolution of current with polarization time under a polarization voltage of 10 mV and Nyquist plots of the impedance of exemplary cellswith a nanosized GDC / EC single-side coated separator (9pm Entek) before and after DC polarization at room temperature - this series of measurements were performed to calculate the Li+transference number of the separator with a commercial liquid electrolyte.

[0041] FIGURE 24 shows galvanostatic cycling curves of an exemplary NMC81 1 / Li cell with an uncoated PE (9pm Entek) separator in 10pL conventional electrolyte (1 M LiPFe in EC-DEC (1 :1 by vol.))

[0042] FIGURE 25 shows Galvanostatic cycling curves of an exemplary NMC81 1 / Li cell with a micro and nanosized GDC / EC single-side coated separator (9pm Entek) in 10pL conventional electrolyte (1 M LiPFe in EC-DEC (1 :1 by vol.)).

[0043] FIGURE 26 shows Galvanostatic cycling curves of an exemplary NMC81 1 / Li cell with a nanosized GDC / EC single-side coated separator (9pm Entek) in 10pL conventional electrolyte (1 M LiPFe in EC-DEC (1 :1 by vol.)).

[0044] FIGURE 27 shows capacity versus cycle number for exemplary NMC811 / Li cells (cathode areal loading is 1 .7 mAhcm2) with the uncoated, micro and nanosized and nanosized GDC / EC single-side coated separators (9pm Entek). The cycling rate is C / 10 for the first three cycles and C / 5 for the subsequent cycles. The electrolyte is 10pL conventional electrolyte (1 M LiPFe in EC-DEC (5:5 by vol.)

[0045] FIGURE 28 shows capacity versus cycle number for exemplary NMC811 / Li cells (cathode areal loading is 2.5 mAhcm-2) with a nanosized GDC / EC single-side coated separator (7pm Entek). The cycling rate is C / 10 for the first three cycles and C / 5 for the subsequent cycles. The electrolyte is 10pL liquid electrolyte (LiFSI-DME- TTE(1 :2:3 by mole) with 1wt% LiNOs and 5wt% FEC.

[0046] FIGURE 29 shows capacity versus cycle number for an exemplary NMC622 / Li pouch cell (cathode areal loading is 3.7 mAhcm-2) implementing a nanosized GDC / EC single-side coated separator (9pm Entek). The electrolyte is LiFSI-DME-TTE (1 :1 .2:3 by mol, 3 g Ah-1).

[0047] FIGURE 30 shows capacity versus cycle number for an exemplary LFP / Li pouch cell (cathode areal loading is 2.6 mAhcm-2) implementing a nanosized GDC / EC single-side coated separator (9pm Entek). The electrolyte is LiFSI-DME-TTE (1 :2:3 by mol) with 1wt% LiNOa and 5wt% EEC (3.5 g Ah-1).

[0048] FIGURE 31 shows capacity versus cycle number for an exemplary LFP / Li 0.5 Ah pouch cell (cathode areal loading is 2.6 mAhcm-2) implementing a nanosized GDC / EC single-side coated separator (9pm Entek). The electrolyte is 3M LiFSI and 0.25M LiDFOB in 40% DME / 60% DOUO.2% DMI (4 g Ah-1).

[0049] FIGURE 32 shows a direct current internal resistance (DCIR) versus the cycle number of the cell shown in FIG. 31.

[0050] FIGURE 33 shows the cycling performance of a coin cell with a coated separator, 3 pm ceramic single-sided coating layer on a 9 pm PE membrane substrate. The anode is 100 pm pure Li metal foil, and the cathode is Ni83-NMC. The active mass loading is 12.3 mg / cm2. For the first 2 formation cycles, the charge and discharge rate is C / 10. In terms of subsequent cycling, the charge rate is 0.2C, and the discharge rate is 1 C. The electrolyte is 1 wt% LiDFOB in 1 M LiPFe EMC / FEC (9:1 by vol.)

[0051] FIGURE 34 shows the cycling performance of a 1 Ah multi-layer (9 layers cathode and 10 layers anode) pouch cell with single-sided coated separators. Each separator is composed of a 3 pm ceramic single-coated coating layer, and the substrate is a 9 pm PE membrane. The anodes are double-sided ~20 pm Li metal foil with 11 pm copper foils as current collectors. Cathodes are Ni83-NMC with an active mass loading is ~14 mg / cm2. In terms of cycling, the charge rate is 0.2C, and the discharge rate is 1 C. The electrolyte is 1 wt% LiDFOB in 1 M LiPFe EMC / FEC (9:1 by vol.) The cell showed a much shorter wetting process compared to the cycling performance in a coin cell configuration.

[0052] The accompanying figures, which are incorporated in and constitute a part of this specification, illustrate several aspects described below.DETAILED DESCRIPTION

[0053] The present invention can be understood more readily by reference to the following detailed description, examples, drawings, and claims, and their previous and following description. However, before the present articles, systems, and / or methods are disclosed and described, it is to be understood that this invention is not limited to the specific or exemplary aspects of articles, systems, and / or methods disclosed unless otherwise specified, as such can, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting.

[0054] The following description of the invention is provided as an enabling teaching of the invention in its best, currently known aspect. To this end, those skilled in the relevant art will recognize and appreciate that many changes can be made to the various aspects of the invention described herein while still obtaining the beneficial results of the present invention. It will also be apparent that some of the desired benefits of the present invention can be obtained by selecting some of the features of the present invention without utilizing other features. Accordingly, those of ordinary skill in the pertinent art will recognize that many modifications and adaptations to the present invention are possible and may even be desirable in certain circumstances and are a part of the present invention. Thus, the following description is again provided as illustrative of the principles of the present invention and not in limitation thereof.DEFINITIONS

[0055] As used herein, the terms "optional" or "optionally" mean that the subsequently described event or circumstance can or cannot occur and that the description includes instances where said event or circumstance occurs and instances where it does not.

[0056] It is appreciated that certain features of the disclosure, which are, for clarity, described in the context of separate aspects, can also be provided in combination in a single aspect. Conversely, various features of the disclosure, which are, for brevity,described in the context of a single aspect, can also be provided separately or in any suitable subcombination.

[0057] As used in the description and the appended claims, the singular forms “a,” “an,” and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, a reference to “a battery” includes two or more such batteries, and a reference to “a ceramic material” includes two or more such ceramic materials and the like.

[0058] It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting. As used in the specification and in the claims, the term “comprising” can include the aspects “consisting of” and “consisting essentially of.” Unless defined otherwise, 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. In this specification and in the claims which follow, reference will be made to a number of terms that shall be defined herein.

[0059] For the terms "for example" and "such as," and grammatical equivalences thereof, the phrase "and without limitation" is understood to follow unless explicitly stated otherwise. It is further understood that these phrases are used for explanatory purposes only. It is further understood that the term “exemplary,” as used herein, means “an example of” and is not intended to convey an indication of a preferred or ideal aspect.

[0060] The expressions "ambient temperature" and "room temperature" as used herein are understood in the art and refer generally to a temperature from about 20 °C to about 35 °C.

[0061] Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the disclosure are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standarddeviation found in their respective testing measurements. Furthermore, when numerical ranges of varying scope are set forth herein, it is contemplated that any combination of these values, inclusive of the recited values, may be used. Further, ranges can be expressed herein as from “about” one particular value and / or to “about” another particular value. When such a range is expressed, another aspect includes from the one particular value and / or to the other particular value.

[0062] All disclosed values also include values that fall within ±10% variation from the disclosed value unless otherwise indicated or inferred. In other words, if a range of 1 to 10 is disclosed, then a range of about 1 to about 10 is disclosed. In such aspects, it is understood that the amount or value in question can be the exact value or a value that provides equivalent results or effects as recited in the claims or taught herein. That is, amounts, sizes, formulations, parameters, and other quantities and characteristics include both exact values but also approximate, larger or smaller values as desired, reflecting tolerances, conversion factors, rounding, measurement error, and the like, and other factors known to those of skill in the art such that equivalent results or effects are obtained. In some circumstances, the value that provides equivalent results or effects cannot be reasonably determined. In general, an amount, size, formulation, parameter, or other quantity or characteristic is "about," "approximate," or "at or about," whether or not expressly stated to be such. Where "about," "approximate," or "at or about" is used before a quantitative value, the parameter also includes the specific quantitative value itself unless expressly stated otherwise.

[0063] As used herein, the term or phrase “effective,” “effective amount,” or “conditions effective to” refers to such amount or condition that is capable of performing the function or property for which an effective amount or condition is expressed. As will be pointed out below, the exact amount or particular condition required will vary from one aspect to another, depending on recognized variables such as the materials employed and the processing conditions observed. Thus, it is not always possible to specify an exact “effective amount” or “condition effective to.” However, it should be understoodthat an appropriate, effective amount will be readily determined by one of ordinary skill in the art.

[0064] When a range is expressed, a further aspect includes from the one particular value and to the other particular value. For example, where the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included in the disclosure, e.g., the phrase "x to y" includes the range from 'x' to 'y' as well as the range greater than 'x' and less than 'y'. The range can also be expressed as an upper limit, e.g., 'x, y, z, or less' and should be interpreted to include the specific ranges of ‘x,’ ‘y,’ ‘z,’ 'about x,' 'about y,' and 'about z' as well as the ranges of 'less than x,' 'less than y, or 'less than z,' or 'less than about x,' 'less than about y, and 'less than about z.' Likewise, the phrase ' x, y, z, or greater' should be interpreted to include the specific ranges of ‘x,’ ‘y,’ ‘z,’ 'about x,' 'about y ,’ and 'about z' as well as the ranges of 'greater than x,' greater than y,' 'greater than z,' or 'greater than about x,' greater than about y,' 'greater than about z.' In addition, the phrase " 'x' to 'y'," where 'x' and 'y' are numerical values, also includes "about 'x' to about 'y'."

[0065] Such a range format is used for convenience and brevity and, thus, should be interpreted flexibly to include not only the numerical values explicitly recited as the limits of the range but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. To illustrate, a numerical range of " 0.1 % to 5%" should be interpreted to include not only the explicitly recited values of 0.1 % to 5% but also include individual values (e.g., 1%, 2%, 3%, and 4%) and the sub-ranges (e.g., 0.5% to 1 .1 %; 5% to 2.4%; 0.5% to 3.2%, and 0.5% to 4.4%, and other possible sub-ranges) within the indicated range.

[0066] Throughout this disclosure, various aspects of the invention can be presented in a range format. It should be understood that the description in range format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the invention. Accordingly, the description of a range should be considered to have specifically disclosed all the possible subranges as well asindividual numerical values within that range. For example, a description of a range such as from 1 to 6 should be considered to have specifically disclosed subranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as individual numbers within that range, for example, 1 , 2, 2.7, 3, 4, 5, 5.3, 6 and any whole and partial increments therebetween. This applies regardless of the breadth of the range.

[0067] In still further aspects, when the specific values are disclosed between two end values, it is understood that these end values can also be included.

[0068] In still further aspects, when the range is given, and exemplary values are provided, it is understood that any ranges can be formed between any exemplary values within the broadest range. For example, if individual numbers 1 , 2, 3, 4, 5, 6, 7, etc. are disclosed, then the ranges 1 -7, 2-7, 3-7, 4-7, 5-7, 6-7, 1 -6, 1 -5, 1 -4, 1 -3, 1 -2, 2-6, 2-5, etc. are also disclosed.

[0069] References in the specification and concluding claims to parts by weight of a particular element or component in a composition denote the weight relationship between the element or component and any other elements or components in the composition or article for which a part by weight is expressed. Thus, in a mixture containing 2 parts by weight of component X and 5 parts by weight, components Y, X, and Y are present at a weight ratio of 2:5 and are present in such a ratio regardless of whether additional components are contained in the mixture.

[0070] A weight percent (wt.%) of a component, unless specifically stated to the contrary, is based on the total weight of the formulation or composition in which the component is included.

[0071] It will be understood that when an element is referred to as being "connected" or "coupled" to another element, it can be directly connected or coupled to the other element, or intervening elements may be present. In contrast, when an element is referred to as being "directly connected" or "directly coupled" to another element, there are no intervening elements present. Other words used to describe the relationshipbetween elements or layers should be interpreted in a like fashion (e.g., "between" versus "directly between," "adjacent" versus "directly adjacent," "on" versus "directly on").

[0072] As used herein, the term "and / or" includes any and all combinations of one or more of the associated listed items.

[0073] It will be understood that although the terms "first," "second," etc., may be used herein to describe various elements, components, regions, layers, and / or sections.These elements, components, regions, layers, and / or sections should not be limited by these terms. These terms are only used to distinguish one element, component, region, layer, or section from another element, component, region, layer, or section. Thus, a first element, component, region, layer, or section discussed below could be termed a second element, component, region, layer, or section without departing from the teachings of example embodiments.

[0074] As used herein, the term "substantially" means that the subsequently described event or circumstance completely occurs or that the subsequently described event or circumstance generally, typically, or approximately occurs.

[0075] Still further, the term “substantially” can, in some aspects, refer to at least about 80 %, at least about 85 %, at least about 90 %, at least about 91 %, at least about 92 %, at least about 93 %, at least about 94 %, at least about 95 %, at least about 96 %, at least about 97 %, at least about 98 %, at least about 99 %, or about 100 % of the stated property, component, composition, or other condition for which substantially is used to characterize or otherwise quantify an amount.

[0076] In other aspects, as used herein, the term “substantially free,” when used in the context of a composition or component of a composition that is substantially absent, is intended to refer to an amount that is then about 1 % by weight, e.g., less than about 0.5 % by weight, less than about 0.1 % by weight, less than about 0.05 % by weight, or less than about 0.01 % by weight of the stated material, based on the total weight of the composition.

[0077] It is understood that the term “salt,” as used herein, refers to a chemical compound that can be formed form a reaction between an acid and a base. It is understood that the term “salt,” as used herein, encompasses both inorganic and organic salts capable of providing the desired properties to the composition. In still further aspects, a cation of the disclosed herein salts is a metal cation.

[0078] Spatially relative terms, such as "beneath," "below," "lower," "above," "upper," “bottom,” “top,” and the like, may be used herein for ease of description to describe one element or feature's relationship to another element(s) or feature(s) as illustrated in the figures. It will be understood that the spatially relative terms are intended to encompass different orientations of the device in use or operation in addition to the orientation depicted in the figures. For example, if the device in the figures is turned over, elements described as "below" or "beneath" other elements or features would then be oriented "above" the other elements or features. Thus, the term "below" can encompass both an orientation of above and below. The device may be otherwise oriented (rotated 90 degrees or at other orientations), and the spatially relative descriptors used herein are interpreted accordingly.

[0079] While aspects of the present invention can be described and claimed in a particular statutory class, such as the system statutory class, this is for convenience only and one of ordinary skill in the art will understand that each aspect of the present invention can be described and claimed in any statutory class. Unless otherwise expressly stated, it is in no way intended that any method or aspect set forth herein be construed as requiring that its steps be performed in a specific order. Accordingly, where a method claim does not specifically state in the claims or descriptions that the steps are to be limited to a specific order, it is in no way intended that an order be inferred in any respect. This holds for any possible non-express basis for interpretation, including matters of logic with respect to the arrangement of steps or operational flow, plain meaning derived from grammatical organization or punctuation, or the number or type of aspects described in the specification.

[0080] The present invention may be understood more readily by reference to the following detailed description of various aspects of the invention and the examples included therein and to the Figures and their previous and following description.SEPARATORS

[0081] It was demonstrated that modified separators used in lithium-ion cells can improve cell electrochemical performance. In certain aspects, the modification can be done by deposition or coating of a ceramic material on the separator. In yet other aspects, the coating can comprise a blend of ceramic material and an organic binder.

[0082] Disclosed herein in some aspects is a separator comprising a substrate having a first surface and an opposite second surface. In still further aspects, a first ceramic layer disposed on at least the first surface of the substrate. In still further exemplary and unlimiting aspects, the separator disclosed herein can exhibit an ionic conductivity of about 0.01 mS / cm to about 100 mS / cm when inserted in an electrolyte, including exemplary values of about 0.025 mS / cm, about 0.05 mS / cm, about 0.075 mS / cm, about 0.1 mS / cm, about 0.25 mS / cm, about 0.5 mS / cm, about 0.75 mS / cm, about 1 mS / cm, about 2.5 mS / cm, about 5 mS / cm, about 7.5 mS / cm, about 10 mS / cm, about 12.5 mS / cm, about 15 mS / cm, about 20 mS / cm, about 30 mS / cm, about 40 mS / cm, about 50 mS / cm, about 60 mS / cm, about 70 mS / cm, about 80 mS / cm, and about 90 mS / cm. It is understood that the ionic conductivity can be in any range formed between any two foregoing values. For example, and without limitations, the ionic conductivity can be about 0.01 mS / cm to about 95 mS / cm, about 0.01 mS / cm to about 80 mS / cm, about 0.01 mS / cm to about 70 mS / cm, about 0.01 mS / cm to about 60 mS / cm, about 0.01 mS / cm to about 50 mS / cm, about 0.01 mS / cm to about 40 mS / cm, about 0.01 mS / cm to about 30 mS / cm, about 0.01 mS / cm to about 20 mS / cm, about 0.01 mS / cm to about 10 mS / cm, about 0.01 mS / cm to about 5 mS / cm, about 0.01 mS / cm to about 1 mS / cm, about 0.01 mS / cm to about 0.5 mS / cm, about 0.01 mS / cm to about 0.1 mS / cm, or about 0.5 mS / cm to about 10 mS / cm, or about 0.5 mS / cm to about 70 mS / cm, or about 1 mS / cm to about 100 mS / cm, and so on.

[0083] In still further aspects, the separator can be used in a rechargeable battery.

[0084] In still further aspects, a second ceramic layer is disposed at the second surface of the substrate. In certain aspects, only the first ceramic layer can be present. While in other aspects, only the second ceramic layer can be present. Yet, in still further aspects, both the first and the second ceramic layers can be present.

[0085] In still further aspects, the first and / or second ceramic layer can exhibit an ionic conductivity of about 1x10-3mS / cm to about 10 mS / cm, including exemplary values of about 2x10-3mS / cm, about 5x10-3mS / cm, about 7x10-3mS / cm, about 1 x10-2mS / cm, about 2x10-2mS / cm, about 5x10-2mS / cm, about 7x10-2mS / cm, about 1 x10-2mS / cm, about 2x10-1mS / cm, about 5x10-1mS / cm, about 7x10-1mS / cm, about 1 mS / cm, about 2 mS / cm, about 3 mS / cm, about 4 mS / cm, about 5 mS / cm, about 5 mS / cm, about 7 mS / cm, about 8 mS / cm, and about 9 mS / cm. It is understood that the first and / or second ceramic layer can exhibit an ionic conductivity that is in any range formed between any two foregoing values. For example, and without limitations, the ionic conductivity of the first and / or second ceramic layer can be about 01x10-3mS / cm to about 95 mS / cm, about 0.01 mS / cm to about 80 mS / cm, about 0.01 mS / cm to about 70 mS / cm, about 0.01 mS / cm to about 60 mS / cm, about 0.01 mS / cm to about 50 mS / cm, about 0.01 mS / cm to about 40 mS / cm, about 0.01 mS / cm to about 30 mS / cm, about 0.01 mS / cm to about 20 mS / cm, about 0.01 mS / cm to about 10 mS / cm, about 0.01 mS / cm to about 5 mS / cm, about 0.01 mS / cm to about 1 mS / cm, about 0.01 mS / cm to about 0.5 mS / cm, about 0.01 mS / cm to about 0.1 mS / cm, or about 0.5 mS / cm to about 10 mS / cm, or about 0.5 mS / cm to about 70 mS / cm, or about 1 mS / cm to about 100 mS / cm, and so on.

[0086] In still further aspects, the first ceramic layer comprises a first blend comprising a first ceramic material and a first binder. Yet in still further aspects, the second ceramic layer comprises a second blend comprising a second ceramic material and a second binder. In still further aspects, the first and the second blends are substantially homogeneous. In yet still in further aspects, the first and the second blends are homogeneous.

[0087] In still further aspects, the first ceramic material can be the same or different from the second ceramic material. While in still further aspects, the first binder can be the same or different from the second binder.

[0088] Without wishing to be bound by any theory, it is assumed that the first and / or second ceramic material coated on the separators can enhance the thermal resistance of separators, while the first and / or second binder can help maintain the structural integrity of the coated layers. The first and / or second ceramic materials enhance the thermal resistance of separators, while the first and / or binders maintain the structural integrity of coating layers. In yet still further aspects, the first and / or second binders can improve the structural integrity of the whole composite separator by providing cohesion and adhesion.

[0089] It is understood that the coating layers (the coating layers as described herein include the first ceramic layer and / or the second ceramic layer) with larger surface area and higher porosity can increase electrolyte affinity and reduce the amount of flammable liquid electrolyte required for efficient battery operation, making the batteries safer. In yet other aspects, when the coating is applied on the separator at an anode side (the first ceramic layer) of the battery, such coating layers can also regulate charge density at the anode-electrolyte interface.

[0090] In still further aspects, any known in the art and suitable ceramic materials can be used to form the first and / or second ceramic layer. It is understood that the ceramic materials as disclosed herein are substantially Li- ion conductive. In yet other aspects, the ceramic materials disclosed herein can be Na and / or K-ion conductive. As disclosed above, the first ceramic layer comprises a first ceramic material, and the second ceramic layer comprises a second ceramic material, wherein the first and the second ceramic materials can be the same or different.

[0091] It is understood that the reference to the ceramic materials includes reference to the first ceramic material, or the second ceramic material, or both.

[0092] For example, ceramic materials are currently used as solid electrolytes in lithium-based batteries. In certain exemplary and unlimiting aspects, garnet-structured Li7-xLa3Zr2-xTaxOi2 (x=0.6)(Ta-doped LLZO, LLZTO) ceramic materials are known to be efficient solid-state electrolytes with ionic conductivity of > ~10-4Scnrr1. Moreover, the LLZTO phase has a cation transference number of one since it is a crystalline material that conducts Li-ions and no other species, which means that LLZTO can be considered a selective interface that only allows the lithium cations to be transferred - a single-ion conductor. In aspects disclosed herein, such ceramic materials can be used to form the first and the second ceramic layers.

[0093] In still further aspects, the ceramic material (the first ceramic material or the second ceramic material) can comprise LLZO, Ta-doped LLZO (LLZTO), LISICON- type materials, NASICON-type materials, perovskite-based materials, sulfide-based ceramics, argyrodite-based materials, LiPON, or any combination thereof.

[0094] , In some aspects, the first ceramic material and / or second ceramic material comprise Li7-xLasZr2-xTaxOi2, Li7LasZr20i2 Lii+XAlxTi2-x(PO4)3 (LATP), Lii+x+yAlxTi2-xSi3- yOi2, LiioGeP2Si2, Lii4Zn(GeO4)4, LiTi2(PO4)3, Li7LasZr20i2, Lio.sLao.sTiOs, Li2S-P2Ss, Li2S-GeS2, Li2S-SiS2, Li2S-SnS2 Li3.8PO2.sNx, LiePSsX, LisYXe, (wherein X is F, Cl, Br, or I), LiGe2(PO4)3, Lii+xAlxGe2-x(PO4)3 (LAGP), or any combination thereof. In still further aspects, the first ceramic material and / or second ceramic material comprise U7- xLasZr2 x TaxOi2, wherein x=0.6.

[0095] In still further aspects, the separator disclosed herein comprises the first and / or second ceramic layers that are substantially free of lithium, potassium, sodium, or a combination thereof. In still further aspects, the first and / or second ceramic layer is substantially non-conductive for ions of lithium, potassium, sodium, or a combination thereof when they are fabricated. It is understood, however, that some conductivity for ions of lithium, potassium, sodium, or a combination thereof can be observed when the separator is inserted into an electrolyte. In yet still further aspects, the ceramic layers are substantially crystalline.

[0096] In yet still further exemplary and unlimiting aspects, the ceramic layers do not conduct alkali-ions through a bulk of a crystalline lattice. It is understood that in such exemplary aspects, the ceramic material does not comprise lithium, potassium, sodium, or any combination thereof. In still further aspects, the ceramic material can comprise ceria. In yet still further aspects, ceria can be dopped with one or more rare earth elements. In yet still further aspects, the first and / or second ceramic material can comprise Cei xGdxOy, wherein x is greater or equal to 0 and less than 1 , and wherein y is selected to account for the valency of each element and overall neutrality. In such aspects, x can be about 0.01 , about 0.05, about 0.1 , about 0.15, about 0.2, about 0.25, about 0.3, about 0.35, about 0.4, about 0.45, about 0.6, about 0.55, about 0.6, about 0.65, about 0.7, about 0.75, about 0.8, about 0.85, about 0.9, and about 0.95. It is understood that x can be in any range formed between any two foregoing values. For example, and without limitations, the x can be about 0.01 mol% to about 0.99 mol%, or about 0.05 mol% to about 0.95 mol%, or about 0.1 mol% to about 0.9 mol%, and so on. In yet still further aspects, the first and / or second ceramic material comprises Ceo.9Gdo.1O1.95.

[0097] It is understood that in some aspects, when x is 0, the ceramic material is substantially doping-free. In still further aspects, Gd behaves as a dopant. It is understood that ceria can also be doped with other rare-earth elements, such as yttrium, samarium, or a combination thereof. In yet still further aspects, ceria can be dopped with zirconium and lanthanides. Yet in still further aspects, any ceramic materials that are configured to be compatible with any of the disclosed herein binder materials, processing solvents and electrolytes can be utilized. For example, and without limitations, the ceramic material can also comprise yttria-stabilized zirconia (YSZ), wherein Y2O3 can be present from greater than 0 mol% to about 20 mol%, including exemplary values of about 0.1 mol%, about 0.5 mol%, about 1 mol%, about 2 mol%, about 3 mol%, about 4 mol%, about 5 mol%, about 6 mol%, about 7 mol%, about 8 mol%, about 9 mol%, about 10 mol%, about 11 mol%, about 12 mol%, about 13 mol%, about 14 mol%, about 15 mol%, about 16 mol%, about 17 mol%, about 18 mol%, and about 19 mol%. It is understood that the Y2O3 can be in any range formedbetween any two foregoing values. For example, and without limitations, the Y2O3 can be greater than 0 mol% to about 20 mol%, or about 0.1 mol% to about 15 mol%, or about 0.01 mol% to about 10 mol%, or about 0.01 mol% to about 5 mol%, or about 0.01 mol% to about 1 mol%, or about 0.01 mol% to about 0.5 mol%, and so on.

[0098] In yet still further aspects, the first and / or second ceramic material can comprise AI2O3, SiO2, ZnO, Ga2Os, or any combination thereof.

[0099] In still further aspects, the first and / or the second binder can be any binder suitable for the desired application. In still further aspects, the first and / or the second binder is a polymeric material. In yet still further aspects, the first and / or the second binder can be any known in the art polymer electrolyte suitable for Li-based, Na- based, or K-based batteries.

[0100] In still further aspects, the first and / or the second binder is a polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), carboxymethylcellulose (CMC), styrene-butadiene rubber (SBR), polyacrylic acid (PAA), polyvinyl alcohol (PVA), polyvinyl butyral (PVB), polyvinylpyrrolidone (PVP), ethyl cellulose (EC), copolymers thereof, or any combination thereof. In yet still further aspects, the binder can comprise polyethylene glycol)diacrylate (PEGDA), polyacrylonitrile (PAN), poly(3,4-ethylenedioxythiphene) (PEDOT), poly(3,4- ethylenedioxythiphene)-polystyrene sulfonate (PEDOT:PSS), polymethyl methacrylate (PMMA), polyvinyl chloride (PVC), poly(urethane) acrylate (PUA), polyethylene glycol (PEG), polycarbonate (PC), poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF- HFP), polypropylene carbonate (PPG), polypropylene glycol (PPG), polydimethylsiloxane (PDMS), poly(vinyl alcohol) (PVA), polycaprolactone (PCL), poly(trimethylene carbonate) (PTMC), copolymers thereof, or any combination thereof.

[0101] It is understood that the term “binder,” as disclosed herein, refers to the first binder, the second binder, or both. In yet in still further exemplary and unlimiting aspects, the first and / or the second binder can comprise PEO. It is understood that PEO binder exhibits a superior adhesion capability, low material costs, and good interfacial contact with the ceramics. PEO is inert and stable in a Li metal cell when thecut-off voltage is not above 4 V vs. Li / Li+. It is understood that to obtain a high ionic conductivity ceramic layer, a desired ratio between the ceramic material and the binder needs to be obtained.

[0102] In yet still further aspects, the binder can comprise EC. In some exemplary and unlimiting aspects, the first and / or second ceramic layers, if present, can comprise the first and / or second ceramic material comprising Ceo.9Gdo 1O1.95 and the first and / or second binder comprising EC.

[0103] In such exemplary and unlimiting aspects, EC can be present as a viscous material having a viscosity of about 30 to about 70 mPa«s, including exemplary values of about 35 mPa«s, about 40 mPa*s, about 45 mPa*s, about 50 mPa*s, about 55 mPa«s, about 60 mPa«s, and about 65 mPa«s. It is understood that the EC can have any viscosity value that falls in any range formed between any two foregoing values. For example, and without limitations, the viscosity can be about 35 mPa*s to about 70 mPa*s, or about 40 mPa«s to about 70 mPa*s, or about 50 mPa«s to about 70 mPa*s, or about 30 mPa«s to about 60 mPa*s, or about 30 mPa«s to about 50 mPa*s, or about 30 mPa*s to about 40 mPa*s, and so on.

[0104] In still further aspects, the first and / or second ceramic material is present in an amount of about 60 wt% to less than about 100 wt% based on the total weight of the blend, including exemplary values of about 62 wt %, about 65 wt %, about 67 wt %, about 70 wt %, about 72 wt %, about 75 wt %, about 77 wt %, about 80 wt %, about 82 wt %, about 85 wt %, about 87 wt %, about 90 wt %, about 92 wt %, about 95 wt %, about 99 wt %, and about 99.99 wt %. It is understood that the first and / or second ceramic material can be present in any range formed between any two foregoing values. For example, and without limitations, the first and / or second ceramic material can be present in an amount of about 60 wt% to about 99 wt%, or about 60 wt% to about 90 wt%, or about 60 wt% to about 80 wt%, or about 70 wt% to about 99 wt% about 80 wt% to about 99 wt%, and so on.

[0105] In still further aspects, the first and / or second binder is present in an amount greater than 0 wt % to about 40 wt% based on the total weight of the blend, including exemplary values of about 0.01 wt %, about 0.1 wt %, about 0.5 wt %, about 1 wt %, about 2 wt %, about 5 wt %, about 7 wt %, about 10 wt %, about 12 wt %, about 15 wt %, about 20 wt %, about 22 wt %, about 25 wt %, about 27 wt %, about 30 wt %, about 32 wt %, about 35 wt %, and about 39 wt %. It is understood that the first and / or second binder can be present in any range formed between any two foregoing values. For example, and without limitations, the first and / or second binder can be present in an amount of about 0.01 wt% to about 40 wt%, or about 0.1 wt% to about 40 wt%, or about 0.5 wt% to about 40 wt%, or about 1 wt% to about 40 wt% about 10 wt% to about 40 wt%, and so on.

[0106] Without wishing to be bound by any theory, it is hypothesized that at a higher ceramic content, higher ionic conductivity can be observed since the Li-ion conductive ceramic can form percolation pathways for Li+transport at the interphase. This hard ceramic coating layer can provide a physical barrier to lithium metal dendrite growth, reducing the risk of internal short circuits.

[0107] In yet still further aspects, the first and / or the second ceramic layer can also comprise a filler. It is understood that the filler in the first and the second ceramic material can be the same or different. In still further aspects, the first and / or the second ceramic layer can also comprise a salt. It is understood that the salt in the first and the second ceramic material can be the same or different. It is further understood that the filler can be added to the substantially homogeneous blends when forming the ceramic layers. Similarly, it is understood that the salts can be added to the substantially homogeneous blends when forming the ceramic layers.

[0108] In some exemplary and unlimiting aspects, the filler and / or salts can further increase the conductivity of the ceramic layer.

[0109] It is understood that any known in the art fillers suitable for the desired application can be utilized. It is understood that the preferable fillers are those that donot negatively affect the ionic conductivity of the coating and, as a result, the ionic conductivity of the separator as a whole.

[0110] In still further aspects, the filler comprises a carbon black, a modified carbon black, a graphene, a multi-layer graphene, carbon fibers, carbon nanotubes, carbon nanospheres, graphite, a reduced graphene oxide, or any combination thereof.

[0111] lt is understood that any known in the art salts suitable for the desired application can be utilized. For example, any known salts that are used in the electrolytes suitable for the Li salts can be utilized. It is further understood that while the exemplary aspects are described as they pertain to Li-based batteries, the disclosure also relates to other aspects as they pertain to Na or K-based batteries.

[0112] In certain aspects, the salt that is present in the blends disclosed herein can comprise lithium bis(fluorosulfonyl)imide, lithium trifluoromethanesulfonate, lithium bis(trifluoromethanesulfonyl)imide, lithium difluoro(oxalato)borate, lithium bis(oxalate) borate, lithium perchlorate, lithium tetrafluoroborate, lithium difluorophosphate, lithium hexafluorophosphate, lithium hexafluroarsenate, lithium tetrachloroaluminate, lithium chlorate, lithium borate, lithium triflate, lithium iodate, or any combination thereof. It is understood that in other aspects, where, for example, the separator is desired for Na- or K-based batteries, similar as disclosed above, salts of Na and K can be added to the blends of the ceramic materials and the binders.

[0113] In still further aspects, if salts are present, they can first be mixed with the binders, thereby increasing the conductivity of the binders. In such exemplary and unlimiting aspects, the salts can be solvated within the binder. In yet still in further aspects, the salts can be added to the blend of the ceramic material and the binder in any desirable order.

[0114] As disclosed above, in certain aspects, some of the disclosed herein ceramic layers are substantially free of salts. Yet in still further aspects, the disclosed herein ceramic layers can be substantially free of salts comprising Li, Na, K, or any combination thereof.

[0115] In still further aspects, the substrate can be any substrate suitable for use in lithium (or Na or K) batteries. For example and without limitations, the substrate can comprise a polymeric film, a glass fiber separator, a cellulose-based separator, or any combination thereof. It is understood that the substrate needs to be stable for the battery operation and not degrade. In certain aspects, the substrate is a polymeric film. In yet still further aspects, the polymeric film can comprise polyolefin. It is understood, however, that the polymeric films can also comprise nylons, polyimides, or any others that can exhibit the desired properties. In still further aspects, if the substrate is a polymeric film comprising a polyolefin, such a polyolefin can comprise polyethylene, polypropylene, copolymers thereof, and a combination thereof.

[0116] The separators disclosed herein can have an overall thickness that is substantially comparable to or smaller than a thickness of commercially available separators. In some exemplary and unlimiting aspects, the separator has a total thickness of less than about 35 microns, less than about 30 microns, less than about 25 microns, less than about 20 microns, less than about 15 microns, less than about 10 microns, or even equal to or less than about 5 microns.

[0117] In yet still further aspects, the separator can have a total thickness of about 1 micron to about less than about 35 microns, including exemplary values of about 1 .5 microns, about 2 microns, about 2.5 microns, about 3 microns, about 3.5 microns, about 4 microns, about 4.5 microns, about 5 microns, about 5.5 microns, about 6 microns, about 6.5 microns, about 7 microns, about 7.5 microns, about 8 microns, about 8.5 microns, about 9 microns, about 9.5 microns, about 10 microns, about 10.5 microns, about 1 1 microns, about 1 1 .5 microns, about 12 microns, about 12.5 microns, about 13 microns, about 13.5 microns, about 14 microns, about 14.5 microns, about 15 microns, about 15.5 microns, about 16 microns, about 16.5 microns, about 17 microns, about 17.5 microns, about 18 microns, about 18.5 microns, about 19 microns, about 19.5 microns, about 20 microns, about 20.5 microns, about 21 microns, about 21 .5 microns, about 22 microns, about 22.5 microns, about 23 microns, about 23.5 microns, about 24 microns, about 24.5 microns, about 25 microns, about 25.5 microns,about 26 microns, about 26.5 microns, about 27 microns, about 27.5 microns, about 28 microns, about 28.5 microns, about 29 microns, about 29.5 microns, about 30 microns, about 30.5 microns, about 31 microns, about 31 .5 microns, about 32 microns, about 32.5 microns, about 33 microns, about 33.5 microns, about 34 microns, and about 34.5 microns. The thickness can fall within any range formed by any of the values disclosed above. In certain aspects, the separator has a total thickness of about 1 micron to about 30 microns, about 5 microns to about 30 microns, about 1 to 25 microns, about 1 to about 20 microns, and so on.

[0118] In still further aspects, the first ceramic layer and / or the second ceramic layer, if present, have a thickness of about 1 micron to about 20 microns, including exemplary values of about 2 microns, about 3 microns, about 4 microns, about 5 microns, about 6 microns, about 7 microns, about 8 microns, about 9 microns, about 10, about 12 microns, about 13 microns, about 14 microns, about 15 microns, about 16 microns, about 17 microns, about 18 microns, and about 19 microns. The thickness can fall within any range formed by any of the values disclosed above. In certain aspects, the first ceramic layer and / or the second ceramic layer can have a thickness of about 1 micron to about 20 microns, about 1 microns to about 15 microns, about 1 to 10 microns, about 1 to 5 microns, 5 microns to about 20 microns, about 10 microns to about 20 microns, and so on.

[0119] In yet still further aspects, the second ceramic layer has the same or different thickness as the first ceramic layer disposed on the first surface of the substrate.

[0120] It is understood that the low overall thickness of the separator disclosed herein, combined with the high conductivity of the ceramic layer and high transference number of lithium (or potassium or sodium in respective batteries), allows for further minimizing the battery size without compromising its performance.

[0121] In still further aspects, the first ceramic layer and the second ceramic layer, if present, comprise a plurality of pores. In still further aspects, the first and / or the second ceramic layer is substantially permeable to a solvent. In still further aspects, the pores have a size of about 2 nm to about 10 microns, including exemplary valuesof about 3 nm, about 4 nm, about 5 nm, about 6 nm, about 7 nm, about 8 nm, about 9 nm, about 10 nm, about 15 nm, about 20 nm, about 30 nm, about 50 nm, about 100 nm, about 200 nm, about 300 nm, about 400 nm, about 500 nm, about 600 nm, about 700 nm, about 800 nm, about 900 nm, about 1 micron, about 2 microns, about 3 microns, about 4 microns, about 5 microns, about 6 microns, about 7 microns, about 8 microns, and about 9 microns.

[0122] In yet still further aspects, the first and / or the second ceramic material present in the ceramic layer can have a particle size on a nanoscale and / or a microscale. In some exemplary and unlimiting aspects, the first and / or ceramic material can have a particle size of about 20 nm to less than about 20 microns, including exemplary values of about 25 nm, about 30 nm, about 40 nm, about 50 nm, about 60 nm, about 70 nm, about 80 nm, about 90 nm, about 100 nm, about 150 nm, about 200 nm, about 250 nm, about 300 nm, about 350 nm, about 400 nm, about 450 nm, about 500 nm, about 550 nm, about 600 nm, about 650 nm, about 700 nm, about 750 nm, about 800 nm, about 850 nm, about 900 nm, about 1 micron, about 1 .5 microns, about 2 microns, about 2.5 microns, about 3 microns, about 3.5 microns, about 4 microns, about 4.5 microns, about 5 micron, about 5.5 microns, about 6 microns, about 6.5 microns, about 7 microns, about 7.5 microns, about 8 microns, about 8.5 microns, about 9 micron, about 9.5 microns, about 10 microns, about 10.5 microns, about 11 microns, about 11 .5 microns, about 12 microns, about 12.5 microns, about 13 micron, about 13.5 microns, about 14 microns, about 14.5 microns, about 15 microns, about 15.5 microns, about 16 microns, about 16.5 microns, about 17 micron, about 17.5 microns, about 18 microns, about 18.5 microns, about 19 microns, and about 19.5 microns. The particle size can fall within any range formed by any of the values disclosed above. In certain aspects, first and / or ceramic material can have a particle size of about 20 nm to about 20 microns, about 50 nm to about 20 microns, about 100 nm to about 20 microns, about 150 nm to about 20 microns, and so on.

[0123] In yet still further aspects, the first ceramic material and the second ceramic material, if present, have a particle size of about 500 nanometers. In still furtheraspects, the ceramic layers can have a first plurality of particles and a second plurality of articles. In such exemplary and unlimiting aspects, the first plurality of particles can have a particle size of about 500 nanometers. While in other exemplary and unlimiting aspects, the second plurality of particles can have a particle size of about 3 to about 20 microns, including exemplary values of about 4 microns, about 5 microns, about 6 microns, about 7 microns, about 8 microns, about 9 microns, about 10 microns, about 11 microns, about 12 microns, about 13 microns, about 14 microns, about 15 microns, about 16 microns, about 17 microns, about 18 microns, and about 19 microns. The second particle size can fall within any range formed by any of the values disclosed above. In certain aspects, the first and / or ceramic material can have a second particle size of about 3 microns to about 20 microns, about 5 microns to about 20 microns, about 7 microns to about 20 microns, about 10 microns to about 20 microns, and so on.

[0124] In still further aspects, the first ceramic layer is uniformly disposed on at least the first surface of the substrate. While in still further aspects, the second ceramic layer is uniformly disposed on at least the second surface of the substrate. In such exemplary and unlimiting aspects, the thickness of the first and / or second ceramic layer is substantially identical across the length and / or width of the separator. However, it is understood that the first thickness and the second thickness can be the same or different. In still further aspects, the first and / or second ceramic layer is continuous.

[0125] In still further aspects, the separator exhibits a lithium transference number greater than about 0.65, greater than about 0.66, greater than about 0.67, greater than about 0.68, greater than about 0.69, greater than about 0.7, greater than about 0.71 , greater than about 0.72, greater than about 0.73, greater than about 0.74, greater than about 0.75, greater than about 0.76, greater than about 0.77, greater than about 0.78, greater than about 0.79, greater than about 0.8, greater than about 0.81 , greater than about 0.82, greater than about 0.83, greater than about 0.84, greater than about 0.85, greater than about 0.86, greater than about 0.87, greater than about 0.88, greater thanabout 0.89, greater than about 0.9, greater than about 0.91 , greater than about 0.92, greater than about 0.93, greater than about 0.94, greater than about 0.95, greater than about 0.96, greater than about 0.97, greater than about 0.98, greater than about 0.99 in the presence of an electrolyte. In yet still further aspects, the separator exhibits a lithium transference number equal to or greater than about 0.7, equal to or greater than about 0.71 , equal to or greater than about 0.72, equal to or greater than about 0.73, equal to or greater than about 0.74, equal to or greater than about 0.75, equal to or greater than about 0.76, equal to or greater than about 0.77, equal to or greater than about 0.78, equal to or greater than about 0.79, equal to or greater than about 0.80, equal to or greater than about 0.81 , equal to or greater than about 0.82, equal to or greater than about 0.83, equal to or greater than about 0.84, equal to or greater than about 0.85, equal to or greater than about 0.86, equal to or greater than about 0.87, equal to or greater than about 0.88, equal to or greater than about 0.89, or equal to or greater than about 0.90 in the presence of an electrolyte.

[0126] In still further aspects, the separator exhibits substantial wettability when inserted into the electrolyte. It is understood that the wettability can be determined by how fast a drop of the electrolyte is dispersed over a surface of the separator and then adsorbed into the separator. It is understood that the wettability can be physically measured by a "wetting angle" where if something is not fully wet, there is a measured angle greater than 0, but if something is completely wet, it shows a wetting angle of 0.

[0127] In still further aspects, the separator can exhibit similar transference numbers for potassium and / or sodium.

[0128] In still further aspects, the ceramic layer can be disposed on the substrate by any known in the art methods. Some of the methods of making it are disclosed below.RECHARGEABLE BATTERIES

[0129] Also disclosed herein is a rechargeable battery comprising any of the disclosed herein separations, an anode material, a cathode material and an electrolyte.

[0130] In certain aspects, the separator disclosed herein is positioned such that the first ceramic layer disposed on the first surface of the substrate is adjacent to the anode. Yet in other aspects, the separator can be positioned such that the second ceramic layer disposed on the second surface of the substrate is adjacent to the cathode. In still further aspects, if only one ceramic layer is present, it can be disposed on the surface of the substrate that is adjacent to the cathode or on the surface of the substrate that is adjacent to the anode. Yet in still further aspects, when the separator comprises the first ceramic layer on the first surface and the second ceramic layer on the second surface of the substrate, the first surface is positioned adjacent to the anode, and the second surface is positioned adjacent to the cathode.

[0131] In still further aspects, the ceramic layer disclosed herein is configured to be substantially wet by the electrolyte.

[0132] In certain aspects, the anode is a lithium metal. In yet other aspects, the anode is a sodium metal. While in still further aspects, the anode is a potassium metal.

[0133] In yet still further aspects, the electrolyte comprises a nonaqueous solvent and a salt. In such exemplary and unlimiting aspects, the nonaqueous solvent can comprise dioxane, dimethoxyethane (DME), ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), N-methyl acetamide (NMA), acetonitrile (ACN), sulfone, sulfolane, 1 ,3-dioxolane, 1 ,2-dioxolane, 1 ,3-dimethyle-2-imidazolidinone (DMI), 1 ,1 ,2,2-tetrafluoroethylene-2,2,3,3,- tetrafluoropropyl ether (TTE), N-methyl 2-pyrrolidone (NMP), fluoroethylene carbonate (EEC), propylene Carbonate (PC), tetrahydrofuran (THE), bis(2,2,2-trifluoroethyl) ether (BTFE) or any combination thereof. Yet in other exemplary and unlimiting aspects, the salt can comprise lithium bis(fluorosulfonyl)imide, lithium trifluoromethanesulfonate, lithium bis(trifluoromethanesulfonyl)imide, lithium difluoro(oxalato)borate, lithium bis(oxalate) borate, lithium perchlorate, lithium tetrafluoroborate, lithium difluorophosphate, lithium hexafluorophosphate, lithium hexafluroarsenate, lithium tetrachloroaluminate, lithium chlorate, lithium borate, lithium iodate, lithium triflate, lithium nitrate, or a combination thereof.

[0134] In still further aspects, the electrolyte can comprise mixtures of the nonaqueous solvents in any suitable and desired ratios. For example and without limitations, the electrolyte can comprise a mixture of EC:DEC in a volume ratio of about 1 :9 to about 9:1 , including exemplary values of about 1 :9, about 1 :4, about 3:7, about 2:3, about 1 :1 , about 3:2, about 7:3, about 4:1 , or about 9:1 .

[0135] Yet in other aspects, the electrolyte can comprise a mixture of DME:TTE in a molar ratio of about 1 :3 to about 2:1 , including exemplary values of about 1 :3, about 1 :1 , or about 2:1 .

[0136] In still further aspects, the electrolyte can comprise a mixture of DME:DOL:DMI, wherein the mixture of DME:DOL is present in a volume ratio of about 9:1 to about 2:3, including exemplary values of about 1 :9, about 1 :4, about 3:7, about 2:3. In yet still further aspects, such an exemplary mixture can comprise about 0.05 wt % to about 5 wt%, including exemplary values of about 0.1 wt %, about 0.25 wt %, about 0.5 wt %, about 0.75 wt %, about 1 wt %, about 1 .2 wt %, about 1 .5 wt %, about 1 .7 wt %, about 2 wt %, about 2.2 wt %, about 2.5 wt %, about 2.7 wt %, about 3 wt %, about 3.2 wt %, about 3.5 wt %, about 3.7 wt %, about 4 wt %, about 4.2 wt %, about 4.5 wt %, and about 4.7 wt % of DMI based on the total weight of the electrolyte. The DMI amount can fall within any range formed by any of the values disclosed above. In certain aspects, the DMI can be present in an amount of about 0.05 wt % to about 5 wt %, about 0.1 wt % to about 5 wt %, about 0.5 wt % to about 5 wt %, about 1 wt % to about 5 wt %, and so on based on the total weight of the electrolyte.

[0137] In yet still in further aspects, any of the disclosed herein solvents or mixtures thereof can comprise any of the disclosed herein salts present in any desirable concentration. In some aspects, the salt can be present in a concentration of about 0.1 M to about 10 M, depending on a specific salt, and including exemplary values of about 0.5 M, about 1 M, about 1 .5 M, about 2 M, about 2.5 M, about 3 M, about 3.5 M, about 4 M, about 4.5 M, about 5 M, about 5.5 M, about 6 M, about 6.5 M, about 7 M, about 7.5 M, about 8 M, about 8.5 M, about 9 M, about 9.5 M. The salt concentration can fall within any range formed by any of the values disclosed above. In certainaspects, the salt can be present in an amount of about 0.1 M to about 10 M, about 0.5 M to about 10 M, about 0.1 M to about 5 M, about 1 M to about 10 M, and so on.

[0138] It is understood that in some exemplary and unlimiting aspects, the amount of salt in the electrolyte can be expressed in weight % and not molarity. In some exemplary aspects, the salt can be present in any desired amount for preferable application. In certain aspects, the salt can be present in an amount greater than 0 wt% to less than 100 wt% based on the total amount of the electrolyte. In certain aspects, the salt can be present in an amount of about 0.1 wt%, about 0.5 wt%, about 1 wt%, about 5 wt%, about 10 wt%, about 20 wt%, about 30 wt%, about 40 wt%, about 50 wt%, about 60 wt%, about 70 wt%, about 80 wt%, and about 90 wt%. The salt amount can fall within any range formed by any of the values disclosed above. In certain aspects, the salt can be present in an amount of about 0.05 wt % to about 90 wt %, about 0.1 wt % to about 85 wt %, about 0.5 wt % to about 80 wt %, about 1 wt % to about 50 wt %, and so on. It is understood that in some aspects, the weight percentage of the salt can refer to the total presence of any salt in the electrolyte. While in other aspects, the weight percentage can describe a particular salt.

[0139] In still further aspects, the electrolytes that can be used in the disclosed herein rechargeable batteries can comprise about 1 M to about 3 M, including exemplary values of about 1 .1 M, about 1 .2 M, about 1 .3 M, about 1 .4 M, about 1 .5 M, about 1 .6 M, about 1 .7 M, about 1 .8 M, about 1 .9 M, about 2 M, about 2.1 M, about 2.2 M, about 2.3 M, about 2.4 M, about 2.5 M, about 2.6 M, about 2.7 M, about 2.8 M, and about 2.9 M of lithium bis(fluorosulfonyl)imide (or about 1 M to about 3 M, about 1 M to about 2.5 M, about 1 M to about 2 M, and so on) dissolved in a mixture of solvents comprising DME and TTE having a ratio of about 1 :3 to about 2:1 , including exemplary values of about 1 :3, about 1 :1 , or about 2:1 .

[0140] In still further aspects, the electrolyte can comprise about 1 M to about 8 M, including exemplary values of about 1 .5 M, about 2 M, about 2.5 M, about 3 M, about 3.5 M, about 4 M, about 4.5 M, about 5 M, about 5.5 M, about 6 M, about 6.5 M, about 7 M, and about 7.5 M of lithium bis(fluorosulfonyl)imide (or about 1 M to about 3 M,about 1 M to about 2.5 M, about 1 M to about 2 M, and so on) dissolved in a solvent comprising DME.

[0141] In still further aspects, the electrolytes that can be used in the disclosed herein rechargeable batteries can comprise about 1 M to about 4 M, including exemplary values of about 1 .1 M, about 1 .2 M, about 1 .3 M, about 1 .4 M, about 1 .5 M, about 1 .6 M, about 1 .7 M, about 1 .8 M, about 1 .9 M, about 2 M, about 2.1 M, about 2.2 M, about 2.3 M, about 2.4 M, about 2.5 M, about 2.6 M, about 2.7 M, about 2.8 M, about 2.9 M, about 3 M, about 3.1 M, about 3.2 M, about 3.3 M, about 3.4 M, about 3.5 M, about 3.6 M, about 3.7 M, about 3.8 M, and about 3.9 M of lithium bis(fluorosulfonyl)imide (or about 1 M to about 3 M, about 1 M to about 2.5 M, about 1 M to about 2 M, and so on) and about 0.05 M to about 0.5 M, including exemplary values of about 0.06 M, about 0.07 M, about 0.08 M, about 0.09 M, about 0.1 M, about 0.15 M, about 0.2 M, about 0.25 M, about 0.3 M, about 0.35 M, about 0.4 M, and about 0.45 M of lithium difluoro(oxalato)borate (or about 0.05 M to about 0.45 M, about 0.05 M to about 0.35 M, about 0.05 M to about 0.25 M, and so on) dissolved in a mixture of solvents comprising about 40 vol% to about 90 vol% of DME, about 10 vol% to about 60 vol% of DOL, and about 0.05 wt% to about 5 wt% of DML In such exemplary aspects, the mixture of solvents can comprise about 40 vol% to about 90 vol% of DME, including exemplary values of about 45 vol%, about 50 vol%, about 55 vol%, about 60 vol%, about 65 vol%, about 70 vol%, about 75 vol%, about 80 vol%, and about 85 vol% (or about 40 vol% to about 90 vol%, about 40 vol% to about 80 vol%, 40 vol% to about 70 vol%, 40 vol% to about 60 vol%, and so on). In such exemplary aspects, the mixture of solvents can comprise about 10 vol% to about 60 vol% of DOL, including exemplary values of about 15 vol%, about 20 vol%, about 25 vol%, about 30 vol%, about 35 vol%, about 40 vol%, about 45 vol%, about 50 vol%, and about 55 vol% (or about 10 vol% to about 60 vol%, about 10 vol% to about 50 vol%, 10 vol% to about 40 vol%, 10 vol% to about 30 vol%, and so on). In still further aspects, the mixture of solvents can comprise about 0.05 wt% to about 5 wt% of DMI, including exemplary values of about 0.1 wt%, about 0.25 wt%, about 0.5 wt%, about 0.75 wt%, about 1 wt%, about 1 .2 wt%, about 1 .5 wt%, about 1 .7 wt%, about 2 wt%, about 2.2 wt%, about 2.5 wt%,about 2.7 wt%, about 3 wt%, about 3.2 wt%, about 3.5 wt%, about 3.7 wt%, about 4 wt%, about 4.2 wt%, about 4.5 wt%, and about 4.7 wt% of DM I based on the total weight of the electrolyte (or about 0.05 wt% to about 5 wt%, about 0.05 wt% to about 4 wt%, about 0.05 wt% to about 3 wt%, about 0.05 wt% to about 2 wt%, and so on). It is understood that unless specifically mentioned otherwise, every value disclosed herein as exemplary values can also form ranges between those values to provide specific amounts or properties of the disclosed elements.

[0142] In still further aspects, the electrolyte can comprise bis(fluorosulfonyl)imide (LiFSI)- DME-TTE electrolyte. It is understood that LiFSI:DME:TTE can be present in any ratio. In some exemplary and unlimiting aspects, the ratio can be about 1 :1 :1 by mole to about 1 :5:5 by mole, including exemplary values of about 1 :1 :2, about 1 :1 .2:2, about 1 :1 .5:2, about 1 :1 .7:2, about 1 :2:2, about 1 :1 :3, about 1 :1 .2:3, about 1 :1 .5:3, about 1 :1 .7:3, about 1 :2:3, about 1 :2.2:3, about 1 :2.5:3, about 1 :2.7:3, about 1 :3:3, about 1 :3.2:3, about 1 :3.5:3, about 1 :3.7:3, about 1 :4:3, about 1 :4:4, about 1 :3:4, about 1 :3:2, about 1 :3:1 , about 1 :4:5, about 1 :2:5, about 1 :3:5, about 1 :5:1 , about 1 :5:2, about 1 :5:4, and the like. In yet still further aspects, the ratio can be about 1 :1 .2:3. While in other aspects, the ratio can be about 1 :2:3. It is understood, however, that any ratio values within the range can be used to form the desired electrolyte.

[0143] In still further aspects, the electrolyte can comprise a mixture of (LiFSI)- DME- TTE with LiNOs and FEC. Again, it is understood that the ratios and concentrations of each component can be selected from any ratios or concentrations disclosed above without any limitations. For example, the (LiFSI)- DME-TTE / LiNOs / FEC electrolyte can comprise (LiFSI)- DME-TTE in a ratio of about 1 :2:3 by more and about 1 wt % of LiNOs and about 5 wt% FEC based on the total weight of the electrolyte.

[0144] In still further aspects, the electrolyte can comprise a mixture of EMC:FEC in a volume ratio of about 12:1 to about 1 :12, including exemplary values of about 11 :1 , about 10:1 , about 9:1 , about 8:1 , about 7:1 , about 6:1 , about 5:1 , about 4:1 , about 3:1 , about 2:1 , about 1 :1 , about 1 :2, about 1 :3, about 1 :4, about 1 :5, about 1 :6, about 1 :7, about 1 :8, about 1 :9, about 1 :10, and about 1 :11.

[0145] In yet still further aspects, wherein the electrolyte comprises about 0.1 M to about 4 M of lithium bis(fluorosulfonyl)imide (or about 0.1 M to about 4 M, about 0.1 M to about 3 M, about 0.1 M to about 2.5 M, about 0.1 M to about 2 M, about 0.1 M to about 1 M, about 0.5 M to about 3 M or about 1 M to about 3 M, and so on).and about 0.1 wt% to about 5 wt% of lithium difluoro(oxalato)borate (or about 0.5 wt% to about 5 wt%, about 0.1 wt% to about 4 wt%, about 0.1 wt% to about 3 wt%, about 0.1 wt% to about 2 wt%, and so on) dissolved in a mixture of solvents comprising a mixture of EMC:FEC in a volume ratio of about 12:1 to about 1 :12.

[0146] In still further aspects, a solid electrolyte interphase is formed between the anode and the first ceramic layer deposited on the first surface of the substrate of the separator. In still further aspects, this solid electrolyte interphase is substantially stable throughout the battery operation.

[0147] In still further aspects, the rechargeable batteries, as disclosed herein, comprise a cathode. It is understood that any known in the art cathode materials that can be useful for the desired purpose can be utilized. In some aspects, the cathode can be a metal cathode or composite cathode. If the metal cathode is used, such an electrochemical cell can be a symmetrical electrochemical cell. In such an exemplary aspect, when the electrochemical cell is symmetrical, both anode and cathode comprise the same material, for example, and without limitation, it can comprise Li. In other words, there are some exemplary aspects where the anode material of the electrochemical cell is Li and the cathode material used in the same cell is also Li. It is understood that the same is true for K and / or Na batteries.

[0148] In still further aspects, the cathode can comprise layered oxides, vanadium- based cathode, sulfur-based cathode, manganese-based cathode, rocksalt cathode, disordered rocksalt cathode, lithium-rich cathode, high voltage ceramic, low voltage ceramic, NMC (nickel-manganese-cobalt oxide) cathode, NCA (nickel-cobalt- aluminum oxide) cathode, LCO (lithium-cobalt oxide) cathode, LFP (lithium iron phosphate) cathode, fluoride-based cathode, sulfur selenium cathode, sulfur selenium tellurium cathode, spinels, olivines, or any combination thereof.

[0149] Yet in still further aspects, the cathode comprises a high density nickel-rich layered transition metal oxide ( Li[NixMnyCoz]O2 (x+y+z = 1)), a lithium iron phosphate (LFP), lithium manganese oxide (LiMn2O4), or nickel-doped lithium manganese oxide (Li[Nio.5Mni.5]04).

[0150] In still further aspects, the cathode can further comprise a filler and / or a binder. It is understood that any known in the art and suitable for the desired applications fillers and binders can be utilized. For example, and without limitations, the filler can comprise a carbon black, a modified carbon black, a graphene, multi-layer graphene, carbon fibers, carbon nanotubes, carbon nanospheres, graphite, a reduced graphene oxide, or any combination thereof. Yet in still further aspects, the binder present in the cathode material can comprise polyvinylidene fluoride (PVDF), polyethylene oxide), cellulose, carboxymethylcellulose (CMC), a polytetrafluoroethylene (PTFE), styrenebutadiene rubber (SBR), polyacrylic acid (PAA), polyvinyl alcohol (PVA), polyvinyl butyral (PVB), polyvinylpyrrolidone (PVP), ethyl cellulose (EC), copolymers thereof, or any combination thereof.

[0151] In still further aspects, the batteries disclosed herein are configured to operate in a temperature range from about 20 °C up to about 100 °C, including exemplary values of about 25 °C, about 30 °C, about 35 °C, about 40 °C, about 45 °C, about 50 °C, about 55 °C, about 60 °C, about 65 °C, about 70 °C, about 75 °C, about 80 °C, about 85 °C, about 90 °C, and about 95 °C (or about 20 °C up to about 100 °C, about 20 °C up to about 90 °C, about 20 °C up to about 70 °C, about 20 °C up to about 60 °C, about 20 °C up to about 50 °C, about 20 °C up to about 40 °C, about 30 °C up to about 100 °C, about 40 °C up to about 100 °C, about 50 °C up to about 100 °C).

[0152] In still further aspects, the rechargeable batteries that comprise the disclosed herein electrolytes and separators exhibit exceptional performance over hundreds of plating / stripping cycles. In still further aspects, the anode in the disclosed herein batteries is substantially free of dendrites during a plating / stripping cycle of a battery operation.

[0153] Yet in still further aspects, the ceramic layer disposed on the first surface of the substrate is substantially free of dendrites during a plating / stripping cycle of a battery operation.

[0154] In some exemplary and unlimiting aspects, disclosed herein is a rechargeable battery comprising: a Li anode material; a cathode material; and an electrolyte, wherein the electrolyte comprises about 1 M to about 4 M of lithium bis(fluorosulfonyl)imide and about 0.05 M to about 0.5 M of lithium difluoro(oxalato)borate dissolved in a mixture of solvents comprising about 40 vol% to about 90 vol% of DME, about 10 vol% to about 60 vol% of DOL, and about 0.05 wt% to about 5 wt% of DMI.

[0155] In such aspects, the electrolytes comprise about 1 M to about 4 M, including exemplary values of about 1 .1 M, about 1 .2 M, about 1 .3 M, about 1 .4 M, about 1 .5 M, about 1 .6 M, about 1 .7 M, about 1 .8 M, about 1 .9 M, about 2 M, about 2.1 M, about 2.2 M, about 2.3 M, about 2.4 M, about 2.5 M, about 2.6 M, about 2.7 M, about 2.8 M, about 2.9 M, about 3 M, about 3.1 M, about 3.2 M, about 3.3 M, about 3.4 M, about 3.5 M, about 3.6 M, about 3.7 M, about 3.8 M, and about 3.9 M of lithium bis(fluorosulfonyl)imide (or about 1 M to about 4 M, about 1 M to about 3 M, about 1 M to about 2.5 M, about 1 M to about 2 M, and so on). and about 0.05 M to about 0.5 M, including exemplary values of about 0.06 M, about 0.07 M, about 0.08 M, about 0.09 M, about 0.1 M, about 0.15 M, about 0.2 M, about 0.25 M, about 0.3 M, about 0.35 M, about 0.4 M, and about 0.45 M of lithium difluoro(oxalato)borate (or about 0.05 M to about 0.45 M, about 0.05 M to about 0.35 M, about 0.05 M to about 0.25 M, and so on) dissolved in a mixture of solvents comprising about 40 vol% to about 90 vol% of DME, about 10 vol% to about 60 vol% of DOL, and about 0.05 wt% to about 5 wt% of DMI. In such exemplary aspects, the mixture of solvents can comprise about 40 vol% to about 90 vol% of DME, including exemplary values of about 45 vol%, about 50 vol%, about 55 vol%, about 60 vol%, about 65 vol%, about 70 vol%, about 75 vol%, about 80 vol%, and about 85 vol% (or about 40 vol% to about 90 vol%, about 40 vol% to about 80 vol%, 40 vol% to about 70 vol%, 40 vol% to about 60 vol%, and so on). In suchexemplary aspects, the mixture of solvents can comprise about 10 vol% to about 60 vol% of DOL, including exemplary values of about 15 vol%, about 20 vol%, about 25 vol%, about 30 vol%, about 35 vol%, about 40 vol%, about 45 vol%, about 50 vol%, and about 55 vol% (or about 10 vol% to about 60 vol%, about 10 vol% to about 50 vol%, 10 vol% to about 40 vol%, 10 vol% to about 30 vol%, and so on). In still further aspects, the mixture of solvents can comprise about 0.05 wt% to about 5 wt% of DMI, including exemplary values of about 0.1 wt %, about 0.25 wt %, about 0.5 wt %, about 0.75 wt %, about 1 wt %, about 1 .2 wt %, about 1 .5 wt %, about 1 .7 wt %, about 2 wt %, about 2.2 wt %, about 2.5 wt %, about 2.7 wt %, about 3 wt %, about 3.2 wt %, about 3.5 wt %, about 3.7 wt %, about 4 wt %, about 4.2 wt %, about 4.5 wt %, and about 4.7 wt % of DMI based on the total weight of the electrolyte (or about 0.05 wt% to about 5 wt%, about 0.05 wt% to about 4 wt%, about 0.05 wt% to about 3 wt%, about 0.05 wt% to about 2 wt%, and so on).

[0156] In still further aspects, such rechargeable batteries can compromise a cathode comprising a high density nickel-rich layered transition metal oxide, a lithium iron phosphate (LFP), Lithium manganese oxide (LiMn2O4), or nickel-doped lithium manganese oxide (Li[Nio.5Mm.5]04).

[0157] In still further aspects, such batteries can comprise a separator with any of the disclosed coatings. Yet in other aspects, such an exemplary battery having the disclosed above electrolyte system and the cathode can comprise a separator that is substantially free of the disclosed herein ceramic layer. In still further aspects, such an exemplary battery having the disclosed above electrolyte system and the cathode can comprise any commercially available separator.

[0158] In still further aspects, any of the disclosed herein batteries exhibit an energy density of about 150 Wh / kg to about 500 Wh / kg, including exemplary values of about 160 Wh / kg, about 170 Wh / kg, about 180 Wh / kg, about 190 Wh / kg, about 200 Wh / kg, about 210 Wh / kg, about 220 Wh / kg, about 230 Wh / kg, about 240 Wh / kg, about 250 Wh / kg, about 260 Wh / kg, about 270 Wh / kg, about 280 Wh / kg, about 290 Wh / kg, about 300 Wh / kg, about 310 Wh / kg, about 320 Wh / kg, about 330 Wh / kg, about 340 Wh / kg,about 350 Wh / kg, about 360 Wh / kg, about 370 Wh / kg, about 380 Wh / kg, about 390 Wh / kg, about 400 Wh / kg, about 410 Wh / kg, about 420 Wh / kg, about 430 Wh / kg, about 440 Wh / kg, about 450 Wh / kg, about 460 Wh / kg, about 470 Wh / kg, about 480 Wh / kg, and about 490 Wh / kg (or about 150 Wh / kg to about 500 Wh / kg, about 150 Wh / kg to about 400 Wh / kg, about 150 Wh / kg to about 300 Wh / kg, about 150 Wh / kg to about 200 Wh / kg, and so on).

[0159] In still further aspects, any of the disclosed herein batteries exhibit a specific discharge capacity of about 50 mA h / g to about 400 mA h / g, including exemplary values of about 60 mA h / g, about 70 mA h / g, about 80 mA h / g, about 90 mA h / g, about 100 mA h / g, about 110 mA h / g, about 120 mA h / g, about 130 mA h / g, about 140 mA h / g, about 150 mA h / g, about 160 mA h / g, about 170 mA h / g, about 180 mA h / g, about 190 mA h / g, about 200 mA h / g, about 210 mA h / g, about 220 mA h / g, about 230 mA h / g, about 240 mA h / g, about 250 mA h / g, about 260 mA h / g, about 270 mA h / g, about 280 mA h / g, about 290 mA h / g, about 300 mA h / g, about 310 mA h / g, about 320 mA h / g, about 330 mA h / g, about 340 mA h / g, about 350 mA h / g, about 360 mA h / g, about 370 mA h / g, about 380 mA h / g, about 390 mA h / g ( or about 50 mA h / g to about 400 mA h / g, about 50 mA h / g to about 350 mA h / g, about 50 mA h / g to about 300 mA h / g, about 50 mA h / g to about 250 mA h / g, about 100 mA h / g to about 400 mA h / g, about 150 mA h / g to about 400 mA h / g, about 200 mA h / g to about 400 mA h / g) when discharged at about 0.1 C to about 10C rate, including exemplary values of about 0.2C, about 0.5C, about 1 C, about 2C, about 3C, about 4C, about 5C, about 6C, about 7C, about 8C, and about 9C rate (or about 0.1 C to about 10C rate, about 0.1 C to about 8C rate, about 0.1 C to about 5C rate, about 0.1 C to about 4C rate, and so on).

[0160] In still further aspects, any of the disclosed herein batteries exhibit a coulombic efficiency greater than about 80%, greater than about 81 %, greater than about 82%, greater than about 83%, greater than about 84%, greater than about 85%, greater than about 86%, greater than about 87%, greater than about 88%, greater than about 89%, greater than about 90%, greater than about 91%, greater than about 92%, greater than about 93%, greater than about 94%, greater than about 95%, greaterthan about 96%, greater than about 97%, greater than about 98%, or greater than about 99% for at least about 150 cycles. In still further aspects, the batteries disclosed herein exhibit the disclosed properties for at least about 200 cycles, or at least about 250 cycles, or at least about 500 cycles, or at least about 1000 cycles.

[0161] In still further aspects, any of the disclosed herein batteries exhibit a capacity retention of at least about 80%, or at least about 81 %, or at least about 82%, or at least about 83%, or at least about 84%, or at least about 85%, or at least about 86%, or at least about 87%, or at least about 88%, or at least about 89%, or at least about 90%, or at least about 91 %, or at least about 92%, or at least about 93%, or at least about 94%, or at least about 95%, or at least about 96%, or at least about 97%, or at least about 98%, or at least about 99% for at least about 150 cycles. In still further aspects, the batteries disclosed herein exhibit the disclosed properties for at least about 200 cycles, or at least about 250 cycles, or at least about 500 cycles, or at least about 1000 cycles.

[0162] Also disclosed herein are systems comprising one or more of any of the disclosed herein batteries. For example, the system can comprise at least about 2, at least about 5, at least about 10, at least about 50, at least about 100, at least about 500, or at least about 1000 batteries.

[0163] Also disclosed herein are articles that can comprise the disclosed herein batteries or systems. For example, the article can comprise a vehicle (land, marine, air, or space-adapted vehicles), a hand-held device, a wearable electronic device, stationary electronic devices, electrical tools, toys, energy storage devices, and the like.METHODS

[0164] Also disclosed herein are methods of making any of the disclosed herein separators. Also disclosed herein are methods of making any of the disclosed herein batteries.

[0165] In certain aspects, disclosed herein are methods depositing a first homogeneous mixture of a first ceramic material and a first binder at a first surface of a substrate; and drying the separator to form a first uniform ceramic layer. In yet still further aspects, the method can further comprise depositing a second homogeneous mixture of a second ceramic material and a second binder on a second surface of the substrate that is opposite to the first surface.

[0166] It is understood that the mixture can be made by any known in the art methods. It is further understood that in some exemplary aspects, the first and / or second homogeneous mixture can be formed by homogeneously blending the first binder and the first ceramic material or the second binder and the second ceramic material, respectively.

[0167] Still further, the step of depositing the second homogeneous mixture of the second ceramic material and the second binder on the second surface of the substrate is done before drying the separator or after drying the separator. In yet still further aspects, the method comprises further drying of the separator to form the second ceramic layer at the second surface of the substrate.

[0168] It is understood that in some aspects, the mixture of the first and / or second binder and the first and / or second ceramic material can comprise a first and / or second solvent, respectively. The first and the second solvents can be the same or different. In such aspects, the mixture can be present as a slurry. It is understood that any known in the art solvents can be used to form the slurry. In certain aspects, the solvent is acetonitrile (ACN), DME, DMF, THF, ethyl alcohol, or any combination thereof, and the like. In yet still further aspects, the solvents can be substantially anhydrous. In still further aspects, after depositing the mixture of the surface(s) of the substrate and drying the first and / or second ceramic layer, the first ceramic layer and / or the second ceramic layer, if present, is substantially free of the first solvent and / or second solvent, respectively. In yet still further aspects, the slurry is disposed on the substrate by the doctor’s blade method. However, it is understood that any method that can provide the desired thickness of the ceramic layers can be utilized.

[0169] It is understood that any of the disclosed herein ceramic materials and binders in any of the disclosed above ratios can be utilized. Still further, the mixture used to deposit the disclosed herein layers can further comprise any of the disclosed herein fillers and / or salts.

[0170] In still further aspects, the binders can have suitable molecular weight. For example and without limitations, the first and / or second binder can be PEO and can have a molecular weight of about 10,000 to about 1 ,000,000 Dalton, including exemplary values of about 50,000, about 100,000, about 250,000, about 500,000, and about 750,000 Daltons (or about 10,000 to about 1 ,000,000 Dalton, about 10,000 to about 800,000 Dalton, about 10,000 to about 500,000 Dalton, about 10,000 to about 250,000 Dalton, and so on). It is understood, however, that any of the disclosed above binders can be used, and they can have a similar to the disclosed above molecular weight.

[0171] In yet still further aspects, the binder can comprise EC. In some exemplary and unlimiting aspects, the first and / or second ceramic layer, if present, can comprise the first and / or second ceramic material comprising Ceo.9Gdo 1O1.95 and the first and / or second binder comprising EC. In such exemplary and unlimiting aspects, the ceramic layer can comprise about 5 wt% of EC.

[0172] In such exemplary and unlimiting aspects, EC can be present as a viscous material having a viscosity of about 30 to about 70 mPa*s, including exemplary values of about 35 mPa«s, about 40 mPa«s, about 45 mPa«s, about 50 mPa«s, about 55 mPa*s, about 60 mPa*s, and about 65 mPa*s (or about 30 mPa«s to about 70 mPa*s, about 30 mPa«s to about 55 mPa«s, about 30 mPa«s to about 45 mPa«s, and so on).

[0173] In certain aspects, the thickness of the layers formed by the methods disclosed herein can depend on a viscosity of the mixture. In certain aspects, the first and / or second mixtures can have a viscosity from about 30 to about 100,000 mPa s, including exemplary values of about 40 mPa s, about 50 mPa s, about 60 mPa s, about 70 mPa s, about 80 mPa s, about 90 mPa s, about 100 mPa s, about 150 mPa s, about250 mPa s, about 500 mPa s, about 750 mPa s, about 1 ,000 mPa s, about 2,250 mPa s, about 5,000 mPa-s, about 7,500 mPa s, about 10,000 mPa s, about 25,000 mPa s, about 50,000 mPa s, and about 75,000 mPa s (or about 30 mPa*s to about 100,000 mPa«s, about 30 mPa«s to about 80,000 mPa«s, about 30 mPa«s to about 50,000 mPa*s, about 30 mPa*s to about 10,000 mPa«s, about 30 mPa«s to about 800 mPa«s, about 30 mPa«s to about 500 mPa«s, about 30 mPa«s to about 100 mPa«s, about 30 mPa*s to about 50 mPa*s, and so on).

[0174] Yet in still further exemplary and unlimiting aspects, the first and / or second ceramic material comprises AI2O3. Yet in still further aspects, the binder can be PVDF.

[0175] The disclosed herein ceramic layers can be deposited on any of the disclosed above substrates. In still further aspects, the disclosed herein ceramic layers can have any of the described above thicknesses.

[0176] In still further aspects, the separators made by the disclosed methods can exhibit any of the disclosed above properties.

[0177] Also disclosed here are methods of making the batteries. The methods comprise providing any of the disclosed above anodes, separators, cathodes, and electrolytes. The batteries formed by the disclosed methods can exhibit any of the disclosed above properties.

[0178] By way of a non-limiting illustration, examples of certain aspects of the present disclosure are given below.EXAMPLES

[0179] The following examples are put forth so as to provide those of ordinary skill in the art with a complete disclosure and description of how the compounds, compositions, articles, devices, and / or methods claimed herein are made and evaluated and are intended to be purely exemplary and are not intended to limit the disclosure. Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.), but some errors and deviations should be accounted for.Unless indicated otherwise, parts are parts by weight, temperature is degrees C or is at ambient temperature, and pressure is at or near atmospheric.EXAMPLE 1

[0180] In this example, disclosed is a 9 pm PE separator (Entek) having a ceramic coating on at least one surface of the PE separator. The ceramic coating described in this example comprises 90 wt% LLZTO and 10 wt % PEO, which can be chemically reactive with electrolytes and lithium metal to provide an ionically conductive and selective surface layer. The total thickness of the ceramic-coated separator can be tailored to be similar to or lower than that of a commercial separator (20 pm) with a coating thickness of ~10 pm. In the instance of the single-side coated ceramic separator, the coated side is the side facing the lithium anode. As described in detail above, it is understood, however, that the ceramic coating can be deposited on both surfaces of an inert separator, such that when the separator is incorporated into a full lithium metal cell, a coated surface faces both the anode and cathode.

[0181] When the coated separator is incorporated into a full lithium metal cell, a stable interfacial layer between the ceramic-coated separator and the lithium metal anode can form in situ upon cycling. After lithium metal reacts with the ceramic coating, a compatible interface suitable for battery operation is formed. This interfacial layer is ionically conductive and electrically insulating, thereby suppressing the formation of lithium dendrites. The ceramic-coated separator is porous and has good wettability, which can minimize the amount of electrolyte added to cells and offer enhanced safety usage. Lastly, the morphology of the coated separator is highly tortuous, providing a physical barrier that dendrites cannot permeate through if they still form during battery cycling.

[0182] The thickness of a single-coated separator can be matched to the conventional separators. The ceramic coating layer has a thickness of ~10 pm, and the base membrane is ~9 pm. For a single side coated separators and double-coatedseparators, the thickness can be ~20 pm and ~30 pm, respectively. It is understood that the thicknesses can be tailored as desired.

[0183] The Li transference number (tLi+) of the single-coated separator can be measured with electrochemical impedance spectroscopy (EIS). The Li transference number of the single-sided coated separator with a commercial liquid electrolyte is about 0.76, whereas the commercial separator is only 0.42. The Li transference number is related to the voltage polarization of the cell during charge / discharge cycling. Without wishing to be bound by any theory, it is understood that the higher tLi+can lead to lower polarization, resulting in better cell performance.EXAMPLE 2LLZTO / PEO Coated Separators

[0184] The present disclosure features separators, including a ceramic coating that can be used in hybrid LMBs, including the cell design, fabrication method, and electrochemical testing results in Li / Li symmetric cells and full hybrid solid-state lithium metal cells. The disclosed herein ceramic coated separators exhibit good wettability, the ability to form a stable interface against lithium metal, mitigate Li dendrite growth, and improve the cycle-life of LMBs. In the example below, the effect of the single and / or double side coated separator on the electrochemical performance of LMBs is demonstrated in Li / Li symmetric cells, full lithium metal cells with high loading LFP and NMC 622 / 811 cathodes in coin cell and pouch cell formats.

[0185] The exemplary LLZTO solid electrolyte has a uniform particle size of 500 nm. The ionic conductivity of the Ta-doped Li?-xLa3Zr2-xTaxOi2 (0<x<1 .0) system at room temperature is shown in FIG. 1 (Y. Li et aL, J. Mater. Chem., 2012, 22, 15357-15361 ). The Li+conductivity reaches a maximum of ~ 1 x 10-3S erm1when x=0.6. Also, LLZTO is a good electronic insulator as its electronic conductivity was not measurable with available instrumentation (EIS).

[0186] The separator, as described in this example, can be made via slurry casting onto a commercial separator consisting of PE, PP, or some combination thereof toform the final coated separator coating, as shown in FIGs. 2A-2B. The slurry comprises a ceramic electrolyte (e.g., Li6.4La3Zn.4Tao.6O12), a polymeric binder, and a solvent and is coated onto one or both sides of the separator substrate. The solvent is then evaporated off to yield the final coated polymeric separator.

[0187] In one example, a PEO (Mw 600,000) is used as a binder. The slurry coating of LLZTO / 10wt% PEO was performed with a doctor's blade, and the thickness was controlled by adjusting the blade gap. The solvent used to form the slurry included acetonitrile (ACN). The volume of the solvent in the slurry can be adjusted to control the coating thickness and slurry viscosity for coating speed. The final coated separator product was dried under vacuum at room temperature overnight (minimum 6 hours) to remove the residual solvent in the coating that could be detrimental to battery performance.

[0188] FIGS. 3A and 3B show the surface morphology of the LLZTO / PEO coating observed with scanning electron microscopy at different magnifications. The coating was uniform, and there were pores allowing electrolyte penetration. The particle size of LLZTO particles was ~500 nanometers. The thickness of the coating was~ 10 pm and could be controlled to ~under 5pm by slurring coating.EXAMPLE 3Hybrid Lithium Metal Battery

[0189] The exemplary separator, as described above, can be incorporated into a hybrid lithium metal battery, as demonstrated in FIGs. 4A-4B. A hybrid lithium battery can include an anode, a cathode, and a coated separator of the present disclosure / / commercial separator between the anode and the cathode and a limited volume of liquid electrolyte. Without wishing to be bound by any theory, it is hypothesized that the liquid electrolyte can interact with the disclosed herein separator coating to provide a superior performance of the final hybrid solid-state battery product.

[0190] It is understood that a similar concept can be used in other secondary batteries. This example, however, relates to a hybrid solid-state lithium battery. In this exemplary hybrid solid-state lithium battery, the anode is metallic lithium, and the cathode can include a nickel-rich lithium layered oxide or an olivine-structured lithium metal phosphate.

[0191] In the present disclosure, the following examples have been prepared to demonstrate the performance of the proposed technology: a hybrid Li / Li symmetric cell with an LLZTO / PEO coated separator, a Li / LFP cell with an LLZTO / PEO coated separator, and a Li / NMC622 / 81 1 cell with an LLZTO / PEO coated separator. These cells were tested under various conditions, such as charged / discharged at rates of 0.1 C (C / 10), 0.2C (C / 5), or 0.33C (C / 3). As used herein, C refers to the charging and discharging rate, where, for example, 1 C refers to charge / discharge in 1 hour, 0.1 C refers to charge-discharge in 10 h, 0.2C refers to charge / discharge in 5 h, and 0.33C refers to charge / discharge in approximately 3 hours.EXAMPLE 4

[0192] In the following Examples, single and double side coated separators for use in a Li / Li symmetrical cell or full lithium metal coin / pouch cell were formed and tested.Hybrid Solid-State Lithium Metal Symmetric Coin Cells

[0193] FIG. 5 is a graph showing the comparison of cycling stability of Li / Li symmetric cells with the commercial base PE (Entek) separator and single-side coated separators, cycled at a current density of 0.5 mA cm-2. The thickness of lithium metal was 500 pm. The electrolyte was 15 pL 1 M LiPFe in EC / DEC(1 :1 ). For the cell with a commercial base PE (Entek) separator, an average overpotential was around 86 mV. After the 200 h stable Li plating / tripping process, the cell started to degrade with the overpotential gradually increased and significant voltage fluctuations as cycling. The cell shorted after 280 h, which could be due to rapid electrolyte depletion and / or lithium dendrite growth. On the contrary, the cell with a single-side coated separator exhibited stable Li plating / stripping up to 400 h, and then the polarization began to increasegradually. The increasing voltage polarization might be due to the increased thickness of the SEI layer as the cycle number increases. After 500 h, the average overpotential was around 55mV, which was more significant than the cell with commercial separators. The significant improvement in cycling stability and overpotential was mainly due to the homogenized current density and better wettability by coating. More importantly, Li dendrites formation was prevented as a result of coating.

[0194] FIG. 6 and FIG. 7 show the results of the AC impedance and DC polarization measurements performed using Li / Li symmetric cells with the commercial base PE (Entek) separator and single-side coated separators. The values of tLi+were determined by the Bruce-Vincent method.

[0195] In the equation, where / ;and Zsare the initial and steady-state cell currents. AV is the de polarization voltage. RB, and RBSrepresent the bulk resistances before and after applying the de voltage. Rnand RISare the respective interfacial resistances bulk resistances before and after applying the de voltage and were recorded by two impedance spectra in the frequency range between 1 Hz and 1 MHz before the polarization and after the steady state has been reached and the de bias potential has been removed. The initial current was attributed to the movements of both cations and anions in the electrolyte (1 M LiPFe in EC / DEC) driven by a de polarization voltage of 10mV. At steady-state, after 1000s of potential holding, the current flow was a result of the movement of only Li ions. Therefore, the tLi+can be largely determined by the ratio of ls / lo- As a result, tLi+value exhibited by the single-coated separator was 0.76, whereas for the commercial separator, the value of tLi+was only 0.42. Without wishing to be bound by any theory, it could be attributed to LLZTO having an extremely high tLi+value (tLi+« 1) and can immobilize the PFe anion, reduce polarization, and mitigate the dendrite growth by regulating the ion distribution. On the single-side coated separator, the high weight percentage of LLZTO (90%) was found to be favorable in immobilizing the PFe', enabling lower polarization, and prohibiting thedendrite formation, which was reflected by the longer cycling stability of Li / Li symmetrical cells compared to cells with the commercial PE (Entek) separator.Hybrid Solid-State LiFePOo / Lithium Metal Coin Cells

[0196] The effect of the coating layer on the cell polarization was investigated in full LFP / Li coin cells (2.6 mAh cm- 2). FIG. 8 compares the discharge voltages of cells with a single-side coated separator and a commercial separator. The thickness of the Li anode was 100 pm. LFP cathode was purchased from Gotion (active mass loading: 15.2 mg cm-2). The electrolyte was 30 pL 3M Lithium bis(trifluoromethanesulfonyl)imide (LiFSI) and 0.25M lithium difluoro(oxalato)borate( LiDFOB) in 40% dimethoxyethane (DME) / 60% 1 ,2-dioxolane (DOL) / 0.2% 1 ,3- dimethyl-2-imidazolidinone (DMI). Cells were cycled at a current density of C / 3 between 3.0-3.5 Vs. Li metal. Upon 100 cycles, the average discharge potential for the cell with a single-side coated separator was 3.35 V vs. Li metal, whereas the average discharge potential for the cell with a commercial separator was 3.32 V vs. Li. The increasing discharge potential of cells with coated separators was attributed to the reduced polarization as a result of a higher transference number.Hybrid Solid-State LiNixMnyCoy02(x=0.6 / y=0.2, or x=0.8 / y=0.1) / Lithium Metal Coin Cells

[0197] FIG. 9 and FIG. 10 illustrate the voltage profiles of the cells with commercial and single-side coated separators cycled at 0.1 C ( first 3 cycles ) and 0.2 C ( the rest cycles) between 3.0 and 4.4 V vs. Li. NMC81 1 cathode was prepared by mixing 90 wt. % the active material, 5 wt. % carbon black, and 5 wt. % polyvinylidene fluoride (PVDF) in N - methyl - 2 - pyrrolidone (NMP) in a vacuum mixer for 2h, casting the slurry on conductive carbon coated Al foils ( 50 pm ) using an automatic film coater with a doctor’s blade, and then drying at 1 10 °C under vacuum for 12 h to remove the NMP solvent. The cathodes were assembled in 2032-type coin cells with 100 pm thick Li foils as the anode and a lean amount of 1 M LiPFe in EC / DEC electrolyte. At 0.1 C, these two cells showed similar voltage profiles. However, upon cycling at C / 5, the cell with a commercial separator showed an increasing discharge voltage polarization,indicating a larger impedance for the cell upon cycling at a higher current rate as a result of lithium dendrite formation and fast consumption of lean electrolyte. By contrast, the voltage polarization of the cell with a single coated separator was very stable due to the coated layer might prevent the lithium dendrite growth and improve the wettability. In addition, it is found that while the thickness of the separator coating (-20 pm) was almost double compared to the commercial Entek separator (9 pm), the effect of increasing thickness on the cell’s internal resistance was negligible. That means that increasing the thickness of the coating layer may lead to a higher transference number because of more LLZTO content but will not negatively affect the cell's internal resistance. More importantly, the cell with a coated separator delivered a higher specific capacity at 0.1 C ( -200 mAh g-1) and 0.2C (-185 mAh g-1) than the cell with a commercial separator, 180 mAh g1at 0.1 C and -165 mAh g-1at 0.2C, respectively. The higher energy density was attributed to a reduced polarization during charging and discharging and an improvement of ion kinetics by increasing the wettability of the coated separator.

[0198] FIG.11 illustrates the comparison of cycling stabilities and coulombic efficiencies of the cells with commercial and single-side coated separators cycled at 0.1 C ( the first 3 cycles ) and 0.2 C ( the rest cycles) between 3.0 and 4.4 V vs. Li. Cells were evaluated under stringent conditions (thin Li foil, -100 pm, and limited electrolyte, -10 pL). The NMC811 cathode was prepared and assembled as described above. The electrolyte was 1 M LiFSI in DME:TTE (1 .2:3 by mole). For the first three cycles at 0.1 C, the cycling behavior of the cell with a commercial separator indicated that with lean electrolyte, electrodes were not fully wet in the first place even though the separator was very thin (9 pm). As cycling, more electrode areas were accessible with electrolytes, resulting in a climbing feature of discharge capacities. After 30 cycles, the capacity started to show a sign of degradation. When it comes to the cell with a single coated separator, the cell delivered a high discharge capacity of more than -200 mAh g-1at 0.1 C without significant capacity climbing because the coated separator well dispersed the electrolyte and wet electrodes. The capacity retention of the cell with a single coated separator was -93.9% after 50 cycles. The averagecoulombic efficiencies of cells with commercial and single-side coated separators were similar, ~99.1 % over 50 cycles. The coulombic efficiency for the first cycle of a cell with a commercial separator was ~ 77.9%, which was lower than that of a cell with a coated separator, 86.2%, indicating lithium anode has a different solid electrolyte interphase (SEI) layer formation mechanism when interaction with LLZTO / PEO coated layer. Less Li ions were consumed to form SEI and might lead to a lower resistance coming from the SEI layer, which was reflected by a dramatically higher discharge capacity(~200 mAh g-1) than the cell with a commercial separator for the first cycling (~125 mAh g-1).Hybrid Solid-State LIFePOo / Lithium Metal Pouch Cells

[0199] The Large-scale fabrication of Li / LFP pouch cells (1 Ah) was provided to verify the applicability of the coated separators in lithium metal batteries. FIG. 12 illustrates the cycling stability of the 1 Ah pouch cell with coated separators. The size of one pouch cell was 62 mm X 45 mm (length by width). One pouch cell contained 10 layers of LFP cathode (active mass loading: 15.2 mg cm-2) and 9 layers of lithium anode (40 pm). The electrolyte was 3M LiFSI and 0.25M LiDFOB in 40% DME / 60% DOL / O.2% DMI, and the added amount was controlled to 4 g Ah1. The cell was cycled at 0.33C between 3.0 and 3.6 vs. Li for 40 cycles, then switched the cut-off voltage to between 3.0 and 3.5 V vs. Li for the subsequent cycles. The discharge capacity was very close to 1 Ah when cycling under two cut-off voltages. For the first cycle, the efficiency was 97.4%, and the discharge capacity was ~1 .1 Ah. The capacity retention was 89.9% and showed an impressive average efficiency of -99.8% (160 cycles).Hybrid Solid-State LINixMnyCoyO2(x=0.6 / y=0.2, or x=0.8 / y=0.1) / Lithium Metal Pouch Cells

[0200] The large-scale Li / NMC622 pouch cell (0.8 Ah) was further fabricated to demonstrate the applicability of the coated separators in lithium metal batteries. FIG. 13 illustrates the cycling stability of the 0.8 Ah pouch cell with double-side coated separators. The size of one pouch cell was 62 mm X 45 mm (length by width). One pouch cell contained 9 layers of NMC622 cathode (active mass loading: 20.5 mg cirr2) and 8 layers of lithium anode (40 pm). 1 M LiFSI in DME:TTE (1 .2:3 by mole) wasoverfilled as an electrolyte. The cell was cycled at 0.33C between 3.0 and 4.0 V vs. Li. The discharge capacity was approximately 0.8 Ah. For the first cycle, the efficiency was 97.4%, and the discharge capacity was -0.82 Ah. The capacity retention was 98.4% and showed an impressive average efficiency of -99.2% (250 cycles).EXAMPLE 5

[0201] Fig. 14 shows a cyclic performance of exemplary cells comprising LiFePC cathode, lithium metal anode, uncoated commercial separator and an exemplary electrolyte comprising 3M Lithium bis(trifluoromethanesulfonyl)imide (LiFSI) and 0.25M lithium difluoro(oxalato)borate( LiDFOB) in 40% dimethoxyethane (DME) / 60% 1 ,2- dioxolane (DOL) / 0.2% 1 ,3-dimethyl-2-imidazolidinone (DMI). It can be seen that the normalized discharge capacity is substantially stable for about 400 cycles and is above 90%.EXAMPLE 6

[0202] In this example, a disclosed herein separator was formed by using a slurry casting process using a doctor blade, as schematically demonstrated in Figs. 15A- 15B. The slurry comprises a ceramic, which can have a varying particle size (e.g., 500 nm size Ceo.9Gdo.1O1.95, GDC, and / or a mixture of micro and nanosizedCeo.9Gdo.1O1.95), a polymeric binder (ethyl cellulose, EC), and a solvent (anhydrous ethyl alcohol). In this example, the coating was applied to one side of the substrate, but it can also be applied to both sides. The solvent is then evaporated off to yield the final coated polymeric separator. In one example, EC (viscosity 30-70 mPa-s) is used as a binder. The slurry coating of GDC / 5wt% EC was performed with a doctor's blade, and the thickness of the coating was controlled by adjusting the blade gap. The solvent used to form the slurry included anhydrous ethyl alcohol. The volume of the solvent in the slurry can be adjusted to control the coating thickness / tortuosity / porosity and slurry viscosity for coating speed. The final coated separator product was dried under vacuum at room temperature overnight (minimum 6 hours) to remove the residual solvent in the coating that could be detrimental to battery performance.

[0203] FIGs. 16A-16B show the surface morphology of the nanosized GDC / EC coating observed with scanning electron microscopy at different magnifications. The coating was generally uniform. The particle size of most primary GDC particles was -500 nanometers. There were a few secondary particles with larger particle sizes. The thickness of the coating was- 8 pm and could be controlled to a minimum of -1 pm by slurring coating.

[0204] FIGs. 17A-17B are scanning electron microscopy (SEM) images of one of the GDC ceramic powders received with different magnifications. Though some primary GDC ceramics were nanosized powders, there were many secondary micro-sized particles. As shown in FIGs. 17B, the particle size of secondary particles was between 3- 20 microns.

[0205] FIG. 18 demonstrates the superior electrolyte wettability of the disclosed coated separator via digital photographs. The uncoated 9 pm PE (Entek) separator and nanosized GDC / EC single-side coated separator are shown after dropping 10 pL liquid electrolyte (LiFSI-DME-TTE, 1 :1 .2:3 by mol.). As the treatment proceeded, the wet portion of the uncoated and coated separators, respectively, was observed to increase at each time step - 3s, 15s, 45s, and 60s. The wetting started nearly instantly for the coated separator, with no liquid droplet forming on the surface of the coated separator after 3s. For the uncoated polyethylene (PE) separator, the electrolyte was not fully absorbed during the same period. It was found that electrolytes could wet the coated separator much faster than the bare PE separator. The coated separator was completely wet after the 60s. On the other hand, exposure of the uncoated PE separator to 10 pL liquid electrolyte resulted in the wetting of approximately 70% of the separator. Without wishing to be bound by any theory, it was hypothesized that the enhanced wettability of the coated separators compared to uncoated PE separators could be due to higher porosity after ceramic coating.EXAMPLE 7

[0206] FIGs. 19A-19C demonstrate the incorporation of the disclosed herein separator into a hybrid lithium metal battery. A hybrid lithium battery can include an anode (Li metal with 100 pm and 40 pm thickness), a cathode (LPF, NMC622, NMC81 1 ), and a coated separator between the anode and the cathode and a limited volume of liquid electrolyte.

[0207] FIG. 20 is a graph showing the comparison of cycling stability of Li / Li symmetric cells with a commercial base PE (Entek) separator, a nanosized GDC / EC coated separator, and a micro / nanosized GDC / EC coated separator, cycled at a current density of 0.5 mAcm-2. The thickness of lithium metal was 100 pm. The electrolyte was 10 pL 1 M LiPFe in EC / DEC (1 :1 ). For the first cycle, all the cells with either uncoated or coated separators exhibited high overpotential, which is associated with the nucleation of Li deposits when initially plating lithium. Then overpotential decreased rapidly towards a local minimum due to an increased surface area for deposition. In addition, for the first few cycles, the overpotential of cells implementing coated separators had a slightly lower overpotential than the cell with an uncoated PE separator because coated separators have higher ionic conductivities compared to PE separators. After the 200 hr stable Li plating / stripping process, the cell started to degrade with the overpotential gradually increased and significant voltage fluctuations as cycling. The average overpotential was ~57 mV. The cell shorted after 270 h, which could be due to rapid electrolyte depletion and / or lithium dendrite growth. On the contrary, the cells with coated separators exhibited much more stable Li plating / stripping up to 450h. The average overpotential of cells with nanosized and micro / nanosized GDC / EC coated separators was ~44 mV and~62 mV, respectively.

[0208] The significant improvement in cycling stability and overpotential was mainly due to the homogenized current density and better wettability achieved by forming the disclosed herein coating. In addition, although cells with coated separators showed similar cycling stabilities, the voltage polarization of the cell using a micro / nanosized GDC / EC coated separator increased significantly as the cycle number increased (after350h), whereas the cell using a nanosized GDC / EC coated separator exhibited a minor increase in overpotential upon the same cycling time, which might be due to the unevenly distributed particle sizes of GDC ceramic powder resulting in uneven current distribution and a non-uniform SEI layer, consuming more electrolyte and leading to significantly increasing voltage polarization.

[0209] FIG. 21 is a graph showing the linear sweep voltammetry (LSV) curves of cells with an uncoated 9 pm PE (Entek) separator and a nanosized GDC / EC single-side coated separator with a scan rate of 10 mV s-1at a potential range from 2.3 to 4.5 V versus Li metal. The measurements were carried out to evaluate and compare the electrochemical stabilities of the original PE separator and coated separator. A lithium plate (29mmx29mmx0.06mm) was used as a counter and reference electrode with a copper current collector, whereas an aluminum foil (25mmx25mmx0.011 mm) was used as a working electrode. The electrolyte was LiFSI-DME-TTE(1 :1 .2:3 by mol). The voltage when the current density increases steadily is expressed as the electrochemical oxidation limit of the separator / electrolyte system. Both bare PE and coated separators exhibit good electrochemical stabilities upon testing the voltage window, as the maximum current shown in FIG. 21 was 15 pA. Without wishing to be bound by any theory, the increased current at 4.4 V vs. Li could possibly be attributed to TTE oxidation. It was also found that the coated separator incorporating the EC binder has higher electrochemical stability. Overall, the cell with a coated separator exhibited a wider stable voltage platform with a lower anodic current coming from the oxidation process compared to the cell with a PE separator. When the voltage was higher than 4.0 V, the current of the cell with a coated separator became stable and did not show a significant increase as the voltage kept increasing, whereas the cell with a PE separator had an increasing current. The improved electrochemical stability could be caused by the incorporation of the EC binder. The cellulose-based polymer is stable at 4.5 V versus Li and has a gelation effect on the electrolyte, becoming more stable under the oxidation process.

[0210] FIGs. 22 and 23 show the results of the AC impedance and DC polarization measurements performed using Li / Li symmetric cells with the uncoated PE (Entek) separator and nanosized GDC / EC single-side coated separators. The values of tLi+were determined by the Bruce- Vincent method.

[0212] In the equation, where / ,and Zsare the initial and steady-state cell currents. AV is the de polarization voltage. RB, and RBSrepresent the bulk resistances before and after applying the de voltage. Rnand RISare the respective interfacial resistances bulk resistances before and after applying the de voltage and were recorded by two impedance spectra on the cell in the frequency range between 1 Hz and 1 MHz before the polarization and after the steady state has been reached and the de bias potential has been removed. Without wishing to be bound by any theory, the initial current was attributed to the movements of both cations and anions in the electrolyte (1 M LiPFe in EC / DEC) driven by a de polarization voltage of 10mV. At a steady state, after 3000s of potential holding, the current flow was a result of the movement of only Li ions.Therefore, the tLi+can be largely determined by the ratio of ls / lo- As a result, tLi+value exhibited by the nanosized GDC / EC single-coated separator was 0.89, whereas for the uncoated PE separator, the value of tLi+was only 0.42. Again, without wishing to be bound by any theory, it could be attributed to GDC having oxygen vacancies by partially substituting Ce4+with a trivalent ion, e.g., Gd3+and being as an electrondeficient filler, it can immobilize the PFe anion, reduce polarization, and mitigate the dendrite growth by regulating the ion distribution. On the nanosized GDC coated separator, the high weight percentage of GDC (95 wt%) was found to be favorable in immobilizing the PFe; enabling lower polarization, and prohibiting the dendrite formation, which was reflected by the longer cycling stability of Li / Li symmetrical cells compared to cells with the commercial PE (Entek) separator.EXAMPLE 8

[0213] FIGs. 24-26 illustrate the voltage profiles of the cells with commercial, nanosized, and micro / nanosized GDC / EC coated separators cycled at 0.1 C ( first 3 cycles ) and 0.2 C ( the rest cycles) between 3.0 and 4.4 V vs. Li, respectively.NMC81 1 cathode was prepared by mixing 90 wt. % the active material, 5 wt. % carbon black, and 5 wt. % polyvinylidene fluoride (PVDF) in N - methyl - 2 - pyrrolidone (NMP) in a vacuum mixer for 2h, casting the slurry on conductive carbon coated Al foils (50 pm) using an automatic film coater with a doctor’s blade, and then drying at 110 °C under vacuum for 12 h to remove the NMP solvent. The as-prepared cathode had a medium-high areal loading of 1.7 mAhcnr2. The cathodes were assembled in 2032- type coin cells with 100 pm thick Li foils as the anode and 10 pL 1 M LiPFe in EC / DEC electrolyte. All cells can be charged and discharged within a voltage window of 3-4.4 V versus Li. Initially, cells showed very similar voltage profiles at 0.1 C. However, as shown in FIG. 24, cells with an uncoated PE separator showed a continuous capacity fading, with only -59 % of the initial capacity left after 100 cycles at 0.2C. In addition, cell overpotentials were significantly enhanced upon cycling because side reactions between Li-metal and carbonate electrolytes would result in severe Li dendrite growth. The formation of the SEI layer and its growth result in increasing internal resistance and capacity loss. By contrast, as shown in FIG. 25 and FIG. 26, the voltage polarizations of the cells with both nanosized and micro / nanosized GDC / EC singleside coated separators were stable, and capacities retention was - 87% and -89%, respectively, which were dramatically higher than the cell with a PE separator. Without wishing to be bound by any theory, it was hypothesized that the significant improvement in terms of voltage polarization and stability is due to the coated layer preventing the lithium dendrite growth and improving the wettability. It was also found that the cell with a nanosized GDC / EC coated separator delivered the highest specific capacity of -185 mAhg-1at 0.2C when compared to the cell with a micro / nanosized GDC / EC coated separator, -177 mAhg-1at 0.2C and a PE separator, 169 mAhg-1at 0.2C, respectively. Without wishing to be bound by any theory, the highest energy density was attributed to a reduced polarization during charging and discharging, animprovement of ion kinetics by increasing the wettability of the coated separator, and more uniform ceramic particle distribution.EXAMPLE 9

[0214] FIG. 27 illustrates the comparison of cycling stabilities and coulombic efficiencies (CEs) of the cells with commercial, nanosized, and micro / nanosized GDC / EC coated separators at 0.1 C (the first 3 cycles) and 0.2 C (the rest cycles) between 3.0 and 4.4 V vs. Li. Cells were evaluated under stringent conditions (thin Li foil, -100 pm, and 10 pH M LiPFe in EC / DEC). The NMC811 cathode was prepared and assembled as described above. For the first few cycles at 0.1 C, the cell with a PE separator showed a climbing feature of the specific capacities, which was attributed to the poor wettability of the uncoated PE separator. When it comes to the cells with nanosized and micro / nanosized GDC / EC coated separators, there was no obvious activation process, indicating even though adding a trace amount of electrolyte, coated separators were able to be well wet. The average CEs of cells with uncoated and coated separators were very similar, -99.3%, indicating side reaction with Li anode existed, which is inevitable when using conventional carbonate electrolyte. The CE for the first cycle of a cell with a commercial separator was - 78.0%, which was lower than that of the cell with a nanosized and a micro / nanosized GDC / EC coated separator, 81 .9% and 81 .1 %, respectively, indicating lithium anode has a different solid electrolyte interphase (SEI) layer formation mechanism when interaction with the GDC / EC coated layer.

[0215] FIG. 28 illustrates the cycling stabilities and coulombic efficiencies of the cell with a nanosized GDC / EC coating layer on a 7 pm Entek separator cycled at 0.1 C (the first 3 cycles) and 0.2 C (the rest cycles) between 3.0 and 4.4 V vs. Li. The NMC81 1 cathode had a high areal loading of 2.5 mAhcm-2. Cells were cycled under challenging conditions (100 pm Li foil and 3.4 g Ah-1electrolyte). The electrolyte was LiFSI-DME-TTE (1 :2:3 by moL) with 1wt% LiNOs and 5wt% FEC, which could have a better compatibility with the Li metal compared to carbonate electrolytes. The initial CE was 82.4 %, and the average CEs were 100.4%. The significant improvementregarding the CE indicated that the electrolyte and coating layer have a synergetic effect on the SEI interface formation and Li plating / stripping. In addition, specific capacities showed a minor degradation and retained -95.3% of the original capacity after 100 cycles at 0.2C.EXAMPLE 10

[0216] The double-layer Li / NMC622 pouch cell was fabricated to demonstrate the applicability of the nanosized GDC / EC coated separators in hybrid solid-state lithium metal batteries. FIG. 29 illustrates the cycling stability and CE of the U / NMC622 pouch cell (42 mAh) with nanosized GDC / EC coated separators. One pouch cell contained 1 layer of NMC622 cathode (3.7 mAhcm-2) and 2 layers of lithium anode (60 pm). Electrolyte was LiFSI-DME-TTE (1 :1 .2:3 by mol.), 3g Ah-1. The cell was cycled at 0.2C between 3.0 and 4.3 CCCV vs. Li. The cut-off current was C / 20. The specific discharge capacity was approximately 165 mAhg-1. For the first cycle, the efficiency was 84.0%, and the average efficiency was 100%. The cell exhibited excellent cycling stability of 100% retention after 50 cycles.

[0217] The double-layer Li / LFP622 pouch cell was fabricated to demonstrate the applicability of the nanosized GDC / EC coated separators in hybrid solid-state lithium metal batteries. FIG. 30 illustrates the cycling stability of the Li / LFP pouch cell with nanosized GDC / EC coated separators. The size of the pouch cell was 25 mm X 25 mm (length by width). One pouch cell contained 1 layer of LFP cathode (2.6 mAhcm-2) and 2 layers of lithium anode (60 pm). The electrolyte was LiFSI-DME-TTE (1 :2:3 by mol) with 1wt% LiNOs and 5wt% FEC, and the added amount was controlled to 3.5 g Ah-1. The cell was cycled at 0.33C between 3.0 and 3.6 V vs. Li for 150 cycles. For the first cycle, the efficiency was 93.8%, and the specific capacity was -150 mAhg-1. The capacity retention was 88.4% and showed an impressive average efficiency of -99.9% (150 cycles).

[0218] To demonstrate the viability of the disclosed technology in larger batteries, 0.5 Ah cells were constructed with a lithium iron phosphate cathode, a lithium metal anodecalendared on a copper foil current collector, a CeC / EC separator coated on Entek EP9, and 3M LiFSI and 0.25M LiDFOB in 40% DME / 60% DOL / O.2% DMI as the electrolyte. After formation, this cell was cycled at a C / 3 charge rate of 3.6V and a 1 C discharge rate of 2.5V. A direct current internal resistance (DCIR) measurement was performed during the discharge step of every 10thcycle at 50% state of charge. This DCIR step consisted of a C / 5 discharge for 10 s and a 1 C discharge for 1 s before resuming normal cell discharge procedures. The resulting cycling data for this 0.5Ah cell is provided in FIG. 31 . The lithium metal anode cell is extremely stable for the first 100 cycles with no signs of degradation. The results of the DCIT step performed every 10 cycles for this cell are shown in FIG. 32. Over the first 100 cycles, the cell only shows an increase in internal resistance of ~5%.EXAMPLE 11

[0219] The single-sided coated separator used in Li / Ni83-NMC pouch cell. The separator was a 9 m PE membrane coated with AI2O3 / PVDF mixture in an exemplary ratio of 90 wt% to 10 wt%. The anode material was 100 pm pure Li metal foil. FIG. 33 illustrates the cycling stability of this exemplary cell. The active mass loading is 12.3 mg / cm2. For the first 2 formation cycles, the charge and discharge rate is C / 10. In terms of subsequent cycling, the charge rate is 0.2C, and the discharge rate is 1 C. The electrolyte is 1 wt% LiDFOB in 1 M LiPFe EMC / FEC (9:1 by vol.).

[0220] FIG. 34 illustrates the cycling performance of a 1 Ah multi-layer (9 layers cathode and 10 layers anode) pouch cell with single-sided coated separators. Each separator comprises a 3 pm ceramic single-coated coating layer (AI2O3 / PVDF mixture in an exemplary ratio of 90 wt% to 10 wt%) disposed on a 9 pm PE membrane. The anodes are double-sided ~20 pm Li metal foil with 1 1 pm copper foils as current collectors. Cathodes are Ni83-NMC with an active mass loading is ~14 mg / cm2. In terms of cycling, the charge rate is 0.2C, and the discharge rate is 1 C. The electrolyte is 1 wt% LiDFOB in 1 M LiPFe EMC / FEC (9:1 by vol.) The cell showed a much shorter wetting process than the cycling performance in a coin cell configuration.EXEMPLARY ASPECTS

[0221] In view of the described electrode materials, batteries, and methods and variations thereof, herein below are described certain more particularly described aspects of the inventions. The particularly recited aspects should not, however, be interpreted to have any limiting effect on any different claims containing different or more general teachings described herein or that the “particular” aspects are somehow limited in some way other than the inherent meanings of the language and formulas literally used therein.

[0222] Example 1 . A separator comprising: a substrate having a first surface an opposite second surface; and a first ceramic layer disposed on at least the first surface of the substrate, wherein the separator exhibits an ionic conductivity of about 0.01 mS / cm to about 100 mS / cm when inserted in an electrolyte and wherein the separator is used in a rechargeable battery.

[0223] Example 2. The separator of any examples herein, particularly example 1 , wherein a second ceramic layer is disposed at the second surface of the substrate.

[0224] Example 3. The separator of any examples herein, particularly examples 1 -2, wherein the ceramic layer comprises a first homogeneous blend comprising a first ceramic material and a first binder.

[0225] Example 4. The separator of any examples herein, particularly examples 2-3, wherein the second ceramic layer comprises a second homogeneous blend comprising a second ceramic material and a second binder.

[0226] Example 5. The separator of any examples herein, particularly example 4, wherein the first ceramic material is the same or different from the second ceramic material.

[0227] Example 6. The separator of any examples herein, particularly example 4 or 5, wherein the first binder is the same or different from the second binder.

[0228] Example 7. The separator of any examples herein, particularly examples 3-6, wherein the first ceramic layer and / or the second ceramic layer, if present, further comprise a filler.

[0229] Example 8. The separator of any examples herein, particularly examples 3-7, wherein the first ceramic layer and / or the second ceramic layer, if present, further comprise a salt.

[0230] Example 9. The separator of any examples herein, particularly example 8, wherein the salt is solvated within the first and / or second binder, respectively.

[0231] Example 10. The separator of any examples herein, particularly example 3-9, wherein the first ceramic material and / or second ceramic material comprise Li? xLasZr2 xTaxOi2, Li?La3Zr20i2 Lii+x AlxTi2-x(PC )3 (LATP), Lii+x+yAlxTi2-xSi3-yOi2, LiioGeP2Si2, Lii4Zn(GeO4)4, LiTi2(PO4)3, Li?La3Zr20i2, LiosLao.sTiOs, Li2S-P2Ss, Li2S-GeS2, Li2S-SiS2, Li2S-SnS2 Li3.8PO2.sNx, LiePSsX, LisYXe, (wherein X is F, Cl, Br, or I), LiGe2(PO4)3, Lii+xAlxGe2-x(PO4)3 (LAGP), or any combination thereof.

[0232] Example 1 1 . The separator of any examples herein, particularly examples 3-10, wherein the first ceramic material and / or second ceramic material comprise Li?-xLasZr2- x TaxOi2, wherein x=0.6.

[0233] Example 12. The separator of any examples herein, particularly examples 3-1 1 wherein the first binder and / or second binder, if present, comprises a polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), carboxymethylcellulose (CMC), styrene-butadiene rubber (SBR), polyacrylic acid (PAA), polyvinyl alcohol (PVA), polyvinyl butyral (PVB), polyvinylpyrrolidone (PVP), ethyl cellulose (EC), copolymers thereof, or any combination thereof.

[0234] Example 13. The separator of any examples herein, particularly examples 1 -7 or 12, wherein the first and / or second ceramic layer is substantially free of lithium, potassium, sodium, or a combination thereof.

[0235] Example 14. The separator of any examples herein, particularly examples 1 -7 or 12-13, wherein the first and / or second ceramic layer is substantially non-conductive for ions of lithium, potassium, sodium, or a combination thereof.

[0236] Example 15. The separator of any examples herein, particularly example 13 or14, wherein the first and / or second ceramic material comprises Ce-i xGdxOy, wherein x is greater or equal to 0 and less than 1 , and wherein y is selected to account for the valency of each element and overall neutrality.

[0237] Example 16. The separator of any examples herein, particularly examples 13-15, wherein the first and / or second ceramic material comprises Ceo.9Gdo.1O1.95.

[0238] Example 17. The separator of any examples herein, particularly examples 1 -7 or 12-14, wherein the first and / or second ceramic material comprises AI2O3.

[0239] Example 8. The separator of any examples herein, particularly examples 13-17, wherein the first and / or second binder is ethyl cellulose (EC).

[0240] Example 19. The separator of any examples herein, particularly example 18, wherein the EC has a viscosity of about 30 to about 70 mPa«s.

[0241] Example 20. The separator of any examples herein, particularly example 17, wherein the binder is PVDF.

[0242] Example 21 . The separator of any examples herein, particularly examples 3-20, wherein the first ceramic material and / or the second ceramic material, if present, are present in an amount of about 60 wt% to less than 100 wt% based on a total weight of the blend.

[0243] Example 22. The separator of any examples herein, particularly examples 3-21 , wherein the first binder and / or the second binder, if present, are present in an amount greater than 0 wt % to about 40 wt% based on a total weight of the blend.

[0244] Example 23. The separator of any examples herein, particularly examples 1 -22, wherein the substrate comprises a polymeric film, a glass fiber separator, cellulose- based separators, or any combination thereof.

[0245] Example 24. The separator of any examples herein, particularly example 23, wherein the polymeric film comprises a polyolefin.

[0246] Example 25. The separator of any examples herein, particularly example 24, wherein the polyolefin comprises polyethylene, polypropylene, copolymers thereof, and a combination thereof.

[0247] Example 26. The separator of any examples herein, particularly examples 1 -25, wherein the separator has a total thickness of less than about 35 microns.

[0248] Example 27. The separator of any examples herein, particularly examples 1 -26, wherein the separator has a total thickness of about 5 microns to about 30 microns.

[0249] Example 28. The separator of any examples herein, particularly examples 1 -27, wherein the first ceramic layer and / or the second ceramic layer, if present, have a thickness of about 1 micron to about 10 microns.

[0250] Example 29. The separator of any examples herein, particularly examples 2-28, wherein a second ceramic layer has the same or different thickness as the first ceramic layer disposed on the first surface of the substrate.

[0251] Example 30. The separator of any examples herein, particularly examples 1 -29, wherein the first ceramic layer and the second ceramic layer, if present, comprise a plurality of pores.

[0252] Example 31 . The separator of any examples herein, particularly example 30, wherein the pores have a size of about 2 nm to about 10 microns.

[0253] Example 32. The separator of any examples herein, particularly examples 3-30, wherein the first ceramic material and the second ceramic material, if present, have a particle size of about 100 nm to less than about 20 microns.

[0254] Example 33. The separator of any examples herein, particularly example 31 , wherein the first ceramic material and the second ceramic material, if present, have a first plurality of particles having a particle size of about 500 nanometers.

[0255] Example 34. The separator of any examples herein, particularly example 32 or 33, wherein the first ceramic material and the second ceramic material, if present, have a second plurality of particles having a particle size of about 3-20 microns.

[0256] Example 35. The separator of any examples herein, particularly examples 1 -34, wherein the first ceramic layer is uniformly disposed on at least the first surface of the substrate.

[0257] Example 36. The separator of any examples herein, particularly examples 2-35, wherein the second ceramic layer is uniformly disposed on at least the second surface of the substrate.

[0258] Example 37. The separator of any examples herein, particularly examples 1 -36, wherein the separator exhibits a lithium transference number greater than about 0.65 in the presence of an electrolyte.

[0259] Example 38. The separator of any examples herein, particularly example 37, wherein the separator exhibits a lithium transference number equal to or greater than about 0.76 in the presence of an electrolyte.

[0260] Example 39. The separator of any examples herein, particularly examples 37 or 38, wherein the separator exhibits a lithium transference number equal to or greater than about 0.89 in the presence of an electrolyte.

[0261] Example 40. The separator of any examples herein, particularly examples 1 -39, wherein the separator exhibits substantial wettability when inserted into the electrolyte.

[0262] Example 41 . A rechargeable battery comprising: the separator of any examples herein, particularly examples 1 -40; an anode material; a cathode material; and an electrolyte.

[0263] Example 42. The rechargeable battery of any examples herein, particularly example 41 , wherein the separator is positioned such that the first ceramic layer disposed on the first surface of the substrate is adjacent to the anode.

[0264] Example 43. The rechargeable battery of any examples herein, particularly example 41 or 42, wherein the separator is positioned such that the second surface of the substrate, with or without the second ceramic layer disposed thereon, is adjacent to the cathode.

[0265] Example 44. The rechargeable battery of any examples herein, particularly examples 41 -43, wherein the anode is lithium metal.

[0266] Example 45. The rechargeable battery of any examples herein, particularly examples 41 -44, wherein the electrolyte comprises a nonaqueous solvent and a salt.

[0267] Example 46. The rechargeable battery any examples herein, particularly example 45, wherein the nonaqueous solvent comprises dioxane, dimethoxyethane (DME), ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), N-methyl acetamide (NMA), acetonitrile (ACN), sulfone, sulfolane, 1 ,3-dioxolane, 1 ,2-dioxolane, 1 ,3-dimethyle-2-imidazolidinone (DMI), 1 ,1 ,2, 2-tetrafluoroethylene-2, 2, 3, 3, -tetrafluoropropyl ether (TTE), N-methyl 2- pyrrolidone (NMP), fluoroethylene carbonate (FEC), propylene Carbonate (PC), tetrahydrofuran (THF), bis(2,2,2-trifluoroethyl) ether (BTFE), or any combination thereof.

[0268] Example 47. The rechargeable battery of any examples herein, particularly example 45-46, wherein the salt comprises lithium bis(fluorosulfonyl)imide, lithium trifluoromethanesulfonate, lithium bis(trifluoromethanesulfonyl)imide, lithium difluoro(oxalato)borate, lithium bis(oxalate) borate, lithium perchlorate, lithium tetrafluoroborate, lithium difluorophosphate, lithium hexafluorophosphate, lithium hexafluroarsenate, lithium tetrachloroaluminate, lithium chlorate, lithium borate, lithium iodate, lithium triflate, lithium nitrate, or a combination thereof.

[0269] Example 48. The rechargeable battery of any examples herein, particularly example 45-47, wherein the electrolyte comprises a mixture of EC:DEC in a volume ratio of about 1 :9 to about 9:1 .

[0270] Example 49. The rechargeable battery of any examples herein, particularly example 45-48, wherein the electrolyte comprises a mixture of DME:TTE in a molar ratio of about 1 :3 to about 2:1 .

[0271] Example 50. The rechargeable battery of any examples herein, particularly example 45-49, wherein the electrolyte comprises a mixture of DME:DOL:DMI, wherein the mixture of DME:DOL is present in a volume ratio of about 9:1 to about 2:3.

[0272] Example 51 . The rechargeable battery of any examples herein, particularly example 50, further comprising about 0.05 wt % to about 5 wt% of DMI based on a total weight of the electrolyte.

[0273] Example 52. The rechargeable battery of any examples herein, particularly examples 45-47, wherein the electrolyte comprises a mixture of EMC:FEC in a volume ratio of about 12:1 to about 1 :12.

[0274] Example 53. The rechargeable battery of any examples herein, particularly example 45-47, wherein the electrolyte comprises about 1 M to about 3 M of lithium bis(fluorosulfonyl)imide dissolved in a mixture of solvents comprising DME and TTE having a ratio of about 1 :3 to about 2:1 .

[0275] Example 54. The rechargeable battery of any examples herein, particularly example 45-47, wherein the electrolyte comprises about 1 M to about 8 M of lithium bis(fluorosulfonyl)imide dissolved in a solvent comprising DME.

[0276] Example 55. The rechargeable battery of any examples herein, particularly examples 45-47, wherein the electrolyte comprises about 1 M to about 4 M of lithium bis(fluorosulfonyl)imide and about 0.05 M to about 0.5 M of lithium difluoro(oxalato)borate dissolved in a mixture of solvents comprising about 40 vol% to about 90 vol% of DME, about 10 vol% to about 60 vol% of DOL, and about 0.05 wt% to about 5 wt% of DMI.

[0277] Example 56. The rechargeable battery of any examples herein, particularly example 45-47, wherein the electrolyte comprises lithium bis(fluorosulfonyl)imide (LiFSI)- DME-TTE electrolyte.

[0278] Example 57. The rechargeable battery any examples herein, particularly example 56, wherein the electrolyte further comprises LiNO3.

[0279] Example 58. The rechargeable battery of any examples herein, particularly examples 56 or 57, further comprising FEC.

[0280] Example 59. The rechargeable battery of any examples herein, particularly example 45-47, wherein the electrolyte comprises about 0.1 M to about 4 M of lithium bis(fluorosulfonyl)imide and about 0.1 wt% to about 5 wt% of lithium difluoro(oxalato)borate dissolved in a mixture of solvents comprising a mixture of EMC:FEC in a volume ratio of about 12:1 to about 1 :12.

[0281] Example 60. The rechargeable battery of any examples herein, particularly examples 41 -57, wherein a solid electrolyte interphase is formed between the anode and the first ceramic layer deposited on the first surface of the substrate of the separator.

[0282] Example 61 . The rechargeable battery of any examples herein, particularly examples 41 -60, wherein the cathode comprises a high density nickel-rich layered transition metal oxide (Li[NixMnyCoz]02 (x+y+z = 1 )), a lithium iron phosphate (LFP), lithium manganese oxide (LiMn2O4), or nickel-doped lithium manganese oxide (□[Nio.5Mn1.5JO4).

[0283] Example 62. The rechargeable battery of any examples herein, particularly example 61 , wherein the cathode further comprises a filler and / or a binder.

[0284] Example 63. The rechargeable battery of any examples herein, particularly example 62, wherein the filler comprises a carbon black, a modified carbon black, a graphene, a multi-layer graphene, carbon fibers, carbon nanotubes, carbon nanospheres, graphite, a reduced graphene oxide, or any combination thereof.

[0285] Example 64. The rechargeable battery of any examples herein, particularly example 62 or 63 wherein the binder comprises polyvinylidene fluoride (PVDF), polyethylene oxide), cellulose, carboxymethylcellulose (CMC), a polytetrafluoroethylene (PTFE), styrene-butadiene rubber (SBR), polyacrylic acid(PAA), polyvinyl alcohol (PVA), polyvinyl butyral (PVB), polyvinylpyrrolidone (PVP), ethyl cellulose (EC), copolymers thereof, or any combination thereof.

[0286] Example 65. The rechargeable battery of any examples herein, particularly examples 41 -64, wherein the anode is substantially free of dendrites during a plating / stripping cycle of a battery operation.

[0287] Example 66. The rechargeable battery of any examples herein, particularly examples 41 -65, wherein the first ceramic layer disposed on the first surface of the substrate is substantially free of dendrites during a plating / stripping cycle of a battery operation.

[0288] Example 67. The rechargeable battery of any examples herein, particularly examples 41 -66, wherein the battery exhibits an energy density of about 150 Wh / kg to about 500 Wh / kg.

[0289] Example 68. The rechargeable battery of any examples herein, particularly examples 41 -67, wherein the battery exhibits an energy density of about 150 Wh / kg to about 300 Wh / kg.

[0290] Example 69. The rechargeable battery of any examples herein, particularly examples 41 -68, wherein the battery exhibits a specific discharge capacity of about 100 mA h / g to about 400 mA h / g when discharged at 0.1 C to 10C rate.

[0291] Example 70. The rechargeable battery of any examples herein, particularly examples 41 -69, wherein the battery exhibits a coulombic efficiency greater than about 80% for at least about 150 cycles.

[0292] Example 71 . The rechargeable battery of any examples herein, particularly examples 41 -70, wherein the battery exhibits a coulombic efficiency of greater than about 99% for at least about 150 cycles.

[0293] Example 72. The rechargeable battery of any examples herein, particularly examples 41 -71 , wherein the battery exhibits a capacity retention of at least about 80% for at least about 150 cycles.

[0294] Example 73. The rechargeable battery of any examples herein, particularly examples 41 -72, wherein the battery exhibits a capacity retention of at least about 90 % for at least about 150 cycles.

[0295] Example 74. A system comprising one or more of the rechargeable batteries of any examples herein, particularly examples 41 -73.

[0296] Example 75. An article comprising one or more of the rechargeable batteries of any examples herein, particularly examples 41 -73 or a system of claim 74.

[0297] Example 76. A method of making the separator of any examples herein, particularly examples 1 -40, wherein the method comprises: depositing a first homogeneous mixture of a first ceramic material and a first binder at a first surface of a substrate; and drying the separator to form a first uniform ceramic layer.

[0298] Example 77. The method of any examples herein, particularly example 76, further comprising depositing a second homogeneous mixture of a second ceramic material and a second binder on a second surface of the substrate that is opposite to the first surface.

[0299] Example 78. The method of any examples herein, particularly example 77, wherein the step of depositing the second homogeneous mixture of the second ceramic material and the second binder on the second surface of the substrate is done before drying the separator or after drying the separator.

[0300] Example 79. The method of any examples herein, particularly examples 77 or 78, wherein the method comprises further drying the separator to form the second ceramic layer at the second surface of the substrate.

[0301] Example 80. The method of any examples herein, particularly examples 77-78, wherein the first ceramic material is the same or different from the second ceramic material.

[0302] Example 81 . The method of any examples herein, particularly examples 77-80, the first binder is the same or different from the second binder.

[0303] Example 82. The method of any examples herein, particularly examples 76-81 , wherein the first homogeneous mixture comprises a first solvent.

[0304] Example 83. The method of any examples herein, particularly examples 77-82, wherein the second homogeneous mixture comprises a second solvent.

[0305] Example 84. The method of any examples herein, particularly examples 77-81 , wherein the first ceramic layer and / or the second ceramic layer, if present, is substantially free of the first solvent and / or second solvent, respectively, after the drying step or after the further drying step.

[0306] Example 85. The method of any examples herein, particularly examples 76-84, wherein the first ceramic material and / or second ceramic material comprise Li? xLasZr2 xTaxOi2, Li?La3Zr20i2 Lii+x AlxTi2-x(PC )3 (LATP), Lii+x+yAlxTi2-xSi3-yOi2, LiioGeP2Si2, Lii4Zn(GeO4)4, LiTi2(PO4)3, Li?La3Zr20i2, LiosLao.sTiOs, Li2S-P2Ss, Li2S-GeS2, Li2S-SiS2, Li2S-SnS2 Li3.8PO2.sNx, LiePSsX, LisYXe, (wherein X is F, Cl, Br, or I), LiGe2(PO4)3, Lii+xAlxGe2-x(PO4)3 (LAGP), or any combination thereof.

[0307] Example 86. The method of any examples herein, particularly examples 76-85, wherein the first ceramic material and / or the second ceramic material comprise Li?. xLasZr2-xTaxOi2, wherein x=0.6.

[0308] Example 87. The method of any examples herein, particularly examples 76- 826, wherein the first homogeneous mixture of the first ceramic material and the first binder further comprises a first filler, and wherein the second homogeneous mixture of the second ceramic material and second first binder, if present, further comprises a second filler.

[0309] Example 88. The method of any examples herein, particularly examples 76-87, wherein the first homogeneous mixture of the first ceramic material and the first binder further comprises a first salt, and wherein the second homogeneous mixture of the second ceramic material and second first binder, if present, further comprises a second salt.

[0310] Example 89. The method of any examples herein, particularly examples 87 or 88, wherein the first filler is the same or different as the second filler.

[0311] Example 90. The method of any examples herein, particularly examples 88-89, wherein the first salt is the same or different as the second salt.

[0312] Example 91 . The method of any examples herein, particularly examples 88-90, wherein the first salt and the second salt, if present, are solvated with the first binder and the second binder, respectively.

[0313] Example 92. The method of any examples herein, particularly examples 76-84, 87, or 89, wherein the first homogeneous mixture of the first ceramic material and the first binder and the second homogeneous mixture of the second ceramic material and second binder, if present, are substantially free of lithium, potassium, sodium, or a combination thereof.

[0314] Example 93. The method of any examples herein, particularly examples 76-84, 87, 89, or 92, wherein the first and / or second ceramic layer is substantially non- conductive for ions of lithium, potassium, sodium, or a combination thereof.

[0315] Example 94. The method of any examples herein, particularly examples 76-93, wherein the first binder and / or the second binder, if present, comprises a polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), carboxymethylcellulose (CMC), sodium carboxymethylcellulose (Na-CMC), styrenebutadiene rubber (SBR), polyacrylic acid (PAA), polyvinyl alcohol (PVA), polyvinyl butyral (PVB), polyvinylpyrrolidone (PVP), ethyl cellulose (EC), copolymers thereof, or any combination thereof.

[0316] Example 95. The method of any examples herein, particularly example 94, wherein the first binder and / or the second binder, if present, is a polyethylene oxide having a molecular weight of about 10,000 to about 1 ,000,000 Dalton.

[0317] Example 96. The method of any examples herein, particularly example 94, wherein the first binder and / or the second binder, if present, is ethyl cellulose (EC).

[0318] Example 97. The method of any examples herein, particularly example 96, wherein the EC has a viscosity of about 30 to about 70 mPa«s.

[0319] Example 98. The method of any one examples herein, particularly examples 92-94 or 96-97, wherein the first and / or second ceramic material comprises Cei- xGdxOy, wherein x is greater or equal to 0 and less than 1 , and wherein y is selected to account for the valency of each element and overall neutrality.

[0320] Example 99. The method of any examples herein, particularly examples 92-94 or 96-98, wherein the first and / or second ceramic material comprises Ceo.9Gdo 1O1.95.

[0321] Example 100. The method of any one examples herein, particularly examples 92-94 or 96-97, wherein the first and / or second ceramic material comprises AI2O3.

[0322] Example 101 . The method of any examples herein, particularly examples 76-99, wherein the first homogeneous mixture and / or the second homogeneous mixture, if present, comprises the first and / or the second ceramic material in an amount of about 60 wt% to less than 100 wt% based on a total weight of solids.

[0323] Example 102. The method of any examples herein, particularly examples 76-100, wherein the first homogeneous mixture and / or the second homogeneous mixture, if present, comprises the first binder and / or the second binder in an amount greater than 0 wt % to about 40 wt% based on a total weight of solids.

[0324] Example 103. The method of any examples herein, particularly examples 76-102, wherein the first homogeneous mixture and / or the second homogeneous mixture, if present, has a viscosity from about 100 to about 100,000 mPa«s.

[0325] Example 104. The method of any examples herein, particularly examples 96-103, wherein the substrate comprises a polymeric film, a glass fiber separator, cellulose-based separators, or any combination thereof.

[0326] Example 105. The method of any examples herein, particularly example 104, wherein the polymeric film comprises a polyolefin.

[0327] Example 106. The method of any examples herein, particularly example 105, wherein the polyolefin comprises polyethylene, polypropylene, copolymers thereof, and a combination thereof.

[0328] Example 107. The method of any examples herein, particularly examples 76-106, wherein the step of depositing is a slurry coating.

[0329] Example 108. The method of any examples herein, particularly examples 77-107, wherein the first ceramic layer and / or the second ceramic layer, if present, has a thickness of about 1 micron to about 10 microns.

[0330] Example 109. The method of any examples herein, particularly examples 76-108, wherein the separator has a total thickness of less than about 35 microns.

[0331] Example 110. The method of any examples herein, particularly examples 76-109, wherein the separator has a total thickness of about 5 microns to about 30 microns.

[0332] Example 11 1. The method of any examples herein, particularly examples 76-110, wherein the second ceramic layer disposed on the second surface of the substrate has the same or different thickness as the first ceramic layer disposed on the first surface of the substrate.

[0333] Example 112. The method of any examples herein, particularly examples 76-111 , wherein the first ceramic layer and the second ceramic layer, if present, comprise a plurality of pores.

[0334] Example 113. The method of any examples herein, particularly example 112, wherein the pores have a size of about 2 nm to about 10 microns.

[0335] Example 114. The method of any examples herein, particularly examples Tel l 3, wherein the first ceramic material and the second ceramic material, if present, have a particle size of about 100 nm to less than about 20 microns.

[0336] Example 115. The method of any examples herein, particularly example 114, wherein the first ceramic material and the second ceramic material, if present, have a first plurality of particles having a particle size of about 500 nanometers.

[0337] Example 116. The method of any examples herein, particularly example 114 or115, wherein the first ceramic material and the second ceramic material, if present, have a second plurality of particles having a particle size of about 3-20 microns.

[0338] Example 117. The method of any examples herein, particularly examples 76-116, wherein the separator exhibits a lithium transference number of greater than about 0.65 in the presence of an electrolyte.

[0339] Example 118. The method of any examples herein, particularly example 117, wherein the separator exhibits a lithium transference number equal to or greater than about 0.76 in the presence of an electrolyte.

[0340] Example 119. The method of any examples herein, particularly examples 117 or 1 18, wherein the separator exhibits a lithium transference number equal to or greater than about 0.89 in the presence of an electrolyte.

[0341] Example 120. The method of any examples herein, particularly examples 76- 119, wherein the separator exhibits substantial wettability when inserted into the electrolyte.

[0342] Example 121 . A rechargeable battery comprising: a Li anode material; a cathode material; and an electrolyte, wherein the electrolyte comprises about 1 M to about 4 M of lithium bis(fluorosulfonyl)imide and about 0.05 M to about 0.5 M of lithium difluoro(oxalato)borate dissolved in a mixture of solvents comprising about 40 vol% to about 90 vol% of DME, about 10 vol% to about 60 vol% of DOL, and about 0.05 wt% to about 5 wt% of DMI.

[0343] Example 122. The rechargeable battery of any examples herein, particularly example 121 , wherein the cathode comprises a high density nickel-rich layered transition metal oxide (Li[NixMnyCoz]02 (x+y+z = 1 )), a lithium iron phosphate (LFP),lithium manganese oxide (LiMn2O4), or nickel-doped lithium manganese oxide (□[Nio.5Mn1.5jO4).

[0344] Example 123. The rechargeable battery of any examples herein, particularly examples 121 -122, further comprising a separator.

[0345] Example 124. The rechargeable battery of any examples herein, particularly examples 121 -123, wherein the anode is substantially free of dendrites during a plating / stripping cycle of a battery operation.

[0346] Example 125. The rechargeable battery of any examples herein, particularly examples 121 -124, wherein the battery exhibits an energy density of about 150 Wh / kg to about 500 Wh / kg.

[0347] Example 126. The rechargeable battery of any examples herein, particularly examples 121 -125, wherein the battery exhibits an energy density of about 150 Wh / kg to about 300 Wh / kg.

[0348] Example 127. The rechargeable battery of any examples herein, particularly examples 121 -126, wherein the battery exhibits a specific discharge capacity of about 100 mA h / g to about 400 mA h / g discharged at 0.1 C rate.

[0349] Example 128. The rechargeable battery of any examples herein, particularly examples 121 -127, wherein the battery exhibits a coulombic efficiency of greater than about 99% for at least about 150 cycles.

[0350] Example 129. The rechargeable battery of any examples herein, particularly examples 121 -128, wherein the battery exhibits a capacity retention of at least about 80% for at least about 150 cycles.

[0351] Example 130. A system comprising one or more of the rechargeable batteries of any examples herein, particularly examples 121 -129.

Claims

WHAT IS CLAIMED IS:1 . A separator comprising: a substrate having a first surface and an opposite second surface; and a first ceramic layer disposed on at least the first surface of the substrate; wherein the first ceramic layer comprises a first homogenous blend comprising a first ceramic material and a first binder; and optionally, a second ceramic layer is disposed at the second surface of the substrate and, wherein the second ceramic layer comprises a second homogeneous blend comprising a second ceramic material and a second binder, wherein the separator exhibits an ionic conductivity of about 0.01 mS / cm to about 100 mS / cm when inserted in an electrolyte and wherein the separator is used in a rechargeable battery.

2. The separator of claim 1 , wherein the first ceramic material is the same or different from the second ceramic material if present, and / or the first binder is the same or different from the second binder, if present.

3. The separator of any one of claims 1 -2, wherein the first ceramic layer and / or the second ceramic layer, if present, further comprise a salt.

4. The separator of claim 3, wherein the salt is solvated within the first and / or second binder, respectively.

5. The separator of any one of claims 1 -4, wherein the first ceramic material and / or second ceramic material comprise Li7-xLa3Zr2-xTaxOi2, Li?La3Zr20i2 Lii+XAlxTi2-x(PO4)3 (LATP), Lii+x+yAlxTi2-xSi3-yOi2, LiioGeP2Si2, Lii4Zn(GeO4)4, LiTi2(PO4)3, Li?La3Zr20i2, Lio.sLao.sTiOs, U2S-P2S5, Li2S-GeS2, Li2S-SiS2, Li2S-SnS2 Li3.8PO2.sNx, Li6PS5X, Li3YX6, (wherein X is F, Cl, Br, or I), LiGe2(PO4)3, Lii+xAlxGe2-x(PO4)3 (LAGP), or any combination thereof.

6. The separator of any one of claims 1 -5, wherein the first ceramic material and / or second ceramic material comprise Li7-xLa3Zr2-xTaxOi2, wherein x=0.6;7. The separator of any one of claims 1 -6 wherein the first binder and / or second binder, if present, comprises a polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), carboxymethylcellulose (CMC), styrenebutadiene rubber (SBR), polyacrylic acid (PAA), polyvinyl alcohol (PVA), polyvinyl butyral (PVB), polyvinylpyrrolidone (PVP), ethyl cellulose (EC), copolymers thereof, or any combination thereof.

8. The separator of any one of claims 1 -2 or 7, wherein the first and / or second ceramic layer is substantially free of lithium, potassium, sodium, or a combination thereof.

9. The separator of claim 8, wherein the first and / or second ceramic material comprises Cei xGdxOy, wherein x is greater or equal to 0 and less than 1 , and wherein y is selected to account for the valency of each element and overall neutrality.

10. The separator of any one of claims 8-9, wherein the first and / or second ceramic material comprises Ceo.9Gdo.1O1.95.11 . The separator of any one of claims 1 -2 or 8, wherein the first and / or second ceramic material comprises AI2O3.

12. The separator of any one of claims 7-11 , wherein the first and / or second binder is ethyl cellulose (EC).

13. The separator of claim 11 , wherein the binder is PVDF.

14. The separator of any one of claims 1 -13, wherein the first ceramic material and / or the second ceramic material, if present, are present in an amount of about 60 wt% to less than 100 wt% based on a total weight of the blend.

15. The separator of any one of claims 1 -14, wherein the first binder and / or the second binder, if present, are present in an amount greater than 0 wt % to about 40 wt% based on a total weight of the blend.

16. The separator of any one of claims 1 -15, wherein the substrate comprises a polymeric film, a glass fiber separator, cellulose-based separators, or any combination thereof.

17. The separator of claim 16, wherein the polymeric film comprises polyethylene, polypropylene, copolymers thereof, and a combination thereof.

18. The separator of any one of claims 1 -17, wherein the separator has a total thickness of less than about 35 microns or about 5 microns to about 30 microns.

19. The separator of any one of claims 1 -18, wherein the first ceramic layer and / or the second ceramic layer, if present, have a thickness of about 1 micron to about 20 microns.

20. The separator of any one of claims 1 -19, wherein the first ceramic layer and the second ceramic layer, if present, comprise a plurality of pores and wherein the pores have a size of about 2 nm to about 10 microns.21 . The separator of any one of claims 1 -20, wherein the first ceramic material and the second ceramic material, if present, have a particle size of about 20 nm to less than about 20 microns.

22. The separator of claim 21 , wherein the first ceramic material and the second ceramic material, if present, have a first plurality of particles having a particle size of about 500 nanometers.

23. The separator of claim 21 or 22, wherein the first ceramic material and the second ceramic material, if present, have a second plurality of particles having a particle size of about 3-20 microns.

24. The separator of any one of claims 1 -23, wherein the separator exhibits a lithium transference number greater than about 0.65, or equal to or greater than about 0.76, or equal to or greater than about 0.89 when exposed to an electrolyte.

25. The separator of any one of claims 1 -24, wherein the separator exhibits substantial wettability when inserted into the electrolyte.

26. A rechargeable battery comprising: the separator of any one of claims 1 -25; an anode material; a cathode material; and an electrolyte.

27. The rechargeable battery of claim 26, wherein the separator is positioned such that the first ceramic layer disposed on the first surface of the substrate is adjacent to the anode and that the second surface of the substrate, with or without the second ceramic layer disposed thereon, is adjacent to the cathode.

28. The rechargeable battery of any one of claims 26-27, wherein the anode is lithium metal.

29. The rechargeable battery of any one of claims 26-28, wherein the electrolyte comprises a nonaqueous solvent and a salt.

30. The rechargeable battery of claim 29, wherein the nonaqueous solvent comprises dioxane, dimethoxyethane (DME), ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), N-methyl acetamide (NMA), acetonitrile (ACN), sulfone, sulfolane, 1 ,3-dioxolane, 1 ,2-dioxolane, 1 ,3-dimethyle-2-imidazolidinone (DMI), 1 ,1 ,2,2-tetrafluoroethylene-2,2,3,3,- tetrafluoropropyl ether (TTE), N-methyl 2-pyrrolidone (NMP), fluoroethylene carbonate (FEC), propylene Carbonate (PC), tetrahydrofuran (THF), bis(2,2,2-trifluoroethyl) ether (BTFE), or any combination thereof.31 . The rechargeable battery of any one of claims 29-30, wherein the salt comprises lithium bis(fluorosulfonyl)imide, lithium trifluoromethanesulfonate, lithium bis(trifluoromethanesulfonyl)imide, lithium difluoro(oxalato)borate, lithium bis(oxalate) borate, lithium perchlorate, lithium tetrafluoroborate, lithium difluorophosphate, lithium hexafluorophosphate, lithium hexafluroarsenate, lithium tetrachloroaluminate, lithiumchlorate, lithium borate, lithium iodate, lithium tritiate, lithium nitrate, or a combination thereof.

32. The rechargeable battery of any one of claims 29-31 , wherein the electrolyte comprises a mixture of EC:DEC in a volume ratio of about 1 :9 to about 9:1 .

33. The rechargeable battery of any one of claims 29-32, wherein the electrolyte comprises a mixture of DME:TTE in a molar ratio of about 1 :3 to about 2:1 .

34. The rechargeable battery of any one of claims 29-33, wherein the electrolyte comprises a mixture of DME:DOL:DMI, wherein the mixture of DME:DOL is present in a volume ratio of about 9:1 to about 2:3.

35. The rechargeable battery of claim 34 further comprising about 0.05 wt % to about 5 wt% of DMI based on a total weight of the electrolyte.

36. The rechargeable battery of any one of claims 29-31 , wherein the electrolyte comprises a mixture of EMC:FEC in a volume ratio of about 12:1 to about 1 :12.

37. The rechargeable battery of any one of claims 29-31 , wherein the electrolyte comprises about 1 M to about 3 M of lithium bis(fluorosulfonyl)imide dissolved in a mixture of solvents comprising DME and TTE having a ratio of about 1 :3 to about 2:1 .

38. The rechargeable battery of any one of claims 29-31 , wherein the electrolyte comprises about 1 M to about 8 M of lithium bis(fluorosulfonyl)imide dissolved in a solvent comprising DME.

39. The rechargeable battery of any one of claims 29-31 , wherein the electrolyte comprises about 1 M to about 4 M of lithium bis(fluorosulfonyl)imide and about 0.05 M to about 0.5 M of lithium difluoro(oxalato)borate dissolved in a mixture of solvents comprising about 40 vol% to about 90 vol% of DME, about 10 vol% to about 60 vol% of DOL, and about 0.05 wt% to about 5 wt% of DMI.

40. The rechargeable battery of any one of claims 29-31 , wherein the electrolyte comprises lithium bis(fluorosulfonyl)imide (LiFSI)- DME-TTE electrolyte.41 . The rechargeable battery of claim 40, wherein the electrolyte further comprises LiNOs.

42. The rechargeable battery of claim 40 or 41 further comprising FEC.

43. The rechargeable battery of any one of claims 29-31 , wherein the electrolyte comprises about 0.1 M to about 4 M of lithium bis(fluorosulfonyl)imide and about 0.1 wt% to about 5 wt% of lithium difluoro(oxalato)borate dissolved in a mixture of solvents comprising a mixture of EMC:FEC in a volume ratio of about 12:1 to about 1 :12.

44. The rechargeable battery of any one of claims 26-43, wherein a solid electrolyte interphase is formed between the anode and the first ceramic layer deposited on the first surface of the substrate of the separator.

45. The rechargeable battery of any one of claims 26-44, wherein the cathode comprises a high density nickel-rich layered transition metal oxide (Li[NixMnyCoz]02 (x+y+z = 1 )), a lithium iron phosphate (LFP), lithium manganese oxide (LiMnpCh), or nickel-doped lithium manganese oxide (LifNio.5Mm.5jO4).

46. The rechargeable battery of claim 45, wherein the cathode further comprises a filler and / or a binder.

47. The rechargeable battery of claim 46, wherein the filler comprises a carbon black, a modified carbon black, a graphene, a multi-layer graphene, carbon fibers, carbon nanotubes, carbon nanospheres, graphite, a reduced graphene oxide, or any combination thereof.

48. The rechargeable battery of claim 45 or 46 wherein the binder comprises polyvinylidene fluoride (PVDF), polyethylene oxide), cellulose, carboxymethylcellulose (CMC), a polytetrafluoroethylene (PTFE), styrene-butadiene rubber (SBR), polyacrylic acid (PAA), polyvinyl alcohol (PVA), polyvinyl butyral (PVB), polyvinylpyrrolidone (PVP), ethyl cellulose (EC), copolymers thereof, or any combination thereof.

49. The rechargeable battery of any one of claims 26-48, wherein the anode is substantially free of dendrites during a plating / stripping cycle of a battery operationand / or wherein the first ceramic layer disposed on the first surface of the substrate is substantially free of dendrites during a plating / stripping cycle of a battery operation.

50. The rechargeable battery of any one of claims 26-49, wherein the battery exhibits an energy density of about 150 Wh / kg to about 500 Wh / kg.51 . The rechargeable battery of any one of claims 26-50, wherein the battery exhibits a specific discharge capacity of about 50 mA h / g to about 400 mA h / g when discharged at 0.1 C to 10C rate.

52. The rechargeable battery of any one of claims 26-51 , wherein the battery exhibits a coulombic efficiency greater than about 80% or greater than about 99% for at least about 150 cycles and / or the battery exhibits a capacity retention of at least about 80 % or greater than about 90% for at least about 150 cycles.

53. A system comprising one or more of the rechargeable batteries of any one of claims 26-52.

54. An article comprising one or more of the rechargeable batteries of any one of claims 26-52 or a system of claim 53.

55. A method of making the separator of any one of claims 1 -25, wherein the method comprises: depositing a first homogeneous mixture of a first ceramic material and a first binder at a first surface of a substrate; optionally depositing a second homogeneous mixture of a second ceramic material and a second binder on a second surface of the substrate that is opposite to the first surface and drying the separator to form a first uniform ceramic layer and optionally to form a second uniform ceramic layer.

56. The method of claim 55, wherein the step of depositing the second homogeneous mixture of the second ceramic material and the second binder on thesecond surface of the substrate, if present, is done before drying the separator or after drying the separator.

57. The method of any one of claims 55-56, wherein the first homogeneous mixture comprises a first solvent and wherein the second homogeneous mixture, if present, comprises a second solvent.

58. The method of claim 57, wherein the first ceramic layer and / or the second ceramic layer, if present, are substantially free of the first solvent and / or second solvent, respectively, after the drying step or after the further drying step.

59. The method of any one of claims 55-58, wherein the first ceramic material and / or second ceramic material comprise Li? xLasZr2xTaxOi2, Li?LasZr20i2 Liux AlxTi2-x(PO4)3 (LATP), Lii+x+yAlxTi2-xSi3-yOi2, LiioGeP2Si2, Lii4Zn(GeO4)4, LiTi2(PO4)s, Li?La3Zr20i2, Lio.sLao.sTiOs, U2S-P2S5, Li2S-GeS2, Li2S-SiS2, Li2S-SnS2 Li3.8PO2.3Nx, Li6PS5X, Li3YX6, (wherein X is F, Cl, Br, or I), LiGe2(PO4)3, Lii+xAlxGe2-x(PO4)3 (LAGP), or any combination thereof.

60. The method of any one of claims 55-59, wherein the first ceramic material and / or the second ceramic material comprise Li?-xLa3Zr2-xTaxOi2, wherein x=0.6.61 . The method of any one of claims 55-60, wherein the first homogeneous mixture of the first ceramic material and the first binder further comprises a first filler, and wherein the second homogeneous mixture of the second ceramic material and second first binder, if present, further comprises a second filler.

62. The method of any one of claims 55-61 , wherein the first homogeneous mixture of the first ceramic material and the first binder further comprises a first salt, and wherein the second homogeneous mixture of the second ceramic material and second first binder, if present, further comprises a second salt.

63. The method of claim 62, wherein the first salt and the second salt, if present, are solvated with the first binder and the second binder, respectively.

64. The method of any one of claims 55-60, or 63, wherein the first homogeneous mixture of the first ceramic material and the first binder and the second homogeneousmixture of the second ceramic material and second binder, if present, are substantially free of lithium, potassium, sodium, or a combination thereof and wherein the first and / or second ceramic layer is substantially non-conductive for ions of lithium, potassium, sodium, or a combination thereof.

65. The method of any one of claims 55-64, wherein the first binder and / or the second binder, if present, comprises a polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), carboxymethylcellulose (CMC), sodium carboxymethylcellulose (Na-CMC), styrene-butadiene rubber (SBR), polyacrylic acid (PAA), polyvinyl alcohol (PVA), polyvinyl butyral (PVB), polyvinylpyrrolidone (PVP), ethyl cellulose (EC), copolymers thereof, or any combination thereof.

66. The method of claim 65, wherein the first binder and / or the second binder, if present, is a polyethylene oxide having a molecular weight of about 10,000 to about 1 ,000,000 Dalton.

67. The method of claim 66, wherein the first binder and / or the second binder, if present, is ethyl cellulose (EC) havinga viscosity of about 30 to about 70 mPa«s.

68. The method of any one claims 65-67, wherein the first and / or second ceramic material comprises Ce-i xGdxOy, wherein x is greater or equal to 0 and less than 1 , and wherein y is selected to account for the valency of each element and overall neutrality.

69. The method of any one of claims 65-68, wherein the first and / or second ceramic material comprises Ceo.9Gdo.1O1.95.

70. The separator of any one of claims 65-67, wherein the first and / or second ceramic material comprises AI2O3.71 . The method of any one of claims 55-69, wherein the first homogeneous mixture and / or the second homogeneous mixture, if present, comprises the first and / or the second ceramic material in an amount of about 60 wt% to less than 100 wt% based on a total weight of solids.

72. The method of any one of claims 55-70, wherein the first homogeneous mixture and / or the second homogeneous mixture, if present, comprises the first binder and / or the second binder in an amount greater than 0 wt % to about 40 wt% based on a total weight of solids.

73. The method of any one of claims 55-71 , wherein the first homogeneous mixture and / or the second homogeneous mixture, if present, has a viscosity from about 100 to about 100,000 mPa s.

74. The method of any one of claims 55-72, wherein the substrate comprises a polymeric film, a glass fiber separator, cellulose-based separators, or any combination thereof.

75. The method of any one of claims 55-73, wherein the step of depositing is a slurry coating.

76. The method of any one of claims 55-74, wherein the first ceramic layer and / or the second ceramic layer, if present, has a thickness of about 1 micron to about 20 microns.

77. The method of any one of claims 55-75, wherein the separator has a total thickness of less than about 35 microns, or about 5 microns to about 30 microns.

78. The method of any one of claims 55-76, wherein the first ceramic layer and the second ceramic layer, if present, comprise a plurality of pores, having a size of about 2 nm to about 10 microns.

79. The method of any one of claims 55-77, wherein the first ceramic material and the second ceramic material, if present, have a particle size of about 20 nm to less than about 20 microns.

80. The method of claim 78, wherein the first ceramic material and the second ceramic material, if present, have a first plurality of particles having a particle size of about 500 nanometers and a second plurality of particles having a particle size of about 3-20 microns.81 . The method of any one of claims 55-79, wherein the separator exhibits a lithium transference number greater than about 0.65, or equal to or greater than about 0.76, or equal to or greater than about 0.89 when exposed to an electrolyte.

82. The method of any one of claims 55-80, wherein the separator exhibits substantial wettability when inserted into the electrolyte.

83. A rechargeable battery comprising: a Li anode material; a cathode material; and an electrolyte, wherein the electrolyte comprises about 1 M to about 4 M of lithium bis(fluorosulfonyl)imide and about 0.05 M to about 0.5 M of lithium difluoro(oxalato)borate dissolved in a mixture of solvents comprising about 40 vol% to about 90 vol% of DME, about 10 vol% to about 60 vol% of DOL, and about 0.05 wt% to about 5 wt% of DM I.

84. The rechargeable battery of claim 83, wherein the cathode materal comprises a high density nickel-rich layered transition metal oxide (Li[NixMnyCoz]02 (x+y+z = 1 )), a lithium iron phosphate (LFP), lithium manganese oxide (LiMn2O4), or nickel-doped lithium manganese oxide (Li[Nio.5Mm.5]04).

85. The rechargeable battery of any one of claims 83-84, further comprising a separator.

86. The rechargeable battery of any one of claims 83-85, wherein the anode material is substantially free of dendrites during a plating / stripping cycle of a battery operation.

87. The rechargeable battery of any one of claims 83-86, wherein the battery exhibits an energy density of about 150 Wh / kg to about 500 Wh / kg.

88. The rechargeable battery of any one of claims 83-87, wherein the battery exhibits a specific discharge capacity of about 500 mA h / g to about 400 mA h / g discharged at 0.1 C rate.

89. The rechargeable battery of any one of claims 83-88, wherein the battery exhibits a coulombic efficiency of greater than about 99% for at least about 150 cycles and, wherein the battery exhibits a capacity retention of at least about 80 % for at least about 150 cycles.

90. A system comprising one or more of the rechargeable batteries of any one of claims 83-89.

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