Metallophilic matrices for rechargeable batteries

Abstract

Disclosed herein is an anode comprising a conductive substrate material comprising an effective amount of a metallophilic seed material catalyzing nucleation of one or more metals comprising Na, Li, K, Mg, Zn, or any combination thereof, wherein the metallophilic seed material is a salt comprising cations of Bi3+, Sb5+, Sb3+, Pb2+, In3+, Te4+, Al3+, Ag+, Fe2+, Fe3+, Mn2+, Co2+, Ni2+, Mo2+ / 3+ / 5+ / 6+, W2+ / 3+ / 5+ / 6+, Nb4+ / 5+, Y3+, La3+, Sr2+ Mg2+ or any combination thereof; and a metallic layer disposed on the conductive substrate, wherein the metallic layer comprises an active anode material comprising Na, Li, K, Mg, Zn, or any combination thereof. Also disclosed herein are electrochemical cells comprising the same.

Description

[0001] METALLOPHILIC MATRICES FOR RECHARGEABLE BATTERIES

[0002] CROSS-REFERENCE TO RELATED APPLICATIONS

[0003]

[0001] This application claims the benefit of priority to United States Provisional Application No. 63 / 667,880, filed July 5, 2024, the disclosure of which is incorporated herein by reference in its entirety.

[0004] STATEMENT ACKNOWLEDGING GOVERNMENT SUPPORT

[0005]

[0002] This invention was made with government support under Grant No. DE- SC0005397 awarded by the Department of Energy. The government has certain rights in the invention.

[0006] FIELD

[0007]

[0003] This application relates generally to negative electrodes in rechargeable batteries.

[0008] BACKGROUND

[0009]

[0004] The burgeoning demand for renewable energy storage and electric vehicles underscores the need for innovative battery technologies to sustain the growth. Lithium-ion batteries (LIBs), despite being the most prevalent energy storage technology, fall short of meeting the evolving demands of modern portable electronic devices, electric vehicles, and smart grids. As an alternative to LIBs for storing energy, sodium-based batteries offer great potential as next-generation energy storage systems due to the abundance and low cost of sodium-based minerals. Sodium metal with a low redox potential (-2.71 V vs. standard hydrogen electrode) and a high theoretical specific capacity (1 ,166 mA h g~1) has garnered considerable research attention as an anode for sodium-metal batteries (SMBs) in recent years.

[0010]

[0005] For decades, significant endeavors have been undertaken to elucidate the mechanisms underlying sodium (Na) deposition, mitigate dendrite formation, and stabilize the solid electrolyte interphase (SEI) in order to unleash the full potential of sodium-metal anodes. Innovative approaches employed previously are the use of solid-state electrolytes, optimization of liquid electrolytes, engineering of sodiophilic hosts / current collector, and constructing interfacial protective layers. However, the preparation procedures of many reported hosts are complicated, posing a challenge for practical viability.

[0011]

[0006] Thus, there remains a need for novel secondary batteries that can overcome these challenges. This disclosure at least partially addresses these and other needs.

[0012] SUMMARY

[0013]

[0007] Disclosed herein is an anode comprising a conductive substrate material comprising an effective amount of a metallophil ic seed material catalyzing nucleation of one or more metals comprising Na, Li, K, Mg, Zn, or any combination thereof, wherein the metallophilic seed material is a salt comprising cations of Bi3+, Sb5+, Sb3+, Pb2+, ln3+, Te4+, Al3+, Ag+, Fe2+, Fe3+, Mn2+, Co2+, Ni2+, MO2+ / 3+ / 5+ / 6+, W2+ / 3+ / 5+ / 6+^ Nb4+ / 5+, y3+, La3+, Mg2+, Sr2+or any combination thereof; and a metallic layer disposed on the conductive substrate, wherein the metallic layer comprises an active anode material comprising Na, Li, K, Mg, Zn, or any combination thereof.

[0014]

[0008] Also disclosed is an electrochemical cell comprising any of the disclosed herein anodes and an electrolyte.

[0015]

[0009] In still further aspects, disclosed is a method comprising: depositing an effective amount of a metallophilic seed material for nucleation of one or more metals comprising Na, Li, K, Mg, Zn or any combination thereof on a conductive substrate, wherein the metallophilic seed material is a salt comprising cations of Bi3+, Sb5+, Sb3+, Pb2+, ln3+, Te4+, Al3+, Ag+, Fe2+, Fe3+, Mn2+, Co2+, Ni2+, MO2+ / 3+ / 5+ / 6+, W2+ / 3+ / 5+ / 6+, Nb4+ / 5+, Y3+, La3+, Mg2+, Sr2+or any combination thereof; and depositing an active anode material to form a metallic layer comprising Na, Li, K, Mg, Zn, or any combination thereof to form any of the disclosed herein anodes.

[0016]

[0010] Yet still disclosed herein is a method comprising: providing any of the disclosed herein anodes, providing an electrolyte; providing a cathode; and providing a separator to form an electrochemical cell.

[0017]

[0011] In accordance with the purposes of the disclosed materials, compounds, compositions, and methods, as embodied and broadly described herein, the disclosed subject matter, in one aspect, relates to compounds and compositions and methods for preparing and using such compounds and compositions.

[0012] Additional advantages will be set forth in part in the description that follows, and in part will be obvious from the description or may be learned by practice of the aspects described below. The advantages described below will be realized and attained by means of the elements and combinations 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 are not restrictive.

[0018] BRIEF DESCRIPTION OF THE FIGURES

[0019]

[0013] The accompanying figures, which are incorporated in and constitute a part of this specification, illustrate several aspects described below.

[0020]

[0014] FIGURE 1 depicts a schematic of a potential mechanism for the formation of an exemplary anode according to one aspect of the disclosure.

[0021]

[0015] FIGURE 2 depicts the synthetic route and mechanism via an illustration of the synthetic route and mechanism after the cycling of Na@CNT-BiFs.

[0022]

[0016] FIGURES 3A-3G depict the characterization and electrochemical performance of Na@CNT-BiFs. FIG. 3A shows digital images of CNT and CNT- BiFs electrodes, comparing the sodiophilicity for molten Na metal. FIG. 3B shows voltage profiles of the Na@CNT-BiFs || Na@CNT-BiFs cells measured at 2 mA cm-2. FIG. 3C shows the Coulombic Efficiency of Na plating / stripping using Cu electrodes with Na@CNT-BiFs or bare Na@CNT at 1 mA cm-2. FIG. 3D shows the voltage-capacity curves of Na plating / stripping using Cu electrodes with Na@CNT- BiFs at a current density of 1 mA cm-2. FIG. 3E shows TOF-SIMS depth profiling of Na?- secondary ions in FIG. 3A after cycling Na@CNT and Na@CNT-BiF3. FIGS. 3F-3G show TOF-SIMS 3D visualization of after cycling Na@CNT-BiFs (FIG. 3F) and Na@CNT (FIG. 3G).

[0023]

[0017] FIGURES 4A-4F depict the morphological characterization of the anode. Top-surface SEM of BiF3-CNT (FIG. 4A), Na@CNT-BiF3(before cycling) (FIG. 4C), and Na@CNT-BiFs (after 200 cycles) (FIG. 4E) are shown. Cross-sectional morphologies of BiFs-CNT (FIG. 4B), Na@CNT-BiFs (before cycling) (FIG. 4D), and Na@CNT-BiFs (after 200 cycles) (FIG. 4F) are also shown.

[0024]

[0018] FIGURES 5A-5F depict electrochemical behaviors and characterization. FIG. 5A shows galvanostatic discharge curves (< 0 V) at a current rate of 1 mA cm-2 in Cu, CNT, and CNT-BiFs electrodes. FIGS. 5B-5C show high-resolution Bi 4f XPS data of BiFs (FIG. 5B) and Na@CNT-BiF3 before cycling (FIG. 5C). FIG. 5D shows depth profiles of Na2_, C_, Na2F_, and NaS- secondary ions, and FIG. 5E shows 3D visualization after many cycles of Na plating in Na@CNT-BiFs. FIG. 5F shows cross-sectional SEMs of C, Bi, F, Na, and S elements mapping in selected areas of Na@CNT-BiF3 after many cycles.

[0025]

[0019] FIGURES 6A-6B depict in-operando X-ray diffraction (XRD) characterization. Charge and discharge curves of Na@CNT || Na@CNT (FIG. 6A) and Na@CNT-BiFs || Na@CNT-BiFs (FIG. 6 B) coin cell, and the corresponding diffraction patterns are shown.

[0026]

[0020] FIGURES 7A-7H depict the characterization and electrochemical performance of Cu-BiFs anodes. Coulombic efficiency and voltage-capacity curves of Na plating / stripping in Cu - 0% BiF3(FIGS. 7A-7B), Cu - 5% BiF3(FIGS. 7C-7D), Cu - 20% BiF3(FIGS. 7E-7F), and Cu - 40% BiF3(FIGS. 7G-7H) at 1 mA cm’2are shown.

[0027]

[0021] FIGURES 8A-8E depict the electrochemical performance of Na@CNT-BiFs and Na@Cu-BiFs. FIG. 8A shows voltage profiles of Na@CNT-BiFs at various cycles. FIG. Figure 8B shows the cycling performances of bare Na and Na@CNT-BiF3 electrodes at a 0.1 C rate FIG. 8C shows cycling performance of Na@CNT-BiF3 electrodes at 1C rate. FIGS. 8D-8E show cycling performances of Na@Cu-BiFs electrodes in coin cell (FIG. 8D) and pouch cell (FIG. 8E) at 0.1 C rate.

[0028] DETAILED DESCRIPTION

[0029]

[0022] The materials, compounds, compositions, articles, and methods described herein may be understood more readily by reference to the following detailed description of specific aspects of the disclosed subject matter and the Examples included therein.

[0030]

[0023] Before the present materials, compounds, compositions, kits, and methods are disclosed and described, it is to be understood that the aspects described below are not limited to specific synthetic methods or specific reagents, as such may, 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.

[0024] Also, throughout this specification, various publications are referenced. The disclosures of these publications in their entirety are hereby incorporated by reference into this application in order to more fully describe the state of the art to which the disclosed matter pertains. The references disclosed are also individually and specifically incorporated by reference herein for the material contained in them that is discussed in the sentence in which the reference is relied upon.

[0031] DEFINITIONS

[0032]

[0025] In this specification and in the claims that follow, reference will be made to a number of terms, which shall be defined to have the following meanings:

[0033]

[0026] 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.

[0034]

[0027] It is appreciated that certain features of the disclosure, which are described for clarity 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.

[0035]

[0028] 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.

[0036]

[0029] 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.

[0037]

[0030] 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.

[0038]

[0031] The term “or” means “and / or.” Recitation of ranges of values is merely intended to serve as a shorthand method of referring individually to each separate value falling within the range unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. The endpoints of all ranges are included within the range and are independently combinable. All methods described herein can be performed in a suitable order unless otherwise indicated herein or otherwise clearly contradicted by context.

[0039]

[0032] 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.

[0040]

[0033] 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 understood that an appropriate, effective amount will be readily determined by one of ordinary skill in the art.

[0041]

[0034] 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'."

[0042]

[0035] 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 subranges 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.

[0043]

[0036] Recitation of ranges of values herein is merely intended to serve as a shorthand method of referring individually to each separate value recited or falling within the range unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited. Ranges provided herein are understood to be shorthand for all of the values within the range. For example, a range of 1 to 50 is understood to include any number, or combination of numbers, from the group consisting of 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 , 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 , 22, 23, 24, 25, 26, 27, 28, 29, 30, 31 , 32, 33, 34, 35, 36, 37, 38, 39, 40, 41 , 42, 43, 44, 45, 46, 47, 48, 49, or 50 or sub-ranges from the group consisting of 10-40, 20-50, 5-35, etc. Similarly, numerical ranges recited herein by endpoints include subranges subsumed within that range (e.g., 1 to 5 includes 1- 1.5, 1.5-2, 2-2.75, 2.75-3, 3-3.90, 3.90-4, 4-4.24, 4.24-5, 2-5, 3-5, 1-4, and 2-4).

[0044]

[0037] As used herein, the term “composition” is intended to encompass a product comprising the specified ingredients in the specified amounts, as well as any product that results, directly or indirectly, from a combination of the specified ingredients in the specified amounts.

[0045]

[0038] 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.

[0046]

[0039] 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.

[0047]

[0040] 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.

[0048]

[0041] 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.

[0049]

[0042] 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. It is understood that this definition also includes the ranges when no word “about” is present.

[0050]

[0043] 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 or based on any other calculations as disclosed. It is understood that this definition also includes the ranges when no word “about” is present.

[0051]

[0044] As used herein, the term “substantially,” in, for example, the context “substantially identical” or “substantially similar,” refers to a method or a system, or a component that is 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% by similar to the method, system, or the component it is compared to. It is understood that this definition also includes the ranges when no word “about” is present.

[0052]

[0045] As used herein, the terms “substantially identical reference composition” and “substantially identical reference article” refer to a reference composition or article comprising substantially identical components in the absence of an inventive component. In another exemplary aspect, the term “substantially,” in, for example, the context “substantially identical reference composition” or “substantially identical reference article,” refers to a reference composition or an article comprising substantially identical components and wherein an inventive component is absent or is substituted with a common in the art component.

[0053]

[0046] By “contact” or other forms of the word, such as “contacted” or “contacting,” it is meant to add, combine, or mix two or more compounds, compositions, or materials under appropriate conditions to produce a desired product or effect. The term “react” is sometimes used when “contacting” results in a chemical reaction.

[0047] 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.

[0054]

[0048] 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.

[0055] ANODES AND ELECTROCHEMICAL CELLS

[0056]

[0049] In certain aspects, disclosed herein is an anode comprising a conductive substrate material comprising an effective amount of a metal lophilic seed material catalyzing nucleation of one or more metals comprising Na, Li, K, Mg, Zn, or any combination thereof. In such exemplary and unlimiting aspects, the metallophilic seed material can be a salt comprising cations of Bi3+, Sb5+, Sb3+, Pb2+, ln3+, Te4+, Al3+, Ag+, Fe2+, Fe3+, Mn2+, Co2+, Ni2+, MO2+ / 3+ / 5+ / 6+, W2+ / 3+ / 5+ / 6+, Nb4+ / 5+, Y3+, La3+, Mg2+, Sr2+or any combination thereof. In yet still further aspects, the anode comprises a metallic layer disposed on the conductive substrate, wherein the metallic layer comprises an active anode material comprising Na, Li, K, Mg, Zn, or any combination thereof.

[0057]

[0050] In still further aspects, the metallic layer comprises Na. Yet in still further aspects, the metallic layer comprises Li. In still further aspects, the metallic layer comprises K. In still further aspects, the metallic layer comprises Mg. In still further aspects, the metallic layer comprises Zn. In yet still further aspects, the metallic layer comprises a combination of any or all of the disclosed herein active anode materials.

[0058]

[0051] In yet still further aspects, the salt comprises anions comprising Ch, F N3-, S2', NO3; or any combination thereof.

[0059]

[0052] It is understood that the seed material disposed within or on the surface of the substrate facilitates nucleation of the active anode material that is then disposed on the surface of the substrate. In such exemplary and unlimiting aspects, the seed material is metallophilic to the specific active anode material or to a combination of one or more active anode materials. In some aspects, it is understood that during the anode formation, the metallic layers of the active anode material first rapidly nucleate on the metallophilic seeds and continue to grow to form the desired thickness of the metallic layer of the substrate. The exemplary and unlimiting mechanism of such formation of the anode is shown in FIG. 1 where the seed material can be packed on the substrate such that a plurality of voids are formed on the substrate and wherein the one or more active materials are deposited within the plurality of voids during the deposition step of the active material.

[0060]

[0053] In yet another aspect, it is understood that metallophilicity can be driven by the specific cations present in the salt. In other aspects, the metallophilicity can be driven by the specific anions present in the salt.

[0061]

[0054] In still further aspects, the conductive substrate can be a sheet, a foil, a mesh, a wire, a foam, or a combination thereof. In certain aspects, the conductive substrate comprises carbon, metal, metal alloy, conductive polymers, or any combination thereof. Yet in still further aspects, the conductive substrate can comprise a plurality of carbon nanotubes, graphene, functionalized graphene, graphite, functionalized graphite, carbon black, modified carbon black, or any combination thereof. In yet another aspect, the substrate comprises a plurality of carbon nanotubes.

[0062]

[0055] In still further aspects, the conductive substrate can comprise a metal foil, metal mesh, metal wire, metal foam, or a combination thereof. In certain aspects, the metal is Cu, Al, Ti, Pt, Au, Ag, W, Mo, Ni, or any combination thereof.

[0056] In still further aspects, the substrate can be at least partially porous. In yet still further aspects, the substrate can be porous. In such aspects, the seed materials can be positioned within at least some of the pores of the substrate, and the nucleation of the one or more anode materials can begin on these seed materials.

[0063]

[0057] In still further aspects, the metallophi lie seed material is incorporated within and / or on a surface of the substrate.

[0064]

[0058] In still further aspects, the effective amount of the metallophilic seed material greater than 0% to 50% weight of the anode, including exemplary values of 0.1 wt%, 0.5 wt%, 1 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%,40 wt%, and 45 wt% based on a total weight of the anode. It is understood that the metallophilic seed material can be present in any amount that falls between any two foregoing values, or it can fall in any range formed by any two foregoing values. For example, and without limitations, the metallophilic seed material can be present in an amount of 0.1 to 45 wt%, 0.1 to 40 wt%, 0.1 to 30 wt%, 0.1 to 20 wt%, 0.1 to 10 wt%, 0.1 to 5 wt%, 0.1 to 1 wt%, 0.1 to 0.5 wt%, 0.1 to 50 wt%, 0.5 to 50 wt%, 1 to 50 wt%, 10 to 50 wt%, 15 to 50 wt%, 20 to 50 wt%, 30 to 50 wt%, 35 to 50 wt%, and so on.

[0065]

[0059] In further aspects, the metallic layer can be any thickness required for the desired application. Yet, in still further aspects, the thickness of the metallic layer is 1 to 500 microns, including exemplary values of 2 microns, 5 microns, 10 microns, 25 microns, 50 microns, 75 microns, 100 microns, 125 microns, 150 microns, 175 microns, 200 microns, 225 microns, 250 microns, 275 microns, 300 microns, 325 microns, 350 microns, 375 microns, 400 microns, 425 microns, 450 microns, and 475 microns. It is understood that the thickness of the metallic layer can have any value that falls between any two foregoing values, or it can fall in any range formed by any two foregoing values. For example, and without limitations, the thickness of the metallic layer can be 1 to 400 microns, 1 to 300 microns, 1 to 200 microns, 1 to 100 microns, 1 to 50 microns, 10 to 500 microns, 50 to 500 microns, 100 to 500 microns, 300 to microns, and so on.

[0066]

[0060] Also disclosed herein is an electrochemical cell comprising: any of the disclosed herein anodes and an electrolyte. In certain aspects, the electrolyte comprises a salt and a non-aqueous solvent. It is understood that the salt can be selected based on the desired application and the active anode materials. In certain aspects, the salt comprises a salt of Na, Li, K, Mg, Zn, or any combination thereof.

[0067]

[0061] In yet still further exemplary and unlimiting aspects, when the active anode material is Na, the salt comprises one or more of sodium fluorophosphate (NaPFe), sodium fluoroborate (NaBF4), sodium tetraphenylborate (NaBPfu), sodium bis(fluorosulfonyl)imide (NaFSI), sodium bis(trifluoromethanesulfonyl)imide (NaTFSI), sodium (fluorosulfonyl)(trifluoromethanesulfonyl)imide (NaFTFSI), sodium perchlorate (NaCIC>4), sodium nitrate (NaNOs), sodium 4,5-dicyano-2- (trifluoromethyl)imidazole (NaTDI), sodium 4,5-dicyano-2- (pentafluoromethyl)imidazole (NaPDI), and sodium difluorooxalato borate (NaDFOB), or any combination thereof. Yet in other aspects, when the active anode material is Li, K, Mg, or Zn, any of the disclosed above potassium and lithium salts can be used in the electrolyte.

[0068]

[0062] In still further aspects, the solvent can comprise one or more solvents. In certain aspects, the non-aqueous solvent can comprise one or more of ethylene carbonate (EC), 1 ,2-dimethoxyethane (DME), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), 1 ,2-dimethoxyethane (DME), fluoroethylene carbonate (FEC), tetrahydrofuran (THF), diethylene glycol dimethyl ether (diglyme), triethylene glycol dimethyl ether (TDEM), tetraethylene glycol dimethyl ether (TEGDME), and vinylene carbonate (VC), Bis(2,2,2-trifluoroethyl) ether (BTFE), 1 ,1 ,2,2-tetrafluoroethyl 2,2,3,3-tetrafluoropropylether (TTE), tris(2,2,2-trilfuoroethyl) orthoformate (TFEO), trimethylphosphate (TMP), triethylphosphate (TEP), or any combination hereof.

[0069]

[0063] In still further aspects, the salt can be present in the electrolyte in any amount that provides the desired conductivity and can be dictated by the solubility of the salt in a specific solvent. In certain aspects, the salt is present in an amount of 0.01 M to 3 M, including exemplary values of 0.05 M, 0.1 M, 0.2 M, 0.3 M, 0.4 M, 0.5 M, 0.6 M, 0.7 M, 0.8 M, 0.9 M, 1 M, 1.1 M, 1.2 M, 1.3 M, 1.4 M, 1.5 M, 1.6 M, 1.7 M, 1.8 M, 1.9 M, 2 M, 2.1 M, 2.2 M, 2.3 M, 2.4 M, 2.5 M, 2.6 M, 2.7 M, 2.8 M, and 2.9 M. In still further aspects, the salt can be present in any amount between any two foregoing values. In yet still further aspects, the sale can be present in an amount that falls within a range formed by any two values described above. For example, the salt can be present in an amount of 0.05 M to 3 M, 0.1 M to 3 M, 0.5 M to 3 M, 1 M to 3 M, 1.5 M to 3 M, 2 M to 3 M, and so on. It is understood, however, that in certain aspects, when the solubility of the salt allows it, the salt can be present in an amount higher than 3 M, higher than 3.5 M, higher than 4 M, higher than 4.5 M, or even higher than 5 M.

[0070]

[0064] In still further aspects, it is understood that the salt amount can be presented in different units, such as molality or weight (wt) %. In aspects where the salt amount is presented in wt%, the weight percent of the salt is calculated based on the total weight of the electrolyte.

[0071]

[0065] In still further aspects, the electrochemical cell can comprise any solid or hybrid electrolyte known in the art. In certain aspects, the electrolyte is a solid electrolyte and comprises an inorganic ceramic / glass-ceramic, organic polymer, and ceramic-polymer composite electrolytes. For example, and without limitations, for sodium-ion batteries, the solid electrolyte can comprise doped and undoped NASICON-type compounds, perovskite-type and anti-perovskite-type compounds, nitrides, oxynitrides, beta-alumina, Cryolite-type, argyrodite-type, or polymer-based electrolytes, or ceramic-polymer composite electrolytes, or any combination thereof. If the electrolyte is polymer-based electrolytes, such electrolytes can further comprise an alkali metal, an alkaline-earth metal salt, or a combination thereof.

[0072]

[0066] In still further aspects, the electrochemical cell further comprises a cathode electrode. Any known in the art cathodes can be used. For example, and without limitations, the cathode electrode can comprise one or more layered oxides, spinel oxides, olivines, polyanion-based cathodes, Prussian Blue analogs, Prussian White analogs, sulfur-based cathodes, selenium-based cathodes, vanadium-based cathodes, or any combination thereof. In yet another aspect, the cathodes are sulfide-based.

[0073]

[0067] In still further aspects, where the electrochemical cell comprises a liquid electrolyte, for example, the electrochemical cell can further comprise a separator. In such aspects, any known in the art separators that are capable of achieving the desired results can be used. For example, and without limitations, the separators can comprise glass fiber, a porous polymer film (e.g., polyethylene- or polypropylene-based material) with or without a ceramic coating, or a composite (e.g., a porous film of inorganic particles and a binder). One exemplary polymeric separator is a polyethylene (PE) membrane. Another exemplary polymeric separator is a polypropylene (PP) membrane. Another exemplary polymeric separator is a Celgard® 3501 surfactant-coated polypropylene membrane. The separator may be infused with any of the disclosed herein electrolytes.

[0074]

[0068] In still further aspects, during the operation of the electrochemical cell, the plated active anode metal exhibits substantially no dendrites in the plating or stripping cycle. Without wishing to be bound by any theory, it is believed that such dendrite-free behavior is due to the nucleation of the anode active materials on the metallophilic seeds present in the substrate.

[0075]

[0069] In still further aspects, the electrochemical cells disclosed herein can exhibit a Coulombic efficiency greater than 80%, greater than 85%, greater than 90%, greater than 95%, or greater than 99% over at least 500 cycles. In yet still further aspects, the electrochemical cells disclosed herein can exhibit a Coulombic efficiency greater than 95%, greater than 96%, greater than 97%, or greater than 98%, greater than 99%, or greater than 99.9% over at least 500 cycles. It is understood that such a Coulombic efficiency can also be observed for at least 700 cycles, at least 1 ,000 cycles, at least 5,000 cycles, at least 10,000 cycles, or at least 20,000 cycles.

[0076]

[0070] In still further aspects, the electrochemical cell exhibits a specific capacity of 100 mAh g-1to 1500 mAh g-1at a discharge rate of at least 0.1 C. For example, the electrochemical cell can exhibit a specific capacity of 100 mAh g'1to 1500 mAh g’1, including exemplary values of 120 mAh g-1, 150 mAh g-1, 200 mAh g’1, 250 mAh g-1’ 300 mAh g'1, 350 mAh g-1, 400 mAh g-1, 450 mAh g-1, 500 mAh g-1, 550 mAh g-1, 600 mAh g-1, 650 mAh g-1, 700 mAh g-1, 750 mAh g-1800 mAh g-1, 850 mAh g-1, 900 mAh g-1, 950 mAh g-1, 1000 mAh g-1, 1050 mAh g-1, 1100 mAh g_1 , 1150 mAh g’1, 1200 mAh g’1, 1250 mAh g’1, 1300 mAh g 1 , 1350 mAh g’1, 1400 mAh g’1, and 1450 mAh g-1, at a discharge rate of at least 0.1 C, of at least 0.2C, of at least 0.5C, of at least 1 C, of at least 2C, of at least 3C, of at least 4C, of at least 5C, and so on. It is understood that the specific capacity can fall between any disclosed above values or can fall within any range formed by the disclosed above values. In certain aspects, the batteries disclosed herein exhibit a specific capacity of 100 mAh g-1to 1500 mAh g’1, 150 mAh g-1to 1500 mAh g-1, 200 mAh g-1to 1500 mAh g-1, 300 mAh g-1to 1500 mAh g-1, 400 mAh g-1to 1500 mAh g-1, 500 mAh g-1to 1500 mAh g-1, 600 mAh g-1to 1500 mAh g-1, 700 mAh g-1to 1500 mAh g-1, 800 mAh g-1to 1500 mAh g’1, 900 mAh g-1to 1500 mAh g’1, 1000 mAh g‘1to 1500 mAh g’1, 1100 mAh g'1to 1500 mAh g-1, 1200 mAh g'1to 1500 mAh g’1, 1300 mAh g'1to 1500 mAh g_1 , 100 mAh g'1to 1300 mAh g'1, 100 mAh g'1to 1100 mAh g’1, 100 mAh g'1to 1000 mAh g-1, 100 mAh g-1to 800 mAh g-1, 100 mAh g-1to 700 mAh g-1, 100 mAh g-1to 500 mAh g-1, and so on at any of the disclosed above discharge rates.

[0077]

[0071] In still further aspects, the electrochemical cells disclosed herein can exhibit a capacity retention of at least 80% over at least 200 cycles. In yet another aspect, the electrochemical cell exhibits a capacity retention of at least 80%, at least 85%, at least 90%, at least 95%, and at least 99% over at least 200 cycles. Yet in still further aspects, the batteries disclosed herein can exhibit a capacity retention of at least 80% over at least 500 cycles. In yet still further aspects, the electrochemical cell exhibits a capacity retention of at least 80%, at least 85%, at least 90%, at least 95%, at least 99%, over at least 500 cycles. It is understood that such capacity retention, for example, at least 80%, at least 85%, at least 90%, at least 95%, at least 99%, can also be observed for at least 700 cycles, at least 1 ,000 cycles, at least 5,000 cycles, at least 10,000 cycles, or at least 20,000 cycles.

[0078]

[0072] In still further aspects, the electrochemical cells disclosed herein are capable of operating in a temperature range from -30 °C to 60 °C, including exemplary values of -25 °C, -20 °C, -15 °C, -10 °C, -5 °C, 0 °C, 5 °C, 10 °C, 15 °C, 20 °C, 25 °C, 30 °C, 35 °C, 40 °C, 45 °C, 50 °C, and 55 °C. It is further understood that the batteries can operate at any value that falls between any foregoing values or in any range formed by any of the disclosed values. For example, the secondary batteries disclosed herein are capable of operating in a temperature range from -25 °C to 60 °C, -10 °C to 60 °C, 0 °C to 60 °C, 10 °C to 60 °C, 20 °C to 60 °C, 30 °C to 60 °C, or 40 °C to 60 °C, or -30 °C to 50 °C, -30 °C to 40 °C, -30 °C to 30 °C, -30 °C to 20 °C, -30 °C to 10 °C, -30 °C to 0 °C, and so on.

[0079]

[0073] In still further aspects, the disclosed herein electrochemical cell is a sodium- ion secondary battery.

[0074] In still further aspects, the disclosed herein electrochemical cells can be used in portable batteries, including those in hand-held and / or wearable electronic devices, such as a phone, watch, or laptop computer; in stationary electronic devices, such as a desktop or mainframe computer; in an electric tool, such as a power drill; in an electric or hybrid land, water, or air-based vehicle, such as a boat, submarine, bus, train, truck, car, motorcycle, moped, powered bicycle, airplane, drone, other flying vehicle, or toy versions thereof; for other toys; for energy storage, such as in storing electric power from wind, solar, wave, hydropower, or nuclear energy and / or in grid storage, or as a stationary power store for small-scale use, such as for a home, business, or hospital.

[0080]

[0075] In addition, according to the present disclosure, the electrochemical cells can be multi-cell electrochemical cells containing at least 10, at least 100, at least 500, between 10 and 10,000, between 100 and 10,000, between 1 ,000 and 10,000, between 10 and 1000, between 100 and 1 ,000, or between 500 and 1 ,000 individual electrochemical cells of the present disclosure. Cells in multi-cell batteries may be arranged in parallel or in series.

[0081] METHODS

[0082]

[0076] Also disclosed herein are methods comprising: depositing an effective amount of a metallophi lie seed material for nucleation of one or more metals comprising Na, Li, K, Mg, Zn or any combination thereof on a conductive substrate, wherein the metallophilic seed material is a salt comprising cations of Bi3+, Sb5+, Sb3+, Pb2+, ln3+, Te4+, Al3+, Ag+, Fe2+, Fe3+, Mn2+, Co2+, Ni2+, MO2+ / 3+ / 5+ / 6+, W2^75^, Nb4+ / 5+, Y3+, La3+, Mg2+, Sr2+or any combination thereof; and depositing an active anode material to form a metallic layer comprising Na, Li, K, Mg, Zn, or any combination thereof to form the anode. In still further aspects, the salt comprises anions comprising Cl’, F, N3-, S2’, NOs’, or any combination thereof.

[0083]

[0077] In yet another aspect, the metallophilic seed is dispersed as a plurality of particles. It is understood that any method of depositing the metallophilic seed can be utilized. For example, and without limitations, the effective amount of the metallophilic seeds can be placed in a solvent. In yet another aspect, the effective amount of the metallophilic seeds can be dissolved in a solvent to form a slurry. If needed, additional binders, such as PVDF, PTFE, PEO, PVP, or any combination thereof, can also be added to the solvent. Any solvent that can provide the desired application can be used. In still further aspects, the metallophilic seed can be deposited on the substrate by immersing the substrate in a solvent comprising the metallophilic seed, by spin coating the metallophilic seed onto the substrate, by drop deposition, spray deposition, physical or chemical vapor deposition, and so on. In still further aspects, if necessary, the substrate with the deposited effective amount of the metallophilic seed material is dried before the active anode material is deposited.

[0084]

[0078] Any of the disclosed above effective amounts of the metallophilic seed material can be used.

[0085]

[0079] In still further aspects, the step of depositing an active anode material comprises melt infusion, electroplating, plasma vapor deposition, chemical vapor deposition, or any combination thereof. It is understood that all these deposition steps are performed in a dry, inert atmosphere. For example, an Ar or N2 gas atmosphere with O2 and H2O contents of < 0.1 ppm can be used.

[0086]

[0080] In still further aspects, the metallic layer is formed in less than 1 min, less than 50 seconds, less than 40 seconds, less than 30 seconds, less than 20 seconds, less than 10 seconds, less than 5 seconds, or less than 1 second. Yet in still further aspects, the metallic layer can be formed in less than 5 hours, less than 1 hour, less than 50 min, less than 30 min, less than 10 min, or less than 5 min. It is understood that the metallic layer can be formed at any time between seconds to hours with certain salts.

[0087]

[0081] In certain aspects, the metallophilic seed material can form a complex between the salt cation and the active anode material. Yet, in other aspects, the metallophilic seed material can form a complex between the salt anion and the active anode material.

[0088]

[0082] In still further aspects, the metallophilic seed is packed on the substrate such that a plurality of voids is formed on the substrate, and wherein the one or more active materials are deposited within the plurality of voids during the deposition step of the active material.

[0089]

[0083] Also disclosed herein are methods comprising: providing any of the disclosed herein anodes, providing any of the disclosed herein electrolytes; providing any of the disclosed herein cathodes; and providing any of the disclosed herein separators to form the electrochemical cell. Yet in still further aspects, the formed cell has substantially no dendrites formed during the electrochemical cell operation.

[0090]

[0084] Disclosed herein are materials, compounds, compositions, and components that can be used for, can be used in conjunction with, can be used in preparation for, or are products of the disclosed methods and compositions. These and other materials are disclosed herein, and it is understood that when combinations, subsets, interactions, groups, etc. of these materials are disclosed, that while specific reference of each various individual and collective combinations and permutation of these compounds may not be explicitly disclosed, each is specifically contemplated and described herein. For example, if a composition is disclosed and a number of modifications that can be made to a number of components of the composition are discussed, each and every combination and permutation that is possible is contemplated explicitly unless specifically indicated to the contrary. Thus, if a class of components A, B, and C is disclosed and a class of components D, E, and F, and an example of a combination composition A-D is disclosed, then even if each is not individually recited, each is individually and collectively contemplated. Thus, in this example, each of the combinations A-E, A- F, B-D, B-E, B-F, C-D, C-E, and C-F is specifically contemplated and should be considered disclosed from the disclosure of A, B, and C; D, E, and F; and the example combination A-D. Likewise, any subset or combination of these is also specifically contemplated and disclosed. Thus, for example, the sub-group of A-E, B-F, and C-E is specifically contemplated and should be considered disclosed from the disclosure of A, B, and C; D, E, and F; and the example combination A-D. This concept applies to all aspects of this disclosure, including, but not limited to, steps in methods of making and using the disclosed compositions. Thus, if there are a variety of additional steps that can be performed, it is understood that each of these additional steps can be performed with any specific aspect or combination of aspects of the disclosed methods, and that each such combination is specifically contemplated and should be considered disclosed. EXAMPLES

[0091]

[0085] The following examples are provided below to illustrate the methods and results associated with the disclosed subject matter. These examples are not intended to be inclusive of all aspects of the subject matter disclosed herein but rather to illustrate representative methods and results. These examples are not intended to exclude equivalents and variations of the present invention, which are apparent to one skilled in the art.

[0092]

[0086] Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperatures, etc.), but some errors and deviations should be acknowledged. Unless indicated otherwise, parts are parts by weight, the temperature is in °C or is at ambient temperature, and pressure is at or near atmospheric. There are numerous variations and combinations of reaction conditions, e.g., component concentrations, temperatures, pressures, and other reaction ranges and conditions, which can be used to optimize the product purity and yield obtained from the described process. Only reasonable and routine experimentation will be required to optimize such process conditions.

[0093] EXAMPLE 1

[0094]

[0087] Disclosed herein are commercial BiFs particles to serve as pre-planted seeds to guide a uniform Na nucleation and deposition in a matrix. The pulverization of BiFs particles, often regarded as a significant drawback when employed as a cathode material, is envisioned in this study as a notable advantage. This behavior facilitates the rearrangement of nucleating seeds, consequently simplifying the process of introducing pre-planted seeds. In addition, BiFs exhibits super-sodiophilic properties, enabling an ultrafast loading of Na metal into a carbon nanotube (CNT) paper current collector within a second of immersion in molten Na metal. Benefiting from these two distinctive features, symmetric cells assembled with the obtained anode exhibit a superior cycle life of > 2,000 h with an extremely low overpotential of only 13.5 mV. A pouch cell paired with a sulfur cathode and the obtained sodiophilic anode with a low negative to positive electrode capacity (N / P) ratio of ~ 2 exhibits stable cycling performance over 50 cycles with a capacity of 661 mAh g“1.

[0095] METHODS

[0088] Preparation of Na@CNT-BiF3 composite: First, BiFs particles were uniformly dispersed on the surface of the CNT material by simply mixing with ethanol, and then the self-supported CNT-BiFs electrode was obtained by a simple filtration. Then, Na disks were heated to 150 °C in a stainless-steel container. After melting, a pair of stainless-steel tweezers was used to remove the impurities until the molten sodium exhibited a shiny metallic luster. Finally, the self-supported CNT- BiFs electrode was soaked in molten sodium to obtain the Na@CNT-BiFs composite. The whole process was carried out inside an Ar-filled glove box with O2 and H2O contents of < 0.1 ppm.

[0096]

[0089] Preparation of Na@Cu-BiFs composite: First, different contents of BiFs and PVDF were added to N-methyl-2-pyrrolidone (NMP) to form a slurry. The slurry was then coated onto a copper foil and dried in a vacuum oven at 60 °C. Then, the Cu-BiFs electrode was soaked in molten sodium to obtain the Na@Cu-BiFs composite. The whole process was carried out inside an Ar-filled glove box with O2 and H2O content of < 0.1 ppm.

[0097]

[0090] Preparation of sulfur cathode: The sulfur cathode was prepared by a conventional melt-diffusion method. Specifically, Ketjen Black carbon and sublimed sulfur in a weight ratio of 1 : 9 were evenly mixed and heated at 155 °C in a sealed vial under an Ar atmosphere for 12 h to achieve a homogeneous sulfur distribution. Then, the as-obtained composite was heated at 200 °C for 30 min to eliminate the excess sulfur from the surface. The sulfur weight in the composite was close to ~ 87 wt%, which was confirmed by comparing the weight of the composites before and after the melt-diffusion process. Furthermore, the 80 wt.% C / S composite, 10 wt.% sodium carboxymethyl cellulose (CMC) binder, 5 wt.% multi-walled carbon nanotubes, and 5 wt.% Super-P was mixed in NMP to form a slurry. The slurry was coated onto a carbon-coated aluminum foil and dried in a vacuum oven at 60 °C. Finally, the dried foil was punched into 10 mm disk electrodes with an areal mass loading of 3 mg cm-2.

[0098]

[0091] Preparation of the electrolyte: Sodium bis(fluorosulfonyl)imide (NaFSI) was dried in a vacuum oven for 24 h at 60 °C. 1 ,2-dimethoxyethane (DME) was dried with molecule sieves for 72 h. The electrolyte was prepared inside an Ar-filled glove box. Particularly, DME was mixed with NaFSI at a molar ratio of 1 : 1 .2 and stirred over 3 h to obtain a transparent solution. Then, 1 ,1 ,2,2-tetrafluoroethyl 2,2,3,3-tetrafluoropropyl ether (TTE) was added to the above solution with the same molar amount as NaFSI.

[0099]

[0092] Characterizations: The morphology characterization was carried out with a scanning electron microscope (FEI Quanta 650 SEM running at 20 kV) equipped with an energy-dispersive X-ray (EDX) spectrometer to study the elemental distribution. Monochromatic Al Ka (1 ,486.6 eV) radiation was used for XPS examination with a Kratos Analytical spectrometer.

[0100]

[0093] Synchrotron X-ray diffraction (XRD): Synchrotron in-operando XRD tests were carried out at the 11-ID-C beamline with the Advanced Photon Source (APS) at Argonne National Laboratory. The beam spot size was 0.5 mm x 0.5 mm, with the X-ray energy at 105.7 keV. The 2D diffraction images were captured with a Perkin Elmer area detector. The sample-to-detector distance was calibrated with a CeO? standard, and the images were combined into 1 D diffraction patterns with the use of the GSAS-II tool. XRD data were continually acquired by rastering back and forth between cells for a duration of 2 min per pattern. Throughout this time, the cells were cycled at a rate of 0.1 C rate from 0.8 to 2.8 V for a complete cycle of charge and discharge. CR2032-style window coin cells were put together inside a glovebox with < 1 ppm of O2 and H2O. To enable X-ray penetration, a 3 mm window was punched through both the top and bottom casings. The windows were sealed with Cu foil (9 pm thick) and Al foil (12 pm thick), respectively, on the anode side and the cathode side. An epoxy composed of Catalyst 15 and Eccobond 45 with a volume ratio of 1 : 1 was applied to the foils as a reliable sealing. To ensure optimal mechanical contact between the CNT / CNT-BiFs electrode and the ion source, two Na metal discs were used as spacers. These house-built cells were assembled in the laboratory and shipped to APS for characterization.

[0101] TABLE 1. Electrochemical performance comparison with some reported representative Na-S batteries work.

[0102] RESULTS AND DISCUSSION

[0103]

[0094] Synthesis route and mechanism: The synthetic route for the Na@CNT- BiFs self-supporting electrodes is schematically shown in FIG. 2; it can be easily prepared by simply mixing CNT and BiFs via ultrasonication, followed by filtration, drying, and diffusion of molten Na liquid. It is worth noting that the CNT-BiFs electrode is super-sodiphilic and can quickly adsorb molten Na metal into the material. Since commercialization is based on Cu foil current collectors rather than simple self-supporting electrodes, excellent electrochemical performance has also been achieved by coating a commercial BiF3 paste onto Cu foil. In addition, the BiFs particles in the Na@CNT-BiF3 and Na@Cu-BiFs electrodes gradually pulverize and uniformly cover the CNT after al loy ing / dealloying of BiF3 with an increasing number of cycles (35, 36), effectively improving the uniformity and electrochemical properties of the Na@CNT-BiF3 and Na@Cu-BiF3 electrode materials.

[0095] Electrochemical performance of sodium-metal anode: To further assess the sodiophilicity of CNT@-BiFs and CNT electrodes for molten Na, the time required for the electrodes to adsorb molten Na metal fully was compared macroscopically (FIG. 3A). Notably, the CNT@BiFs electrode fully adsorbed molten Na metal within a second, whereas the CNT electrode took 52 s, demonstrating the high sodiophilicity of BiFs particles in significantly improving the sodiophilicity of CNT@BiFs. The cycling stability of the Na@CNT-BiFs anode was further assessed with symmetric cells at a current density of 2 mA cm-2and an areal capacity of 2 mA h cm"2. As seen in FIG. 3B, the symmetric cell with Na@CNT-BiFs displays an overpotential of only 6 mV initially, followed by a slight increase of up to 13.5 mV, but shows a remarkable lifespan of over 2,000 h. The Coulombic efficiency (CE) is a vital parameter to reflect the side reactions between electrodes and electrolytes. The CE of the cell with the Cu || Na@CNT electrode exhibits strong irregular fluctuations (FIG. 3C), which may be due to the CNT surface having poor sodiophilicity. The lack of an effective nucleation surface leads to a loss of active Na during plating / stripping, accompanied by a reconstruction and cracking of the SEI. For comparison, the Cu||Na@CNT-BiF3 cell maintains a well-maintained CE of 99% after 350 cycles, demonstrating a significant improvement in Na plating / stripping reversibility. Additionally, the corresponding discharge-charge curves of the Cu || Na@CNT-BiFs cell show a low Na nucleation overpotential with constant, overlapping plateaus during repetitive cycling (FIG. 3D).

[0104]

[0096] To further investigate the interphase composition formed on the surface of the Na@CNT and Na@CNT-BiFs, time-of-flight - secondary ion mass spectrometric (TOF-SIMS) depth profiling was employed, which is an advanced technique to identify the chemical composition of the solid surface within its depth (37, 38). As shown in FIG. 3E, the depth profiles reveal the uniformity of Na infiltration into the matrix in Na@CNT and Na@CNT-BiFs anode via the Na2“ secondary-ion as a representative species. The Na2' intensity in the Na@CNT anode shows two peaks consecutively and then decreases continuously, which indicates that the poor sodiophilicity of Na@CNT results in the non-uniform incorporation of metallic Na. The 3D reconstruction of the elemental depth profiles of Na@CNT in FIG. 3G further reaffirms the inhomogeneous Na metal distribution. It is reasonable to posit that the non-uniformity leads to dendrite formation and irregular cycling, as observed in FIG. 3C. On the other hand, the continuous signal for Na?' intensity in Na@CNT-BiF3 indicates a uniform infiltration of Na metal despite the presence of large BiFs particles in the CNT. In further support, the 3D reconstruction of the Na@CNT-BiFs electrode in FIG. 3F shows a homogeneous Na?" signal over the whole investigated depth. The continual abundance of seeding sites leads to a consistent performance of the cell, observed in FIGS. 3C-3D.

[0105]

[0097] Sodium storage mechanism and the behavior of Sodium-metal anode: In addition, to clearly observe the morphological changes of Na metal at the CNT- BiFs electrode microscopically, the top-surface and cross-sectional SEM images of CNT-BiFs, Na@CNT-BiFs (before cycling), and Na@CNT-BiFs (after 200 cycles) electrodes are compared in FIGS. 4A-4F. FIGS. 4A-4B show uniformly distributed, large (micron-sized) BiFs particles in the CNT-BiFs electrode. The top-surface and cross-sectional morphologies of the CNT-BiFs electrode after adsorbing molten Na are shown in FIGS. 4C-4D, which show the top-surface and cross-sectional morphologies of the CNT-BiFs electrode after adsorbing molten Na (before cycling). As seen, the BiFs particles on the top surface are smaller, which may be due to the rapid pulverization and dispersion of the particles during the adsorption of molten Na metal. In addition, from the cross-sectional SEM image, it can be seen that there are still many pores and gap structures after the adsorption of Na metal, which can effectively buffer the volume expansion during the cycling process. To this end, the structural changes of the Na@CNT-BiFs electrode after 200 cycles can be observed in FIGS. 4E-4F. The SEM images show that the surface BiF3 particles are smaller and more uniformly distributed. In addition, the pores in the cross-sectional SEM are filled and thus become denser, which may be attributed to the continuous alloyi ng / de-alloy ing of BiFs during the cycling process. The repeated alloying process causes BiFs to break down into small particles that get homogenously distributed, such that they occupy more volume compared to the initial stage. Thus, the void spaces that existed in the Na@CNT-BiFs electrode before cycling were filled during the Na plating process.

[0106]

[0098] To better understand the Na storage mechanism, Na plating behavior on Cu, CNT, and CNT-BiFs substrates was studied. The potential-capacity curves in FIG. 5A show a deep dip in the potential caused by the Na-metal nucleation barrier. This nucleation potential for Cu, CNT, and CNT-BiFs are, respectively, 428, 383, and 129 mV. The low overpotential for CNT-BiFs indicates that it is a highly favorable substrate to plate Na-metal with a fast Na+diffusion rate. It also means that BiFs is labile for conversion by efficiently reacting with Na. The conversion was confirmed by comparing the X-ray photoelectron spectroscopy (XPS) data of CNT-BiFs (FIG. 5B) and Na@CNT-BiFs (FIG. 5C). As expected, the spectrum of CNT-BiFs shows the Bi 4f7 / 2 peak at 160.8 eV. On plating Na on the CNT-BiFs electrode, a new Bi 4f? / 2 peak at 155.8 eV corresponding to metallic Bi is observed. This peak appears at a lower binding energy than expected for metallic Bi (156.9 eV), potentially due to the formation of Na-Bi alloy, indicating that the Na is not just physically plated but rather chemically reacting with and converting BiFs. Furthermore, the peak for BiFs persists even after sodium plating, implying that BiFs progressively undergoes pulverization followed by conversion to metallic Bi with cycling. This steady conversion process ensures continuous availability of BiFs, which acts as seeds and thus ensures uniform plating.

[0107]

[0099] To better understand the surface and bulk characteristics of the Na@CNT- BiFs anode cycled in a localized high-concentration electrolyte (LHCE), ToF-SIMS on the cycled anode was performed. The LHCE includes sodium bis(fluorosulfonyl) imide (NaFSI) : 1 ,2- dimethoxyethane (DME) : 1 , 1 ,2,2-tetrafluoroethyl 2, 2,3,3- tetrafluoropropyl ether (TTE) in 1 : 1 .2 : 1 (molar ratio). FIG. 5D shows the depth profiles, and FIG. 5E shows the 3D reconstruction of the secondary-ion species, such as Na2_, C-, NasF-, and NaS-, which are representative of, respectively, metallic Na, CNT, BiFs, and LHCE electrolytes. It can be seen from the depth profiles and 3D model that the signals for Na2- and C- gradually increase to reach a uniform and stable level by the end of sputtering, which is similar to the trend of secondary ion Na2- signal in the original Na@CNT-BiFs anode (FIG. 3F), suggesting that the structure of CNT matrix and the homogenous Na distribution are maintained across cycling. In addition, the SEI layer was analyzed by the secondary ions Na2F- and NaS-. First, the signal of Na2F gradually decreases until about 2,000 s of sputtering time, and then it stabilizes, indicating that a compact NaF-rich SEI is formed, as seen in the 3D reconstruction. This layer suppresses the growth of dendrites while providing fast ion transport, which is responsible for the high CE observed. The NaS- signal from the electrolyte follows a trend similar to that of Na?F- in the SEI layer, which indicates that the inorganic-rich NaF and Na2S layers protect the underlying Na-metal from continuous electrolyte exposure and decomposition. FIG. 5F displays the cross-sectional SEM micrograph along with the elemental mapping distributions of C, Bi, F, Na, and S elements across a cycled Na@CNT-BiFs anode. The carbon signal is uniformly distributed in the whole crosssection, which confirms that the structure of the electrode remains intact and stable. The concentration of F and S near the surface aligns with the ToF-SIMS data, reaffirming the NaF and Na2S layers shield the Na-metal from electrolyte degradation.

[0108]

[0100] The above studies show that the Na@CNT-BiFs forms and maintains a stable interface through cycling. To better understand the mechanism by which Na- metal can easily diffuse into a matrix of BiFs and to understand the chemical difference in the Na stripping / plating behavior between the CNT and CNT-BiFs anodes, synchrotron-based in-operando X-ray diffraction (XRD) experiments were performed. FIGS. 6A-6B present the in-operando XRD results of Na || CNT and Na || CNT-BiFs cells cycled with the LHCE in custom coin cells with a window, as described in previous work (39). The cells were tested at 1 mA cm'2for one full plating / stripping process, during which the XRD pattern was simultaneously recorded to probe the Na plating / stripping with a small volume where the X-rays are focused, as presented by the contour plot next to the voltage profile.

[0109]

[0101] In the contour plot of the cell with Na@CNT anode (FIG. 6A), peaks corresponding to Na metal plating on the CNT matrix can be detected when about 0.5 mAh cm'2is plated, and the peak intensity grows stronger with continuous plating. While stripping, the intensity reduces, but a faint intensity is still detected at the end of the stripping process, which can act as the nucleation site during the subsequent plating steps. In contrast, as shown in FIG. 6B, during the sodium plating process of CNT-BiFs anode, strong Na metal and BiFs characteristic peaks are present at the beginning of the plating step. The intensity of the Na-metal peak is much stronger in the case of CNT-BiFs compared to pure CNT, indicating that the probed volume quickly fills with Na metal, owing to BiFs acting as a strong seeding layer, while the sparse Na distribution in the case of CNT is reflected in a weaker signal. This also points to the good sodiophilicity of the matrix with BiFs. By the time 0.5 mAh cm'2is plated, the signal for NasBi can be observed, while the Na metal signal intensifies. This indicates that the conversion-alloying process drives the dense plating of Na in the matrix. The formation of NasBi and NaBi, as indicated by the in-situ XRD along with the presence of NaF signal in the ToF-SIMS and SEM data in FIGS. 6A-6F suggests that the facile conversion of BiFs into Na-Bi alloys and NaF is the reason for the high sodiophilicity of a BiFs-containing matrix, which allows for the ultra-quick melt-infusion of Na metal.

[0110]

[0102] During the stripping process, the characteristic peak of NasBi is gradually transformed into NaBi, and the characteristic peak of Na metal is gradually weakened. The remaining Na metal and the NaBi alloy act as an excelling seeding layer in the subsequent plating step, thus guiding a dendrite-free nucleation and growth of Na (40, 41 ). In essence, the addition of BiFs improves the sodiophilicity of CNT, resulting in a highly reversible Na plating / striping and alloying / de-alloying process for Na@CNT-BiFs anode. Overall, from the above XRD data, in a melt- infiltrated Na@CNT-BiF3 anode, the following (electro)chemical process can be envisioned:

[0111]

[0103] Plating process:

[0112] Na++ e~ -> Na

[0113] Bi3++ 6e~ + 3Na+-» Na3Bi

[0114]

[0104] Stripping process:

[0115] Na3Bi -> NaBi + 2e~ + 2Na+Na -> Na++ e~

[0116]

[0105] Electrochemical performance of Na@CNT-BiF3 and Na@Cu-BiFs: Generally, self-supporting electrodes can provide higher energy density, but practical applications necessitate the use of Cu foil as the current collector. Hence, for further practical and scalable applications, the electrochemical performance of BiFs coated onto a Cu collector was tested. Here, different contents of BiFs electrodes were assembled into Na || Cu cells to characterize the CE and corresponding voltage profile curves for sodium plating / stripping. FIGS. 7A-7B show the CE and the corresponding voltage profiles for the blank control group of Cu anode with 0% BiFs. It is observed that the CE is very unstable, and the voltage profiles fluctuate with high sodium-metal nucleation potentials and low-capacity.

[0117] These fluctuations may be due to the dendrite growth leading to a short circuit of the cell. FIGS. 7C-7H compare the CE with the corresponding voltage profiles for the Cu anodes with 5% BiFs, 20% BiFs, and 40% BiFs. The CE is increased when 5% BiFs is added, and its voltage profiles are relatively smooth, with the CE being stabilized only after cycling up to 100 cycles. However, the CE becomes much more stable when BiFs is added up to 20%, and the corresponding voltage profiles are stable with a low Na metal nucleation overpotential. When BiFs is increased to 40%, the cells cycle with relatively good stability. However, the CE fluctuations are slightly increased compared to those with 20% BiF3. Therefore, a 20% BiF3 addition improves both the sodiophilicity of the electrode and keeps the Na loss at less than 5% in the first cycle.

[0118]

[0106] To demonstrate the practical application of the conversion composite anode, a high-energy C / S cathode was matched with bare Na and Na@CNT-BiFs anodes to make Na-S cells. In these cells, the sulfur loading is 3 mg cm-2, and the electrolyte-to-sulfur (E / S) ratio is controlled to be 7 pL mg-1with an ultra-low N / P ratio of 2.8 to showcase the stability of the anode. FIG. 8A displays the voltage profiles of Na@CNT-BiFs || C / S cell at different cycles at 0.1 C rate (1C = 1675 mA g-1) within the voltage range of 0.8 - 2.8 V. It is noteworthy that there is no obvious irreversible capacity loss region with Na polysulfide (NaPSs) transformation in the voltage profiles of the initial cycles. The stability of the charge / discharge curves implies that the Na@CNT-BiFs anode surface is resistant to the shuttle of polysulfides.

[0119]

[0107] The Na@CNT-BiFs || C / S cell presents an initial discharge capacity of 1 ,010 mA h g-1' as shown in FIG. 8B. Even through 200 cycles, the capacity remains at 862 mA h g-1, corresponding to a capacity retention of 85%. The CE at the 200th cycle is nearly 100%, which demonstrates that minimal polysulfide shuttling occurs during cycling. On the other hand, the cell with a bare Na anode exhibits poor cycling performance, with rapid capacity fade within 75 cycles, and ultimately displays a very low capacity of only 165 mA h g_1after 150 cycles. Furthermore, the CE fluctuates during cycling, suggesting irreversible reactions between the electrolyte and the bare Na-metal anode lead to capacity loss. In essence, the Na@CNT-BiFs anode exhibits significant potential for high-performance Na-S batteries, featuring impressive capacity, minimal capacity decay, and a prolonged cycling lifespan, outperforming numerous Na-S batteries (Table S1 , Supporting Information). The Na@CNT-BiFs || C / S cell was further tested at a higher current density of 1 C rate to reveal the kinetics of the reaction and the structural stability of the anode. FIG. 8C shows that the Na@CNT-BiFs || C / S cell can still provide a discharge capacity of 674 mA h g-1even after 700 cycles, corresponding to a capacity retention of 77%, indicating a highly reversible reaction in the cell.

[0120]

[0108] As mentioned before, Na@Cu-BiFs is a practical alternative to the freestanding Na@CNT-BiFs as it has a metallic current collector, allowing for the processing of large electrodes. To validate this, the cycling performance of the Na@Cu-BiF3 1| C / S cell was tested with a sulfur loading of 3 mg cm'2, a low E / S of 7 pL mg'1, a low N / P ratio of 2, and at a current of 0.1 C, as shown in FIG. 8D. The Na@Cu-BiF3 anode exhibits an initial capacity of 735 mA g'1and excellent cycling stability, with a capacity retention of close to 100% after 100 cycles. The presence of a Cu current collector affords the construction of Na-S pouch cells, as tabs can be easily welded. This, Na@Cu-BiFs || C / S pouch cells were assembled to validate this concept, featuring a 2 mg cm'2loading, a low E / S of 4 pL mg-1, and a low N / P ratio of 2. As depicted in FIG. 8E, the pouch cell presents a capacity of 661 mAh g-1at 0.1 C rate after 50 cycles, indicating the effective utilization of sulfur even when operating with low E / S and limited N / P ratios. These results highlight the promise of integrating Na@Cu-BiFs in the development of high-performance, practically feasible Na-S batteries.

[0121] CONCLUSION

[0122]

[0109] In summary, BiFs is demonstrated to be a super-sodiophilic seed for Nametai anodes in sodium-metal batteries. When BiFs is integrated into a matrix of CNT, molten Na metal can be incorporated into the substrate in a facile and rapid manner owing to the conversion-alloying reaction of BiFs. The Na@CNT-BiF3 anode thus forms a NaF- and Na2S-rich interphase with the electrolyte when cycled in an LHCE. This interphase is compact yet robust, to prevent continuous electrolyte degradation at the anode, which enables long-term cycling. The constant pulverization and conversion of BiFs through cycling provides an efficient seed layer that suppresses dendrite formation. In addition to the free-standing format, BiFs can be coated onto a metallic current collector, such as Cu foil, and mixed with molten Na metal to yield an anode. The Na@Cu-BiFs anodes could be easily incorporated into prototype pouch cells, which showed excellent cycling stability in Na-S batteries, especially while operating at a low N / P ratio of 2. This work provides a simple, scalable approach forward to Na-anode protection and is also instructive for other metal batteries with different working conditions.

[0123] EXEMPLARY ASPECTS

[0124]

[0110] In view of the described processes and compositions, hereinbelow are described certain more particularly described aspects of the disclosures. These 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 composites and formulas literally used therein.

[0125]

[0111] Example 1 : An anode comprising a conductive substrate material comprising an effective amount of a metallophilic seed material catalyzing nucleation of one or more metals comprising Na, Li, K, Mg, Zn, or any combination thereof, wherein the metallophilic seed material is a salt comprising cations of Bi3+, Sb5+, Sb3+, Pb2+, ln3+, Te4+, Al3+, Ag+, Fe2+, Fe3+, Mn2+, Co2+, Ni2+, MO2+ / 3+ / 5+ / 6+, ^+ / 3+ / 5+ / 6+ Nb4+ / 5+, Y3+, La3+, Mg2+, Sr2+or any combination thereof; and a metallic layer disposed on the conductive substrate, wherein the metallic layer comprises an active anode material comprising Na, Li, K, Mg, Zn, or any combination thereof.

[0126]

[0112] Example 2: The anode of any one of the examples herein, particularly example 1 , wherein the salt comprises anions comprising Cl F; N3S2; NOs or any combination thereof.

[0127]

[0113] Example 3: The anode of any one of the examples herein, particularly examples 1-2, wherein the metallic layer comprises Na.

[0128]

[0114] Example 4: The anode of any one of the examples herein, particularly examples 1-3, wherein the conductive substrate is a sheet, a foil, a mesh, a wire, a foam, or a combination thereof.

[0129]

[0115] Example 5: The anode of any one of the examples herein, particularly examples 1-4, wherein the conductive substrate comprises carbon, metal, metal alloy, conductive polymers, or any combination thereof.

[0116] Example 6: The anode of any one of the examples herein, particularly examples 1-5, wherein the conductive substrate comprises a plurality of carbon nanotubes, graphene, functionalized graphene, graphite, functionalized graphite, carbon black, modified carbon black, or any combination thereof.

[0130]

[0117] Example 7: The anode of any one of the examples herein, particularly examples 1-6, wherein the conductive substrate comprises a metal foil, metal mesh, metal wire, metal foam, or a combination thereof.

[0131]

[0118] Example 8: The anode of any one of the examples herein, particularly examples 1-7, wherein the metallophilic seed material is incorporated within and / or on a surface of the substrate.

[0132]

[0119] Example 9: The anode of any one of the examples herein, particularly examples 1-8, wherein the metallophilic seed material is packed within and / or the surface of the substrate such that the one or more active anode materials are nucleated on the conductive substrate to form the metallic layer.

[0133]

[0120] Example 10:. The anode of any one of the examples herein, particularly examples 1-9, wherein the effective amount of the metallophilic seed material is greater than 0% to 50% weight of the anode.

[0134]

[0121] Example 11 :. An electrochemical cell comprising: an anode electrode of any one of the examples herein, particularly examples 1-10; and an electrolyte.

[0135]

[0122] Example 12:. The electrochemical cell of the examples herein, particularly example 11 , wherein the electrolyte comprises a salt and a non-aqueous solvent.

[0136]

[0123] Example 13:. The electrochemical cell of the examples herein, particularly example 12, wherein the salt comprises a salt of Na, Li, K, Mg, Zn, or any combination thereof.

[0137]

[0124] Example 14:. The electrochemical cell of any one of the examples herein, particularly examples 11-13, wherein the non-aqueous solvent comprises one or more of ethylene carbonate (EC), 1 ,2-dimethoxyethane (DME), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), 1 ,2- dimethoxyethane (DME), fluoroethylene carbonate (FEC), tetrahydrofuran (THF), diethylene glycol dimethyl ether (diglyme), triethylene glycol dimethyl ether (TDEM), tetraethylene glycol dimethyl ether (TEGDME), and vinylene carbonate (VC), Bis(2,2,2-trifluoroethyl) ether (BTFE), 1 , 1 ,2,2-tetrafluoroethyl 2, 2,3,3- tetrafluoropropylether (TTE), tris(2,2,2-trilfuoroethyl) orthoformate (TFEO), trimethylphosphate (TMP), triethylphosphate (TEP), or any combination hereof.

[0138]

[0125] Example 15:. The electrochemical cell of any one of the examples herein, particularly examples 11-14, wherein the salt comprises one or more of sodium fluorophosphate (NaPFe), sodium fluoroborate (NaBF4), sodium tetraphenylborate (NaBPh4), sodium bis(fluorosulfonyl)imide (NaFSI), sodium bis(trifluoromethanesulfonyl)imide (NaTFSI), sodium (fluorosulfonyl)(trifluoromethanesulfonyl)imide (NaFTFSI), sodium perchlorate (NaCIO4), sodium nitrate (NaNOs), sodium 4,5-dicyano-2-(trifluoromethyl)imidazole (NaTDI), sodium 4,5-dicyano-2-(pentafluoromethyl)imidazole (NaPDI), and sodium difluorooxalato borate (NaDFOB), or any combination thereof.

[0139]

[0126] Example 16:. The electrochemical cell of any one of the examples herein, particularly examples 11-15, wherein the salt is present in an amount of 0.01 M to 3 M.

[0140]

[0127] Example 17:. The electrochemical cell of any one of the examples herein, particularly examples 11-16, further comprising a cathode electrode, wherein the cathode electrode comprises one or more layered oxides, spinel oxides, olivines, polyanion-based cathodes, Prussian Blue analogs, Prussian White analogs, sulfide-based cathodes, selenium-based cathodes, sulfur-based cathodes, vanadium-based cathodes, or any combination thereof.

[0141]

[0128] Example 18:. The electrochemical cell of any one of the examples herein, particularly examples 11-17, further comprising a separator.

[0142]

[0129] Example 19:. The electrochemical cell of any one of the examples herein, particularly examples 11-18, wherein during operation of the electrochemical cell, the plated active anode metal exhibits substantially no dendrites in the plating or stripping cycle.

[0143]

[0130] Example 20:. The electrochemical cell of any one of the examples herein, particularly examples 11-19, wherein the electrochemical cell exhibits a coulombic efficiency of greater than 95%.

[0131] Example 21 :. The electrochemical cell of any one of the examples herein, particularly examples 11-20, wherein the electrochemical cell exhibits a specific capacity of 100 mAh g-1to 1 ,500 mAh g-1at a discharge rate of at least 0.1 C.

[0144]

[0132] Example 22:. The electrochemical cell of any one of the examples herein, particularly examples 11-21 , wherein the electrochemical cell exhibits a capacity retention of at least 80% over at least 200 cycles.

[0145]

[0133] Example 23:. The electrochemical cell of any one of the examples herein, particularly examples 11-22, wherein the electrochemical cell exhibits a capacity retention of at least 80% over at least 500 cycles.

[0146]

[0134] Example 24:. The electrochemical cell of any one of the examples herein, particularly examples 11-23, wherein the electrochemical cell is capable of operating in a temperature range of -30 °C to 60 °C.

[0147]

[0135] Example 25:. The electrochemical cell of any one of the examples herein, particularly examples 11-24, wherein the electrochemical cell is a sodium-ion secondary battery.

[0148]

[0136] Example 26:. A method comprising: depositing an effective amount of a metallophilic seed material for nucleation of one or more metals comprising Na, Li, K, Mg, Zn or any combination thereof on a conductive substrate, wherein the metallophilic seed material is a salt comprising cations of Bi3+, Sb5+, Sb3+, Pb2+, ln3+, Te4+, Al3+, Ag+, Fe2+, Fe3+, Mn2+, Co2+, Ni2+, MO2+ / 3+ / 5+ / 6+, VV2+;3+ / 5+ / 6+, Nb4+ / 5+, Y3+, La3+, Mg2+, Sr2+or any combination thereof; and depositing an active anode material to form a metallic layer comprising Na, Li, K, Mg, Zn, or any combination thereof to form the anode of any one of examples 1-9.

[0149]

[0137] Example 27:. The method of example the examples herein, particularly 26, wherein the salt comprises anions comprising CL, F N3-, S2', NOs', or any combination thereof.

[0150]

[0138] Example 28:. The method of the examples herein, particularly example 26 or 27, wherein the metallophilic seed is dispersed as a plurality of particles.

[0151]

[0139] Example 29:. The method of any one of the examples herein, particularly examples 26-28, wherein the effective amount of the metallophilic seed material is greater than 0% to 50% weight of the anode.

[0140] Example 30:. The method of any one of the examples herein, particularly examples 26-29, the step of depositing an active anode material comprises melt infusion, electroplating, plasma vapor deposition, chemical vapor deposition, or any combination thereof.

[0152]

[0141] Example 31 :. The method of any one of the examples herein, particularly examples 26-30, wherein the metallic layer is formed in less than 10 seconds.

[0153]

[0142] Example 32:. The method of any one of the examples herein, particularly examples 26-31 , wherein the metallophilic seed material forms a complex between the salt cation and the active anode material.

[0154]

[0143] Example 33: The method of any one of the examples herein, particularly examples 26-31 , wherein the metallophilic seed material forms a complex between the salt anion and the active anode material.

[0155]

[0144] Example 34: The method of any one of the examples herein, particularly examples 26-31 , wherein the metallophilic seed is packed on the substrate such that a plurality of voids is formed on the substrate and wherein the one or more active materials are deposited within the plurality of voids during the deposition step of the active material.

[0156]

[0145] Example 35: A method comprising: providing an anode of any one of the examples herein, particularly examples 1-10, providing an electrolyte; providing a cathode; and providing a separator to form the electrochemical cell of any one of the examples herein, particularly examples 11-25.

[0157]

[0146] Example 36: The method of the examples herein, particularly example 35, wherein substantially no dendrites are formed during the electrochemical cell operation.

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Claims

CLAIMSWhat is claimed is:1 . An anode comprising a conductive substrate material comprising an effective amount of a metallophilic seed material catalyzing nucleation of one or more metals comprising Na, Li, K, Mg, Zn, or any combination thereof, wherein the metallophilic seed material is a salt comprising cations of Bi3+, Sb5+, Sb3+, Pb2+, ln3+, Te4+, Al3+, Ag+, Fe2+, Fe3+, Mn2+, Co2+, Ni2+, MO2+ / 3+ / 5+ / 6+, W2+ / 3+ / 5+ / 6+!Np4+ / 5+, Y3+, La3+, Mg2+, Sr2+or any combination thereof; and a metallic layer disposed on the conductive substrate, wherein the metallic layer comprises an active anode material comprising Na, Li, K, Mg, Zn, or any combination thereof.

2. The anode of claim 1 , wherein the salt comprises anions comprising Cl R, N3', S2; NO3-, or any combination thereof.

3. The anode of any one of claims 1-3, wherein the conductive substrate is a sheet, a foil, a mesh, a wire, a foam, or a combination thereof, and comprises carbon, metal, metal alloy, conductive polymers, or any combination thereof.

4. The anode of any one of claims 1-3, wherein the metallophilic seed material is packed within and / or on the surface of the substrate such that one or more active anode materials are nucleated on the conductive substrate to form the metallic layer.

5. The anode of any one of claims 1-4, wherein the effective amount of the metallophilic seed material is greater than 0% to 50% weight of the anode.

6. An electrochemical cell comprising: an anode electrode of any one of claims 1-5; and an electrolyte comprising a salt and a non-aqueous solvent.

7. The electrochemical cell of claim 6, wherein the salt comprises a salt of Na, Li, K, Mg, Zn, or any combination thereof and wherein the non-aqueous solvent comprises one or more of ethylene carbonate (EC), 1,2-dimethoxyethane (DME), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), 1 ,2-dimethoxyethane (DME), fluoroethylene carbonate (FEC), tetrahydrofuran (THF), diethylene glycol dimethyl ether (diglyme),triethylene glycol dimethyl ether (TDEM), tetraethylene glycol dimethyl ether (TEGDME), and vinylene carbonate (VC), Bis(2,2,2-trifluoroethyl) ether (BTFE), 1 ,1 ,2,2-tetrafluoroethyl 2,2,3,3-tetrafluoropropylether (TTE), tris(2,2,2- trilfuoroethyl) orthoformate (TFEO), trimethylphosphate (TMP), triethylphosphate (TEP), or any combination hereof,8. The electrochemical cell of claim 6 or 7, wherein the salt comprises one or more of sodium fluorophosphate (NaPFe), sodium fluoroborate (NaBF4), sodium tetraphenylborate (NaBPFu), sodium bis(fluorosulfonyl)imide (NaFSI), sodium bis(trifluoromethanesulfonyl)imide (NaTFSI), sodium (fluorosulfonyl)(trifluoromethanesulfonyl)imide (NaFTFSI), sodium perchlorate (NaCIC>4), sodium nitrate (NaNOs), sodium 4,5-dicyano-2- (trifluoromethyl)imidazole (NaTDI), sodium 4,5-dicyano-2- (pentafluoromethyl)imidazole (NaPDI), and sodium difluorooxalato borate (NaDFOB), or any combination thereof.

9. The electrochemical cell of any one of claims 6-8, further comprising a cathode electrode, wherein the cathode electrode comprises one or more layered oxides, spinel oxides, olivines, polyanion-based cathodes, Prussian Blue analogs, Prussian White analogs sulfide-based cathodes, selenium- based cathodes, sulfur-based cathodes, vanadium-based cathodes, or any combination thereof.

10. The electrochemical cell of any one of claims 6-9, wherein during operation of the electrochemical cell, a plated active anode metal exhibits substantially no dendrites in the plating or stripping cycle and wherein the electrochemical cell exhibits coulombic efficiency of greater than 95%.

11. The electrochemical cell of any one of claims 6-10, wherein the electrochemical cell exhibits a specific capacity of 100 mAh g-1to 1 ,500 mAh g-1at a discharge rate of at least 0.1C.

12. The electrochemical cell of any one of claims 6-11 , wherein the electrochemical cell exhibits a capacity retention of at least 80% over at least 200 cycles.

13. The electrochemical cell of any one of claims 6-12, wherein the electrochemical cell is a sodium-ion secondary battery.

14. A method comprising:depositing an effective amount of a metallophilic seed material for nucleation of one or more metals comprising Na, Li, K, Mg, Zn or any combination thereof on a conductive substrate, wherein the metallophilic seed material is a salt comprising cations Bi3+, Sb5+, Sb3+, Pb2+, ln3+, Te4+, Al3+, Ag+, Fe2+, Fe3+, Mn2+, Co2+, Ni2+,Mo2+ / 3+ / 5+ / 6+, w2+ / 3+ / 5+ / 6+, Nb4+ / 5+, Y3+, La3+, Mg2+, Sr2+or any combination thereof; and depositing an active anode material to form a metallic layer comprising Na, Li, K, Mg, Zn, or any combination thereof to form the anode of any one of claims 1-5.

15. The method of claim 14, wherein the salt comprises anions comprising Cl; F; N3; S2; NO , or any combination thereof.

16. The method of claim 14 or 15, wherein the metallophilic seed is dispersed as a plurality of particles.

17. The method of any one of claims 14-16, wherein the metallic layer is formed in less than 10 seconds.

18. The method of any one of claims 14-17, wherein the metallophilic seed material forms a complex between the salt cation and the active anode material, or wherein the metallophilic seed material forms a complex between the salt anion and the active anode material.

19. The method of any one of claims 14-18, wherein the metallophilic seed is packed on the substrate such that a plurality of voids is formed on the substrate, and wherein the one or more active materials are deposited within the plurality of voids during the deposition step of the active material.

20. A method comprising: providing the anode of any one of claims 1-5, providing an electrolyte; providing a cathode; and providing a separator to form the electrochemical cell of any one of the claims 6-13.

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