WO2024173554A1 - Robust polymer electrolytes with tunable properties via molecular layer deposition - Google Patents

Abstract

Embodiments of the present disclosure pertain to methods of fabricating a polymeric composition on a surface by depositing at least one metal source and at least one organic molecule onto the surface to result in the formation of the polymeric composition. The polymeric composition includes alternating metal-organic molecule units, where the metal is derived from the metal source. The methods of the present disclosure may also include a step of incorporating the formed polymeric composition as a component of an energy storage device, such as a polymer electrolyte or an electrode. Further embodiments of the present disclosure pertain to an energy storage device that includes the polymeric composition of the present disclosure.

Description

TITLE

ROBUST POLYMER ELECTROLYTES WITH TUNABLE PROPERTIES VIA MOLECULAR LAYER DEPOSITION

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to U.S. Provisional Patent Application No. 63/445,856, filed on February 15, 2023. The entirety of the aforementioned application is incorporated herein by reference.

BACKGROUND

[0002] Energy storage device components, such as polymer electrolytes, suffer from numerous limitations. For instance, such limitations for polymer electrolytes include relatively low ionic conductivities, poor interfaces, low Li⁺ transference number, and low electrochemical and thermal stability. Numerous embodiments of the present disclosure aim to address the aforementioned limitations.

SUMMARY

[0003] In some embodiments, the present disclosure pertains to methods of fabricating a polymeric composition on a surface. In some embodiments, the methods of the present disclosure include a step of depositing at least one metal source and at least one organic molecule onto the surface. In some embodiments, the depositing results in the formation of the polymeric composition. In some embodiments, the polymeric composition includes alternating metal-organic molecule units, where the metal is derived from the metal source.

[0004] In some embodiments, the methods of the present disclosure also include a step of incorporating a formed polymeric composition as a component of an energy storage device. In some embodiments, the formed polymeric composition is incorporated as a polymer electrolyte of the energy storage device. In some embodiments, the formed polymeric composition is incorporated as a component of an electrode of the energy storage device. [0005] Additional embodiments of the present disclosure pertain to an energy storage device that includes the polymeric composition of the present disclosure. In some embodiments, the energy storage device is a battery. In some embodiments, the battery includes, without limitation, all solid-state batteries, alkali metal-based batteries, lithium-ion based batteries, lithium batteries, sodium batteries, potassium batteries, or combinations thereof.

BRIEF DESCRIPTION OF THE DRAWINGS

[0006] A better understanding of the present invention can be obtained when the following detailed description is considered in conjunction with the following drawings.

[0007] FIGS. 1A-1C provide depictions of various energy storage devices in accordance with various embodiments of the present disclosure.

[0008] FIG. 2 shows the structures of various alkali metal precursors as sources of lithium (Li), sodium (Na), and potassium (K) for polymer electrolyte formation.

[0009] FIG. 3 shows the structures of various high molecular weight organic precursors for polymer electrolyte formation.

[0010] FIG. 4 provides a schematic illustration of a general molecular layer deposition (MLD) process for growing alkali metal-containing polymers of high molecular weight using alkali metal precursors and organic precursors.

[0011] FIGS. 5A-5D provide another schematic illustration of a general MLD process for growing alkali metal-containing polymers of high molecular weight using lithium tert-butoxide (LTB) as alkali metal precursors and H-[O-R]_n-OH as organic precursors of high molecular weight. The MLD process typically consists of four steps for each MLD cycle: dosing LTB (FIG. 5A); purging oversupplied LTB and byproduct tert-Butyl alcohol (FIG. 5B); dosing H-[O-R]_n-OH (FIG. 5C); and purging oversupplied H-[O-R]_n-OH and byproduct H2 (FIG. 5D). These four steps can repeated for the formation of thick films.

[0012] FIGS. 6A-6C illustrate the growth of lithium- triethanolamine (LiTEA) polymer electrolytes via LMD. FIG. 6A provides a schematic illustration of the LiTEA formation process through MLD. FIG. 6B provides quartz crystal microbalance (QCM) measurements of the MLD- formed LiTEA in 50 cycles at 150 °C. FIG. 6C shows the QCM profile of three consecutive MLD LiTEA growth cycles in the stable growth region. [0013] FIGS. 7A-7B show data related to the characterization of LiTEA films. FIG. 7A shows scanning electron microscopy (SEM) images of pristine nitrogen-doped graphene nanosheets (N- GNS), 100-MLD-cycle LiTEA over graphene nanosheets (N-GNS), and 200-MLD-cycle LiTEA over N-GNS. FIG. 7B shows high-resolution X-ray photoelectron spectroscopy (XPS) analyses of LiTEA films: Li Is, N Is, C Is, and O Is spectra.

[0014] FIGS. 8A-8B illustrate the beneficial effects of LiTEA on Li anodes. FIG. 8A illustrates the effects of the MLD LiTEA coating on Li anodes in Li||Li symmetric cells, compared to a bare Li||Li cell at a current density 2 mA/cm² and a capacity of 1 mAh/cm². Compared to the bare Li/Li cell, all the MLD LiTEA coatings with 40, 80, 100, 200, 300, 400, and 500 cycles (named as LiTEA-40, LiTEA-80, LiTEA- 100, LiTEA-200, LiTEA-300, LiTEA-400, and LiTEA-500, respectively) can significantly improve the stability of Li anodes for long-term cyclability. FIG. 8B shows enlarged segments of the overpotential profiles of FIG. 8A. The electrolyte was 1 M bis(trifluoromethane)sulfonamide lithium salt (LiTFSI, Sigma Aldrich) in 1,3-dioxolane (DOL) and 1,2-dimethoxyethane (DME) (1:1, v/v).

[0015] FIGS. 9A-9B illustrate the beneficial effects of LiTEA on Li anodes. FIG. 9A shows the effects of the MLD LiTEA coating on Li anodes in Li||Li symmetric cells, compared to bare Li||Li cell at a current density 5 mA/cm² and a capacity of 1 mAh/cm². Compared to the bare Li||Li cell, all the MLD LiTEA coatings with 40, 80, 100, 200, 300, 400, and 500 cycles (named as LiTEA- 40, LiTEA-80, LiTEA- 100, LiTEA-200, LiTEA-300, LiTEA-400, and LiTEA-500, respectively) can significantly improve the stability of Li anodes for long-term cyclability. FIG. 9B shows enlarged segments of the overpotential profiles of FIG. 9A. The electrolyte was 1 M bis(trifluoromethane)sulfonamide lithium salt (LiTFSI, Sigma Aldrich) in 1,3-dioxolane (DOL) and 1,2-dimethoxyethane (DME) (1:1, v/v).

[0016] FIGS. 10A-10B provide analyses on cycled Li||Li cells. Shown are SEM images of the surfaces (FIG. 10A) and the cross-sections (FIG. 10B) of the cycled bare, LiTEA-40, LiTEA-80, and LiTEA-200 electrodes after 500 Li-stripping/plating cycles at 2 mA/cm² and 1 mAh cm².

[0017] FIGS. 11A-11B show x-ray photoelectron spectroscopy (XPS) depth profiling on bare (FIG. 11A) and LiTEA-200 (FIG. 11B) electrodes after 10 and 50 Li stripping/plating cycles at 2 mA/cm² and 1 mAh/cm². [0018] FIGS. 12A-12D show the evolutions of bare Li and LiTEA200-caoted Li after 24-hour stripping (or plating) in Li||Li symmetric cells, observed by scanning electron microscopy (SEM). FIG. 12A shows the SEM observations of the morphological changes of the bare Li electrode after 24-h stripping at 2 mA/cm². FIG. 12B shows the SEM observations of the morphological changes of the bare Li electrode after 24-h plating at 2 mA/cm². FIG. 12C shows the SEM observations of the morphological changes of the LiTEA200-coated Li electrode after 24-h stripping at 2 mA/cm². FIG. 12D shows the SEM observations of the morphological changes of the LiTEA200- coated electrode after 24-h plating at 2 mA/cm². The electrolyte was 1 M bis(trifluoromcthanc)sulfonamidc lithium salt (LiTFSI, Sigma Aldrich) in 1,3-dioxolanc (DOL) and 1,2-dimethoxyethane (DME) (1:1, v/v) (Sigma Aldrich).

[0019] FIGS. 13A-13D show the evolutions of bare Li and LiTEA200-caoted Li after 48-hour stripping/plating (i.e., a 24-hour stripping followed by a 24-hour plating) or 48-hour plating/stripping (i.e., a 24-hour plating followed by a 24-hour stripping) in Li||Li symmetric cells, observed by SEM. FIG. 13A shows the SEM observations of the morphological changes of the bare Li electrode after 48-h stripping/plating at 2 mA/cm². FIG. 13B shows the SEM observations of the morphological changes of the bare Li electrode after 48-h plating/stripping at 2 mA/cm². FIG. 13C shows the SEM observations of the morphological changes of the LiTEA200-coated Li electrode after 48-h stripping/plating at 2 mA/cm². FIG. 13D shows the SEM observations of the morphological changes of the LiTEA200-coated electrode after 48-h plating/stripping at 2 mA/cm². The electrolyte was 1 M bis(trifluoromethane)sulfonamide lithium salt (LiTFSI, Sigma Aldrich) in 1,3-dioxolane (DOL) and 1,2-dimethoxyethane (DME) (1:1, v/v).

[0020] FIG. 14 shows the beneficial effects of LiTEA coating in Li||NMC811 lithium metal batteries. Compared to bare Li||NMC811 cell, the LiTEA200-Li||NMC811 cell improved by 25% while the LiTEA200-Li||Li2S20-NMC811 cell improved by 61% in capacity retention. All these results clearly demonstrate the beneficial effects of the LiTEA coating. Here, 1 C = 200 mA/g. The electrolyte was 1 .2 M LiPFe in ethylene carbonate (EC)/ethylmethyl carbonate (EMC) (3:7 by weight). DETAILED DESCRIPTION

[0021] It is to be understood that both the foregoing general description and the following detailed description are illustrative and explanatory, and are not restrictive of the subject matter, as claimed. In this application, the use of the singular includes the plural, the word “a” or “an” means “at least one”, and the use of “or” means “and/or”, unless specifically stated otherwise. Furthermore, the use of the term “including”, as well as other forms, such as “includes” and “included”, is not limiting. Also, terms such as “element” or “component” encompass both elements or components comprising one unit and elements or components that include more than one unit unless specifically stated otherwise.

[0022] The section headings used herein are for organizational purposes and are not to be construed as limiting the subject matter described. All documents, or portions of documents, cited in this application, including, but not limited to, patents, patent applications, articles, books, and treatises, are hereby expressly incorporated herein by reference in their entirety for any purpose. In the event that one or more of the incorporated literature and similar materials defines a term in a manner that contradicts the definition of that term in this application, this application controls.

[0023] Lithium-ion batteries (LIBs) are penetrating the market of electric vehicles and have dominated portable electronics. However, better battery technologies over state-of-the-art LIBs are still urgently needed, which are expected to provide more reliable safety, higher energy density, lower cost, and longer lifetime.

[0024] To achieve these goals, the currently widely used organic liquid electrolytes must be optimized. Organic liquid electrolytes include lithium salts dissolved in flammable organic solvents. As one of the key components of LIBs, they are ionically conductive but electronically insulating. They act as the ion transport pathway in LIBs. The cell capacity, working temperature range, safety issues and cyclability of LIBs are influenced significantly by the selected electrolyte.

[0025] Catastrophic failure of LIBs often begins with ignition of the liquid electrolytes. In addition to safety concerns, liquid electrolytes have also hindered many promising electrode materials from commercialization, such as lithium (Li) metal anodes, sodium (Na) metal anodes, silicon (Si) anodes, sulfur (S) cathodes, and oxygen (O2) cathodes. [0026] To overcome these issues of liquid electrolytes, solid electrolytes (SEs) have been widely investigated. SEs can be categorized into inorganic and polymeric SEs (i.e., iSEs and pSEs, respectively).

[0027] Polymers are nonvolatile and essentially nonflammable. There are three types of pSEs: gel polymer electrolytes (GPEs), solvent-free solid polymer electrolytes (SPEs), and composite polymer electrolytes (CPEs).

[0028] To be successfully used as a polymer electrolyte, a polymer should preferably possess certain properties. Such properties may include ionic conductivity of 10'⁴ S/cm or higher at ambient temperature, a Li⁺ transference number that is close to unity, great mechanical strength, electrochemical window up to 4-5 V versus Li/Li⁺, and optimal chemical and thermal stability. Ionic conductivity is an important property of polymer electrolytes.

[0029] SPEs are dry solid polymer electrolytes. In literature, they generally consist exclusively of polymer matrices and Li salts as solutes without the addition of liquid solvents as plasticizers and can be easily prepared by solvent-casting, hot molding, or extrusion techniques. However, the ionic conductivity of SPEs is usually unsatisfactory (typically less than 10'⁵ S/cm at room temperature). Among all the SPEs, polyethylene oxide (PEO) is the most frequently applied polymer matrix.

[0030] As an intermediate state between organic liquid electrolytes and SPEs, GPEs are composed of polymer matrices, liquid solvents as plasticizers, lithium salts, and additives such as inorganic fillers. Due to the impregnation with liquid electrolytes, GPEs in general have high ionic conductivity (up to 10’^! S/cm at room temperature) but poor mechanical strength. The latter has made them impossible in batteries.

[0031] CPEs are attempted to overcome the disadvantages of SPEs. Inorganic fillers are generally added into the SPEs to develop CPEs with the purpose of enhancing the ionic conductivity and mechanical strength. The fillers employed can be further sub-divided into non-ionically conductive (passive) fillers and ionically conductive (active) fillers.

[0032] Compared to the currently widely used organic liquid electrolytes, pSEs have prominent advantages such as low flammability, easy processability, and more tolerance to vibration, shock, and mechanical deformation. They also provide better electrode/electrolyte interfacial contact as well as compatibility than that of inorganic solid electrolytes. [0033] However, polymer electrolytes are still experiencing many difficulties and disadvantages. Such limitations, include, without limitation, the following: (1) relatively low ionic conductivities, for it is still quite challenging to achieve an ionic conductivity of 10'³ S/cm for SPEs at room temperature; (2) poor interfaces; (3) low Li⁺ transference number; and (4) low electrochemical and thermal stability. Numerous embodiments of the present disclosure aim to address the aforementioned limitations.

[0034] Methods of fabricating polymeric compositions

[0035] In some embodiments, the present disclosure pertains to methods of fabricating a polymeric composition on a surface. In some embodiments, the methods of the present disclosure include a step of depositing at least one metal source and at least one organic molecule onto the surface. In some embodiments, the depositing results in the formation of the polymeric composition. In some embodiments, the polymeric composition includes alternating metal-organic molecule units, where the metal is derived from the metal source.

[0036] Metal sources

[0037] The metals in the polymeric compositions of the present disclosure may be derived from various metal sources. For instance, in some embodiments, the metal source includes an alkali metal source. In some embodiments, the alkali metal source includes, without limitation, Li, Na, K, or combinations thereof.

[0038] In some embodiments, the metal source includes a lithium source. In some embodiments, the lithium source includes, without limitation, lithium tert-butoxide (LTB, LiO'Bu). lithium hexamethyldisilazide [LiHMDS, Li(N(SiMes)2)], lithium trimethylsilanolate (LiTMSO, LiOSiMc.!), Li(thd) (thd = 2,2,6,6-tetramethyl-3,5-heptanedionate), or combinations thereof. In some embodiments, the lithium source includes lithium tert-butoxide (LTB, LiO'Bu).

[0039] In some embodiments, the metal source includes a sodium source. In some embodiments, the sodium source includes, without limitation, sodium tert-butoxide (NaO^fBu), sodium trimethylsilanolate (NaTMSO), Li(thd) ((thd = 2,2,6,6-tetramethyl-3,5-heptanedionate)), or combinations thereof. [0040] In some embodiments, the metal source includes a potassium source. In some embodiments, the potassium source includes, without limitation, potassium tert-butoxide ( KO'Bu), potassium trimethylsilanolate (KTMSO), K(thd) ((thd = 2,2,6,6-tetramethyl-3,5-heptanedionate)), or combinations thereof.

[0041] Organic molecules

[0042] The methods of the present disclosure may utilize various types of organic molecules. For instance, in some embodiments, the organic molecule includes a general formula of H-[O-R]_n-OH. In some embodiments, n is an integer of 1 or more. In some embodiments, R represents the organic molecule. In some embodiments, the organic molecule includes, without limitation, diethanolamine (DEA), triethanolamine (TEA), glycerol (GL), triglycerol (TGL), glycerol propoxylate (GLP), glycerol ethoxylate (GLE), trimethylolpropane ethoxylate (TMPE), polyethylene glycol (PEG), chitosan (CS), hydroquinone (HQ), ethylene glycol (EG), diols, triols, polyols, hydroquinone (HQ), tetrafluorohydroquinone (FHQ), 1 ,4-benzenedicarboxylic acid (BDC), 2,6-naphthalene dicarboxylic acid (NDC) 1,2-ethanediol (EDO), 1,4-butanediol (BDO), 1,6-hexanediole (HDO), fumaric acid (FC), 2,4-hexadiyene-l,6-diol (HDD), 1,2,4- trihydroxybenzene (THB), lactic acid (LC), 2,2-bis(hydroxymethyl)-l,3-propanediole (BHMPD), alpha-thioglycerol (TGL), 1,2,4-butanetriol (BT), 1,2,5,6-hexanetriol (HT), 2-hydroxy methyl- 1,3- propanediol (HMPD), l-(4-nitrophenyl)glycerol (NPGL), or combinations thereof.

[0043] Depositing metal sources and organic molecules

[0044] Various methods may be utilized to deposit metal sources and organic molecules onto a surface. For instance, in some embodiments, the depositing includes the following sequential steps: (a) depositing the metal source onto the surface, where the depositing results in the coupling of the metal to the surface; (b) depositing the organic molecule onto the surface, where the depositing results in the coupling of the organic molecule to the metal coupled to the surface; and (c) depositing the metal source onto the surface, where the depositing results in the coupling of the metal to the organic molecule coupled to the surface. [0045] In some embodiments, steps (b) and (c) are repeated multiple times. For instance, in some embodiments, steps (b) and (c) are repeated at least 2 times. In some embodiments, steps (b) and (c) are repeated at least 20 times. In some embodiments, steps (b) and (c) are repeated at least 40 times. In some embodiments, steps (b) and (c) are repeated at least 80 times. In some embodiments, steps (b) and (c) are repeated at least 100 times. In some embodiments, steps (b) and (c) are repeated at least 200 times. In some embodiments, steps (b) and (c) are repeated at least 300 times. In some embodiments, steps (b) and (c) arc repeated at least 400 times. In some embodiments, steps (b) and (c) are repeated at least 500 times. In some embodiments, the depositing results in the formation of a layered polymeric composition.

[0046] In some embodiments, the depositing occurs by a method that includes, without limitation, molecular layer deposition (MLD), atomic layer deposition (ALD), or combinations thereof. In some embodiments, the depositing occurs by molecular layer deposition (MLD).

[0047] Polymeric compositions

[0048] The methods of the present disclosure may be utilized to form various types of polymeric compositions. Additional embodiments of the present disclosure pertain to the formed polymeric compositions. The formed polymeric compositions generally include alternating metal-organic molecule units.

[0049] The polymeric compositions of the present disclosure can include various metals. For instance, in some embodiments, the metals include one or more alkali metals. In some embodiments, the one or more alkali metals include, without limitation, lithium (Li), sodium (Na), and potassium (K), or combinations thereof.

[0050] The polymeric compositions of the present disclosure can include various organic molecule units. For instance, in some embodiments, the organic molecule units include, without limitation, diethanolamine (DEA), triethanolamine (TEA), glycerol (GL), triglycerol (TGL), glycerol propoxylate (GLP), glycerol ethoxylate (GLE), trimethylolpropane ethoxylate (TMPE), polyethylene glycol (PEG), chitosan (CS), hydroquinone (HQ), ethylene glycol (EG), diols, triols, polyols, hydroquinone (HQ), tetrafluorohydroquinone (FHQ), 1 ,4-benzenedicarboxylic acid (BDC), 2,6-naphthalene dicarboxylic acid (NDC) 1,2-ethanediol (EDO), 1,4-butanediol (BDO), 1 ,6-hexanediole (HDO), fumaric acid (FC), 2,4-hexadiyene-l ,6-diol (HDD), 1 ,2,4- trihydroxybcnzcnc (THB), lactic acid (LC), 2,2-bis(hydroxymcthyl)-l,3-propancdiolc (BHMPD), alpha-thioglycerol (TGL), 1,2,4-butanetriol (BT), 1,2,5,6-hexanetriol (HT), 2-hydroxy methyl- 1,3- propanediol (HMPD), l-(4-nitrophenyl)glycerol (NPGL), or combinations thereof. In some embodiments, the organic molecule units include, without limitation, alkyl groups, alkene groups, alkyne groups, carbonyl groups, carboxylic acid groups, alcohol groups, ether groups, phenol groups, amido groups, amide groups, amine groups, methyl groups, ethyl groups, isopropyl groups, isobutyl groups, glycerol groups, aromatic groups, phenyl groups, benzene groups, quinone groups, or combinations thereof.

[0051] In some embodiments, the formed polymeric composition includes the following formula:

-//-M-[0-R]_n-0-M-//-

[0052] In some embodiments, M represents the metals from the metal source. In some embodiments, R represents the organic molecule. In some embodiments, n is an integer of 1 or more. In some embodiments, n may vary to adjust a polymer’s properties. In some embodiments, -//- represents the alternating metal-organic molecule units.

[0053] In some embodiments, R includes, without limitation, alkyl groups, alkene groups, alkyne groups, carbonyl groups, carboxylic acid groups, alcohol groups, ether groups, phenol groups, amido groups, amide groups, amine groups, methyl groups, ethyl groups, isopropyl groups, isobutyl groups, glycerol groups, aromatic groups, phenyl groups, benzene groups, quinone groups, or combinations thereof.

[0054] In some embodiments, M includes one or more alkali metals. In some embodiments, the one or more alkali metals include, without limitation, lithium (Li), sodium (Na), potassium (K), or combinations thereof. In some embodiments, M is lithium (Li), and R is triethanolamine (TEA). [0055] The polymeric compositions of the present disclosure can have various thicknesses. For instance, in some embodiments, the formed polymeric composition has a thickness of about 0.5 nm to about 2000 nm. In some embodiments, the formed polymeric composition has a thickness of about 50 nm to about 500 nm. In some embodiments, the formed polymeric composition has a thickness of about 50 nm to about 100 nm. In some embodiments, the formed polymeric composition has a thickness of about 50 nm to about 75 nm.

[0056] The polymeric compositions of the present disclosure can have various masses. For instance, in some embodiments, the polymeric compositions of the present disclosure have masses that range from about 100 ng/cm² to about 2,000 ng/cm². In some embodiments, the polymeric compositions of the present disclosure have masses that range from about 500 ng/cm² to about 1,000 ng/cm². In some embodiments, the polymeric compositions of the present disclosure have masses that range from about 700 ng/cm² to about 900 ng/cm². In some embodiments, the polymeric compositions of the present disclosure have masses of more than about 500 ng/cm². In some embodiments, the polymeric compositions of the present disclosure have masses of more than about 600 ng/cm². In some embodiments, the polymeric compositions of the present disclosure have masses of more than about 700 ng/cm². In some embodiments, the polymeric compositions of the present disclosure have masses of more than about 750 ng/cm².

[0057] In some embodiments, the formed polymeric composition includes a plurality of stacked layers. In some embodiments, each layer includes the same metal-organic molecule units. In some embodiments, each layer includes a different metal-organic molecule unit.

[0058] The formed polymeric compositions of the present disclosure may be in various forms. For instance, in some embodiments, the formed polymeric composition is in the form of a metal alkoxide-based polymer, a homopolymer of a metal alkoxide-based polymer, a heteropolymer of a metal alkoxide-based polymer, or combinations thereof. In some embodiments, the polymeric composition is in the form of lithium-conducting polymers, sodium-conducting polymers, potassium conducting polymers, or combinations thereof.

[0059] Surfaces [0060] The polymeric compositions of the present disclosure may be applied to various surfaces. For instance, in some embodiments, the surface includes a substrate. In some embodiments, the surface includes a plurality of hydroxyl groups. In some embodiments, the plurality of hydroxyl groups is operational for anchoring the polymeric composition.

[0061] In some embodiments, the surface includes a surface of an electrode. In some embodiments, the polymeric composition forms a coating on the surface of the electrode. In some embodiments, the electrode includes an anode, such as a lithium anode. In some embodiments, the electrode includes a cathode.

[0062] Incorporation as an energy storage device component

[0063] In some embodiments, the methods of the present disclosure also include a step of incorporating a formed polymeric composition as a component of an energy storage device. The polymeric compositions of the present disclosure may be incorporated as various energy storage device components. For instance, in some embodiments, the formed polymeric composition is incorporated as a polymer electrolyte of the energy storage device. In some embodiments, the formed polymeric composition is incorporated as a solid-state polymer electrolyte of the energy storage device.

[0064] In some embodiments, the formed polymeric composition is incorporated as a component of an electrode of the energy storage device. In some embodiments, the formed polymeric composition is incorporated as a surface coating of the electrode. In some embodiments, the electrode includes an anode. In some embodiments, the electrode includes a lithium anode. In some embodiments, the electrode includes a sodium anode. In some embodiments, the electrode includes a potassium anode. In some embodiments, the electrode includes a cathode.

[0065] Energy storage devices

[0066] Additional embodiments of the present disclosure pertain to an energy storage device that includes the polymeric composition of the present disclosure. In some embodiments, the polymeric composition includes alternating metal-organic molecule units.

[0067] Energy storage device components [0068] The polymeric compositions of the present disclosure may serve as various components of energy storage devices. For instance, in some embodiments, the polymeric composition is a component of an electrode. In some embodiments, the polymeric composition is a surface coating on the electrode. In some embodiments, the electrode is an anode. In some embodiments, the electrode includes a sodium anode. In some embodiments, the electrode includes a potassium anode. In some embodiments, the anode is a lithium anode. In some embodiments, the electrode is a cathode.

[0069] In some embodiments, the polymeric composition is a component of a polymer electrolyte. In some embodiments, the electrolyte is a solid-state polymer electrolyte.

[0070] The polymeric compositions of the present disclosure may serve as components of various energy storage devices. For instance, in some embodiments, the energy storage device is a battery. In some embodiments, the battery includes, without limitation, all solid-state batteries, alkali metal-based batteries, lithium-ion based batteries, lithium batteries, sodium batteries, potassium batteries, or combinations thereof.

[0071] Metals and organic molecules

[0072] Polymeric compositions in the energy storage devices of the present disclosure can include various metals. For instance, in some embodiments, the metal includes an alkali metal. In some embodiments, the alkali metal includes, without limitation lithium (Li), sodium (Na), potassium (K), or combinations thereof.

[0073] Polymeric compositions in the energy storage devices of the present disclosure can include various organic molecules. For instance, in some embodiments, the organic molecule includes, without limitation diethanolamine (DEA), triethanolamine (TEA), glycerol (GL), triglycerol (TGL), glycerol propoxylate (GLP), glycerol ethoxylate (GLE), trimethylolpropane ethoxylate (TMPE), polyethylene glycol (PEG), chitosan (CS), hydroquinone (HQ), ethylene glycol (EG), diols, triols, polyols, hydroquinone (HQ), tetrafluorohydroquinone (FHQ), 1,4- benzenedicarboxylic acid (BDC), 2,6-naphthalene dicarboxylic acid (NDC) 1,2-ethanediol (EDO), 1 ,4-butanediol (BDO), 1 ,6-hexanediole (HDO), fumaric acid (FC), 2,4-hexadiyene- 1 ,6-diol (HDD), 1 ,2,4-trihydroxybcnzcnc (THB), lactic acid (LC), 2,2-bis(hydroxymcthyl)-l,3- propanediole (BHMPD), alpha-thioglycerol (TGL), 1,2,4-butanetriol (BT), 1,2,5,6-hexanetriol (HT), 2-hydroxymethyl-l,3-propanediol (HMPD), l-(4-nitrophenyl)glycerol (NPGL), or combinations thereof. In some embodiments, the organic molecule includes, without limitation alkyl groups, alkene groups, alkyne groups, carbonyl groups, carboxylic acid groups, alcohol groups, ether groups, phenol groups, amido groups, amide groups, amine groups, methyl groups, ethyl groups, isopropyl groups, isobutyl groups, glycerol groups, aromatic groups, phenyl groups, benzene groups, quinone groups, or combinations thereof.

[0074] In some embodiments, the polymeric compositions in the energy storage devices of the present disclosure include the following formula:

-//-M-[0-R]_n-0-M-//-

[0075] In some embodiments, M represents the metal. In some embodiments, R represents the organic molecule. In some embodiments, n is an integer of 1 or more. In some embodiments, n may vary to adjust a polymer’s properties. In some embodiments, -II- represents the alternating metal-organic molecule units.

[0076] In some embodiments, R includes, without limitation alkyl groups, alkene groups, alkyne groups, carbonyl groups, carboxylic acid groups, alcohol groups, ether groups, phenol groups, amido groups, amide groups, amine groups, methyl groups, ethyl groups, isopropyl groups, isobutyl groups, glycerol groups, aromatic groups, phenyl groups, benzene groups, quinone groups, or combinations thereof. In some embodiments, M includes one or more alkali metals. In some embodiments, the one or more alkali metals includes, without limitation Li, Na, K, or combinations thereof. In some embodiments, M is lithium (Li) and R is triethanolamine (TEA). [0077] The polymeric compositions in the energy storage devices of the present disclosure can have various thicknesses. For instance, in some embodiments, the polymeric composition has a thickness of about 0.5 nm to about 2000 nm. In some embodiments, the formed polymeric composition has a thickness of about 50 nm to about 100 nm. In some embodiments, the polymeric composition has a thickness of about 50 nm to about 100 nm. In some embodiments, the polymeric composition has a thickness of about 50 nm to about 75 nm.

[0078] In some embodiments, the polymeric composition includes a plurality of stacked layers. In some embodiments, each layer includes the same metal-organic molecule units. In some embodiments, each layer includes a different metal-organic molecule unit. In some embodiments, the polymeric composition is in the form of a metal alkoxide-based polymer, a homopolymer of a metal alkoxide-based polymer, a heteropolymer of a metal alkoxide-based polymer, or combinations thereof.

[0079] The energy storage devices of the present disclosure can have various structures and arrangements. For instance, in some embodiments illustrated in FIG. 1A, the energy storage devices of the present disclosure are in the form of solid-state battery 10, which includes anode 12, polymer electrolyte 14, and cathode 16. In this Example, the polymeric composition of the present disclosure is a component of polymer electrolyte 14. Additionally, the polymeric composition includes a plurality of stacked layers 18, 19, 20, and 21

[0080] In some embodiments illustrated in FIG. IB, the energy storage devices of the present disclosure are in the form of liquid battery 30, which includes anode 31 , polymer electrolyte 32, liquid electrolyte 33, and cathode 34. In this Example, the polymeric composition of the present disclosure is a component of polymer electrolyte 32.

[0081] In some embodiments illustrated in FIG. 1C, the energy storage devices of the present disclosure are in the form of liquid battery 40, which includes anode 41, liquid electrolyte 42, polymer electrolyte 43, and cathode 44. In this Example, the polymeric composition of the present disclosure is a component of polymer electrolyte 43.

[0082] Additional embodiments [0083] Reference will now be made to more specific embodiments of the present disclosure and experimental results that provide support for such embodiments. However, Applicant notes that the disclosure below is for illustrative purposes only and is not intended to limit the scope of the claimed subject matter in any way.

[0084] Example 1. Formation of Polymer Electrolytes with Tunable Properties

[0085] Conventional methods of fabricating satisfactory polymer electrolytes, including powderbased processing, wet chemical processing, and high viscosity processing, have numerous limitations. In particular, the resultant polymer electrolytes in general have a limited ionic conductivity. The polymer electrolytes typically have thicknesses of several tens of microns, thereby limiting the volume energy density of batteries. Furthermore, polymer electrolytes fabricated by conventional processes widely suffer from interfacial issues when they are assembled in battery cells.

[0086] Recently, molecular layer deposition (MLD) has emerged as a new technique enabling accurate growth of pure polymers and hybrid polymers in a controllable mode. Several recent studies have reported lithium-containing polymers via MLD, which bonded lithium atoms to a repeated polymeric segment (monomer or repeated unit). These lithium-containing polymers have shown some potential as polymer electrolytes in lithium batteries. However, the organic precursors used for providing repeated units are usually low in molecular weight. This might have helped achieve high ionic conductivity, but have also underlaid some undesirable properties, such as low mechanical strength, inferior chemical resistance, and limited electrochemical stability. Thus, new MLD processes are urgently needed for producing new polymers as solid electrolytes with improved properties in lithium-ion batteries (LIBs) and emerging battery systems.

[0087] In this Example, Applicant describes the development of new MLD processes bonding alkali metal atoms (including lithium (Li), sodium (Na), and potassium (K)) to repeating units of high molecular weight molecules. In addition to achieving high ionic conductivity, the resultant Li/Na/K-containing polymer electrolytes also enable high mechanical strength, increased chemical resistance, and improved electrochemical stability. [0088] The products formed can be used as promising solid polymer electrolytes or surface coatings in lithium, sodium, or potassium batteries. The resultant lithium, sodium, or potassium batteries enable better safety, higher energy density, lower cost, and longer lifetime. The benefits of polymer electrolytes via the MLD processes in this Example lie in the following aspects: (1) improved properties, in terms of ionic conductivity, mechanical strength, chemical resistance, and electrochemical stability; (2) free of interfacial contact issues due to chemical bonding between the MLD polymeric coatings and battery electrodes; (3) low temperatures of less than 200 °C; (4) high-quality conformal and uniform coverage; and (5) accurate film thicknesses ranging from nano to micron controlled at the molecular level, depending on the needs in application.

[0089] Example 1,1. Alkali metal precursors

[0090] Alkali metal precursors are sources of alkali metals (i.e., Li, Na, and K). The alkali metal precursors used in this Example include lithium-containing precursors, sodium-containing precursors, and potassium-containing precursors.

[0091] Example 1.1.1. Lithium-containing precursors

[0092] To produce Li-conducting polymer electrolytes in this Example, there are four compounds usable as Li-containing precursors, including lithium tert-butoxide (LTB, LiO'Bu), lithium hexamethyldisilazide [LiHMDS, Li(N(SiMe₃)2)], lithium trimethylsilanolate (LiTMSO, LiOSiMc ), and Li(thd) (thd = 2,2,6,6-tetramethyl-3,5-heptanedionate). These Li-containing precursors are used as lithium sources in this Example’s MLD processes for Li-conducting polymer electrolytes. Their molecular structures are shown in FIG. 2, in which t-Bu is tert-butyl (i.e., -C(CH₃)₃).

[0093] Example 1.1.2. Sodium-containing precursors

[0094] To produce Na-containing polymers in this Example, there are NaO'Bu, NaTMSO, and Na(thd) serving as Na-containing precursors (FIG. 2).

[0095] Example 1.1.3. Potassium-containing precursors

[0096] To produce K-containing polymers in this Example, there are KO^£Bu, KTMSO, and K(thd) serving as K-containing precursors (FIG. 2).

[0097] Example L2. Organic precursors [0098] To couple with the above-stated Li/Na/K-containing precursors and provide various polymeric chains or backbones of polymer electrolytes, in this Example the organic precursors of high molecular weight are listed in FIG. 3. These organic precursors in FIG. 3 has a general format of H-[O-R]_n-OH, where n is the repeating times of a repeatable unit (i.e., a monomer) and R is used in these molecular structures to represent the “Rest of the molecule”. Except for diethanolamine (BEA), triethanolamine (TEA), and triglycerol (TGL), the other precursors can be selected with a varying number average molecular weight (AG), ranging from 50 - 1000 g/mole. The number average molecular weight (AG) gives the average of the molecular masses of the individual macromolecules. In other words, it is the total weight of the sample divided by the number of molecules in the sample (i.e., M_n =

where N, is the number of molecules having Mt weight in the polymer sample and Mi is the weight of a particular molecule of the sample). The number of repeating units, n, is often called the degree of polymerization, which relates the amount of monomer that has been converted to polymer.

[0099] Example 1.3. MLP Processes for alkali metal-containing polymers with adjustable repeating units

[00100] In this Example, using one of alkali metal precursors in FIG. 2 to couple with one of the organic precursors of high molecular weight (i.e., H-[O-R]_n-OH) in FIG. 3, a variety of alkali metal-containing polymers can be produced with a varying repeatable unit of K/Na/Li-[O-R]_n-O- Li//Na/K, as illustrated in FIG. 4, in which -[O-R]n-O- is the repeatable organic unit contributed by the organic precursors in FIG. 3. Through adjusting the structure and molecular weight of - [O-R]u-O-, the resultant alkali metal-containing polymers enable desirable mechanical, chemical, and physical properties.

[00101] FIGS. 5A-5D illustrate an MLD process for growing Li-containing polymers as solid electrolytes, using lithium rf-butoxide (LTB) and an organic precursor of high molecular weight. The MLD process operates under a cyclic mode to build up the film thickness of the polymer electrolyte, in which the LTB precursor is dosed to react with a substrate surface with hydroxyl functional groups (-OH) (FIG. 5A) and deposit Li on the substrate surface (FIG. 5B). [00102] Once the surface hydroxyl groups deplete completely, a purge is applied to remove the byproduct tert-Butyl alcohol (i.e., HOCfCHa ) thoroughly (FIG. 5C). Then, another organic precursor of high molecular weight (i.e., H-[O-R]_n-O-H) is dosed to fully react with the surface Li atoms and form a new surface layer of -[O-R]_n-OH with the byproduct of H2. This second surface reaction will terminate automatically once all surface Li atoms have been bonded to -[O-R]_n-OH and recover the surface to the coverage of -OH (FIG. 5D). The completion of the second surface reaction is followed by another purge to remove the byproduct H2 completely. Upon this point, one complete MLD cycle has been conducted. If needed, more MLD cycles can be performed to achieve the desirable film thickness. Similarly, the LTB precursor can be replaced by any other alkali metal-containing precursors (e.g., the precursors listed in FIG. 2) to couple with any organic precursors (e.g.. the precursors listed in FIG. 3) of high molecular weight for growing alkali-metal- containing polymers as solid electrolytes.

[00103] Example L4. Proof of Concept

[00104] Using lithium tert-butoxide (LTB) and triethanolamine (TEA) as precursors, a new MLD process (as illustrated in FIG. 6A) is confirmed by the measurements of quartz crystal microbalance (QCM) (FIGS.6B and 6C), which is used for growing a new Li-containing polymer, LiTEA. FIG. 6B shows the linear growth of the MLD LiTEA with increasing cycles, indicating controllably repeatable growth.

[00105] To determine the GPC in A/cycle, Applicant further deposited LiTEA films over nitrogen-doped graphene nanosheets (N-GNS) (FIG. 7A) at 150 °C. The N-GNS features its high surface area and thin wrinkles of < 3 nm. Observing the thickness changes of the N-GNS wrinkles after the LiTEA deposition of 100 and 200 MLD cycles using scanning electron microscopy (SEM) (FIG. 7A), Applicant concluded that the average GPC of the MLD LiTEA is ~3.6 A/cycle.

[00106] Applicant further postulated the overall reaction of the MLD LiTEA as follows in Equation 1 :

SLiO'Bu + N(CH₂CH2OH)3 N(CH₂CH₂01i)₃ + SHO'Bu (1) [00107] The reaction in Equation 1 indicates that the LiTEA has a unit structure of N(CH2CH201i)3. To verify this postulation, Applicant conducted X-ray photoelectron spectroscopy (XPS) measurements on the composition of the deposited LiTEA films on Si wafers. In FIG. 7B, the Li Is x-ray photoelectron spectroscopy (XPS) spectra show only one peak at 56.0 eV, ascribed to Li-O. The N Is spectra exhibit one peak at 402.0 eV, assigned to N-C or oxidized nitrogen compound. The C Is spectra show two evident peaks at 285.4 and 284.1 eV, due to C- N/C-OH and Li-O-C. The two weak peaks at 288.5 and 287.9 eV are related to O=C-OH and N- C=O/C=O bonds. The O I s spectra show two peaks at 529.5 eV and 530.8 eV, owing to O²‘ in Li-0 bonds and a peak at 531.5 eV attributed to C-O-Li or adsorbed H2O.

[00108] Applicant’s XPS analyses revealed that the deposited LiTEA film contains 16.7 at.% of Li, 5.8 at.% of N, 37 at.% of C, and 40.5 at.% of O. The atomic ratio of Li, N, and C is consistent to Applicant’s postulation on the LiTEA unit structure N(CH2CH201i)3 (i.e., nearly 3:1:6). Applicant also noticed that there is a higher O content than that of Applicant’s postulated unit structure. This might be due to some H2O adsorbed in the LiTEA film during the sample loading process. In addition, synchrotron-based X-ray diffraction (XRD) measurements disclosed that the LiTEA film grown on N-GNS has no peaks observed, indicating an amorphous nature of the MLD- deposited LiTEA.

[00109] To demonstrate their ionically conductive nature, the resultant LiTEA films were deposited on Li metal chips as a protective coating to inhibit undesirable reactions between the Li chip and a liquid electrolyte. The LiTEA films on Li chips could be tuned for different thicknesses by simply adjusting MLD cycles and then they are named by their MLD cycles. For example, LiTEA-40, LTEA-80, LiTEA- 100, LiTEA-200, LiTEA-300, LiTEA-400, and LiTEA-500 mean the LiTEA films on Li chips deposited for 40, 80, 100, 200, 300, 400, and 500 MLD cycles, respectively.

[00110] LiTEA-coated Li chips were compared with bare Li chips in Li||Li symmetric cells. They were assembled into Li||Li symmetric coin cells in the Ar-filled glove box, which are tested under two different current densities (2 and 5 mA/cm²) but the same capacity of 1 mAh/cm². In the glove box, oxygen and water were controlled less than 0.01 ppm. Celgard 2325 membrane was used as the separator. The electrolyte was 1 M bis(trifluoromethane)sulfonamide lithium salt (LiTFSI) in 1,3-dioxolane (DOL) and 1 ,2-dimethoxyethane (DME) (1:1, v/v). [00111] Applicant assembled these LiTEA-coated Li electrodes with the same coating thickness into Li||Li symmetric coin cells and investigated their electrochemical cycling performance, compared with bare Li||Li cells. Under a fixed areal capacity of 1 mAh/cm², these different Li||Li cells were tested for their Li-stripping/plating cyclability at two different current densities of 2 and 5 mA/cm². Applicant’s results revealed that, at 2 mA/cm² (FIGS. 8A-8B), an LiTEA coating of > 40 MLD cycles (—14 nm) is necessary to achieve a desirable protection. Comparable to the bare Li||Li cell, the LiTEA-40||LiTEA-40 cell could only survive for less than 500 cycles. This might be due to its thin coating layer. Both of these two cells evolved in their overpotentials increasing quickly from ~50 to 160 mV in less than 400 Li-stripping/plating cycles. In contrast, both the LiTEA-8O||LiTEA-8O and LiTEA- 100||LiTEA- 100 cells could achieve exceptional cyclability up to 5500 Li-stripping/plating cycles without any failure.

[00112] The cells exhibited a highly similar evolution in overpotential, which was relatively high at the first cycle, -100 mV, but stabilized at -30 mV after 700 Li-stripping/plating cycles. Very encouragingly, a further increase in the LiTEA coating film thickness could still accomplish stable cyclability in all the cases up to 500 MLD cycles (-180 nm) but only varied the stabilized overpotentials in 5500 Li-stripping/plating cycles (FIGS. 8A-8B).

[00113] Applicant noticed that the LiTEA-200||LiTEA-200 realized the lowest stabilized overpotential of -20 mV while the stabilized overpotentials increased to -50, -85, and -100 mV for the LiTEA-3OO||LiTEA-3OO, LiTEA-400||LiTEA-400, and LiTEA-5OO||LiTEA-5OO cells, respectively (FIGS. 8A-8B). These results indicated that, in terms of the stabilized overpotential, there is an optimal coating thickness for the LiTEA film, i.e., LiTEA-200 (-72 nm). A thinner coating might not protect Li anodes well while a thicker coating could hinder the transport of Li⁺ ions through the coating layer.

[00114] At a much higher current density of 5 mA/cm², Applicant’ s results also verified that the LiTEA coating is compelling and helped Li||Li cells achieve long-term stable cyclability (FIGS. 9A-9B). As the control, the bare Li||Li cell could only sustain a low overpotential of < 80 mV for only 800 Li-stripping/plating cycles. Thereafter, its overpotential quickly increased up to 1.0 V after -1300 Li-stripping/plating cycles, indicating a failure of the cell cycling. The LiTEA- 40||LiTEA-40 cell could improve its cyclability to a limited extent, sustaining a comparable overpotential of < 80 mV in the first initial 1000 Li-stripping/plating cycles. Thereafter, the cell overpotential increased significantly and reached -300 mV upon the completion of 2000 cycles, where the cell was regarded a failure.

[00115] In contrast, the LiTEA-8O||LiTEA-8O and LiTEA- 100||LiTEA- 100 cells showed little evolution in their cycling overpotential and could sustain a low overpotential of -80 mV for over 10000 Li-stripping/plating cycles without any failure. Similarly, the LiTEA-200||LiTEA-200 cell could enable a stable but lower overpotential of 68 mV after 10000 Li-stripping/plating cycles without any failure. In addition, Li||Li symmetric cells with thicker LiTEA coatings (LiTEA-300, 400, and 500) still could realize stable long-term cyclability without failures, but just increased the cell overpotential to some extent and sustained an overpotential of 82, 95, and 99 mV after 10000 cycles, respectively, compared to the LiTEA-200||LiTEA-200 cell. Particularly, all these LiTEA- coated cells with a coating of > 80 MLD cycles are still under testing without any failures. These results in FIGS. 8A-8B and 9A-9B commonly indicate that the LiTEA films are ionically conductive. They are also chemically and electrochemically stable in the electrolyte of 1 M 1:1 DOL:DME. In Li||Li symmetric cells, the LiTEA-200 is optimal for achieving the best cell performance, in terms of cell overpotential.

[00116] To better understand the protective effects of the LiTEA coating, Applicant observed the morphological evolutions of the cycled Li electrodes. FIG. 10A shows the surface of four Li electrodes (bare, LiTEA-40, LiTEA-80, and LiTEA-200) after 500 Li-stripping/plating cycles at 2 mA/cm² and 1 mAh/cm². Both the bare and LiTEA-40 Li electrodes exhibit a porous structure. In contrast, the surface of the LiTEA-80 and LiTEA-200 electrodes were much smoother and denser. Applicant further verified this through observing the cross-sections of the bare, LiTEA-40, LiTEA- 80 and LiTEA-200 electrodes after 500 Li-stripping/plating cycles using SEM (FIG. 10B). One can observe that the bare electrode after the cycling has been significantly corroded with the substantial formation of solid electrolyte interphase (SEI). In contrast, the LiTEA coatings have evidently protected Li metal from the corrosions. In particular, thicker LiTEA coatings could help remain more Li uncorroded. Very impressively, the cross-section of the LiTEA-200 is nearly intact with very little SEI, and the thickness of the Li layer almost remained unchanged after 500 Li- stripping/plating cycles (FIG. 10B). These results further verified that the LiTEA films are ionically conductive and inert in the electrolyte of 1 M LiTESI in 1:1 DOL:DME.

[00117] Furthermore, Applicant employed XPS depth profiling to investigate the surface composition evolution of four Li electrodes: bare Li (FIG. 11A) and LiTEA-200 electrodes (FIG. 11B) after 10 and 50 Li-stripping/plating cycles. FIG. 11 A reveals that, after 10 Li- stripping/plating cycles, the E and O signals in the bare Li electrode are considerable and relatively stable with film depth within the sputter time of 1000 s, while the other signals of Li, C, and S are much weaker. These results indicate that there was a very thick SEI layer formed on the bare Li electrode after 10 Li-stripping/plating cycles. The detected E and O signals are most likely from the decomposition of LiTFSI salt and the ether solvent. After 50 Li-stripping/plating cycles, the bare Li electrode shows much stronger E signal, indicating the formation of a thicker SEI layer on Li electrode (FIG. 11A). In sharp contrast, the F signal is almost undetectable on the LiTEA-200 electrode after 10 stripping/plating cycles (FIG. 11B).

[00118] On the other hand, the O and C signals show similar evolutionary trend, which drop and then level off. It should be pointed out that the evident C and O signals are mainly due to the LiTEA film rather than the decomposed electrolyte compared to that of the cycled bare Li electrodes. These results indicate that there had little SEI formed on the LiTEA-200 electrode during cycling. Similar results can be observed on the LiTEA-200 electrode after 50 stripping/plating cycles (FIG. 11B). This further verifies that the LiTEA MLD film is chemically and electrochemically stable and serves as an exceptional protective film over Li electrodes in the ether electrolyte. These observations are consistent with the results of FIGS. 8A-8B, 9A-9B, and 10A-10B.

[00119] To further demonstrate the protective effects of this novel LiTEA coating, Applicant conducted a comparative study under an extremely high areal capacity, 48 mAh/cm², in which an LiTEA-200||LiTEA-200 cell and a bare Li||Li cell performed an extremely long 24-h Li- stripping on one Li electrode (an extremely long 24-h plating occurred simultaneously on the opposing electrode) at a current density of 2 mA/cm². As shown in FIGS. 12A-12D, the bare Li electrode after the 24-h stripping was widely covered by craters (as circled by dashed lines) and bumps (or highlands, the areas other than the circles) (FIG. 12A(i), which are partially enlarged in FIG. 12A(ii)). The highlands are smooth while the craters contain many porous structures (FIGS. 12A(iii) and (iv)). One can identify that the highland areas are intact parts of the pristine Li surface area while the craters are the stripped pails. Applicant believes that the porous structures (FIGS. 12A(iii) and (iv)) in the craters are the stripping residuals (i.e., the SEI layer). Without being bound by theory, the craters have stripped Li first, and then the highlands became the new areas for Li-stripping. This had led to a non-uniform stripping process on bare Li electrodes. Consequently, the stripping areas might change with time.

[00120] In addition, the opposite bare Li after a 24-h plating process was also observed (FIG. 12B). A significant amount of dendritic Li has been deposited on the original Li surface (FIG. 12B(i)). Moreover, it could be seen from FIG. 12B(ii) that the deposited Li was separated from the originally bare Li which was flat and smooth (FIG. 12B(iii)), while the deposited Li was in micron-sized dendritic structures (FIG. 12B(iv)). [00121] The separation of the bare Li surface and the dendritic structures was caused by the SEI layer formed on both of them. The formation of this SEI layer consumed Li and the electrolyte. In sharp contrast, the surface of the LiTEA-200 electrode after 24-h stripping remained extremely clean and has no craters and bumps observed. Additionally, Applicant noticed that there were many fractures on the LiTEA coating (FIG. 12C). The fracture gaps between the broken pieces of the LiTEA coating are ~1 pm. The opposite LiTEA-200 electrode after 24-h plating (FIG. 12D) was also nearly clean and smooth with a few of dendritic Li sporadically. These results indicate that Li could be deposited underneath the LiTEA MLD coating. In other words, the LiTEA coating arc Li-ion-conducting but electronically insulating.

[00122] Applicant further examined the surface of the bare Li and the LiTEA-200 electrodes after one 48-h Li-stripping/plating cycle (i.e., a 24-h stripping followed by a 24-h plating). It was observed that the bare Li electrode after a 48-h Li-stripping/plating cycle (FIG. 13A) was covered with a thick porous layer of Li dendrites, which is similar as the morphology shown in FIG. 12B. The opposite bare Li after 48-h Li-plating-stripping (FIG. 13B) has a similar appearance as shown in FIG. 12A, exhibiting numerous craters and highlands. In contrast, the LiTEA-200 electrode after a 48-h Li-stripping/plating cycle (FIG. 13C) was almost clean on the surface and merely decorated with a few of Li dendritic structures as shown in FIG. 12D. The LiTEA coating was fractured with 1-2 pm gaps (FIG. 13C(iv)). Similarly, the LiTEA-200 electrode after 48-h Li- plating/stripping (FIG. 13D) was very clean and covered with small broken pieces of the LiTEA coating, and only a few of Li dendrites could be observed.

[00123] Based on all the aforementioned results, Applicant concluded that bare Li could not realize uniform Li-stripping/plating while the LiTEA MLD coating could realize uniform Li- stripping/plating. More importantly, the LiTEA coating could provide optimal protection over Li electrodes, ascribed to its ionically conductive and electronically insulating nature.

[00124] Furthermore, Li anodes and NMC811 (LiNio.sMno.1Coo.1O2) cathodes were assembled into Li||NMC811 coin cells in the Ar-filled glove box. In the glove box, oxygen and water were controlled less than 0.01 ppm. Celgard 2325 membrane was used as the separator. The electrolyte was 1.2 M LiPFo in ethylene carbonate (EC)/ethylmethyl carbonate (EMC) (3:7 by weight). Each cell contained 20 pl of the electrolyte. All the assembled cells were rested for 20 hours prior to their electrochemical tests at room temperature. Galvanostatic charge-discharge was carried out using a Neware battery test system. The cells were cycled at different C-rates via a constant current (CC) mode in the voltage range 3.0 - 4.3 versus Li/Li⁺ (FIG. 14). Apparently, the LiTEA coating exhibited optimal protection effects and greatly boosted the cyclability of the LiTEA200- Li||NMC811 and LiTEA200-Li||Li₂S20-NMC811 cells, in which Li₂S20-NMC811 is the NMC811 cathode was coated by 20 cycles of Li₂S (i.e., Li₂S20) via atomic layer deposition (ALD).

[00125] Without further elaboration, it is believed that one skilled in the art can, using the description herein, utilize the present disclosure to its fullest extent. The embodiments described herein are to be construed as illustrative and not as constraining the remainder of the disclosure in any way whatsoever. While the embodiments have been shown and described, many variations and modifications thereof can be made by one skilled in the ail without departing from the spirit and teachings of the invention. Accordingly, the scope of protection is not limited by the description set out above, but is only limited by the claims, including all equivalents of the subject matter of the claims. The disclosures of all patents, patent applications and publications cited herein are hereby incorporated herein by reference, to the extent that they provide procedural or other details consistent with and supplementary to those set forth herein

Claims

CLAIMS:

1. A method of fabricating a polymeric composition on a surface, said method comprising: depositing at least one metal source and at least one organic molecule onto the surface, wherein the depositing results in the formation of the polymeric composition, wherein the polymeric composition comprises alternating metal-organic molecule units, and wherein the metal is derived from the metal source.

2. The method of claim 1, wherein the metal source comprises an alkali metal source.

3. The method of claim 2, wherein the alkali metal source is selected from the group consisting of Li, Na, K, or combinations thereof.

4. The method of claim 1, wherein the metal source comprises a lithium source.

5. The method of claim 4, wherein the lithium source is selected from the group consisting of lithium tert-butoxide (LTB, LiO'Bu), lithium hexamethyldisilazide [LiHMDS, Li(N(SiMe3)2)], lithium trimethylsilanolate (LiTMSO, LiOSiMe3), Li(thd) (thd = 2,2,6,6-tetramethyl-3,5- heptanedionate), or combinations thereof.

6. The method of claim 4, wherein the lithium source comprises lithium tert-butoxide (LTB, LiC Bu).

7. The method of claim 1, wherein the metal source comprises a sodium source.

8. The method of claim 7, wherein the sodium source is selected from the group consisting of sodium tert-butoxide (NaO^fBu), sodium trimethylsilanolate (NaTMSO), Li(thd) ((thd = 2, 2,6,6- tetramethyl-3,5-heptanedionate)), or combinations thereof.

9. The method of claim 1, wherein the metal source comprises a potassium source.

10. The method of claim 1, wherein the potassium source is selected from the group consisting of potassium tert-butoxide (KO^£Bu), potassium trimethylsilanolate (KTMSO), K(thd) ((thd =

2.2.6.6-tetramethyl-3,5-heptanedionate)), or combinations thereof.

11. The method of claim 1, wherein the organic molecule comprises a general formula of H-[O- R]n-OH, wherein n is an integer of 1 or more, and wherein R represents the organic molecule.

12. The method of claim 1, wherein the organic molecule is selected from the group consisting of diethanolamine (DEA), triethanolamine (TEA), glycerol (GL), triglycerol (TGL), glycerol propoxylate (GLP), glycerol ethoxylate (GLE), trimethylolpropane ethoxylate (TMPE), polyethylene glycol (PEG), chitosan (CS), hydroquinone (HQ), ethylene glycol (EG), diols, triols, polyols, hydroquinone (HQ), tetrafluorohydroquinone (FHQ), 1 ,4-benzenedicarboxylic acid (BDC), 2,6-naphthalene dicarboxylic acid (NDC) 1,2-ethanediol (EDO), 1,4-butanediol (BDO),

1.6-hexanediole (HDO), fumaric acid (FC), 2,4-hexadiyene-l,6-diol (HDD), 1,2,4- trihydroxybenzene (THB), lactic acid (LC), 2,2-bis(hydroxymethyl)-l,3-propanediole (BHMPD), alpha-thioglycerol (TGL), 1,2,4-butanetriol (BT), 1,2,5,6-hexanetriol (HT), 2-hydroxymethyl-l,3- propanediol (HMPD), l-(4-nitrophenyl)glycerol (NPGL), or combinations thereof.

13. The method of claim 1, wherein the depositing comprises the following sequential steps:

(a) depositing the metal source onto the surface, wherein the depositing results in the coupling of the metal to the surface,

(b) depositing the organic molecule onto the surface, wherein the depositing results in the coupling of the organic molecule to the metal coupled to the surface, and

(c) depositing the metal source onto the surface, wherein the depositing results in the coupling of the metal to the organic molecule coupled to the surface.

14. The method of claim 13, wherein steps (b) and (c) are repeated multiple times.

15. The method of claim 13, wherein steps (b) and (c) are repeated at least 2 times.

16. The method of claim 1, wherein the depositing occurs by a method selected from the group consisting of molecular’ layer deposition (MLD), atomic layer deposition (ALD), or combinations thereof.

17. The method of claim 1, wherein the depositing occurs by molecular’ layer deposition (MLD).

18. The method of claim 1, wherein the formed polymeric composition comprises the following formula:

-//-M-[O-R]_n-O-M-//-, wherein M represents the metals from the metal source, wherein R represents the organic molecule, wherein n is an integer of 1 or more, and wherein -//- represents the alternating metal-organic molecule units.

19. The method of claim 18, wherein R is selected from the group consisting of alkyl groups, alkene groups, alkyne groups, carbonyl groups, carboxylic acid groups, alcohol groups, ether groups, phenol groups, amido groups, amide groups, amine groups, methyl groups, ethyl groups, isopropyl groups, isobutyl groups, glycerol groups, aromatic groups, phenyl groups, benzene groups, quinone groups, or combinations thereof.

20. The method of claim 18, wherein M comprises one or more alkali metals selected from the group consisting of Li, Na, K, or combinations thereof.

21. The method of claim 1, wherein the formed polymeric composition has a mass of more than about 750 ng/cm².

22. The method of claim 1, wherein the formed polymeric composition has a thickness of about 0.5 nm to about 2000 nm.

23. The method of claim 1, wherein the polymeric composition is in the form of a metal alkoxide-based polymer, a homopolymer of a metal alkoxide-based polymer, a heteropolymer of a metal alkoxide-based polymer, or combinations thereof.

24. The method of claim 1, wherein the surface comprises a plurality of hydroxyl groups, wherein the plurality of hydroxyl groups is operational for anchoring the polymeric composition.

25. The method of claim 1, wherein the surface comprises a surface of an electrode.

26. The method of claim 25, wherein the polymeric composition forms a coating on the surface of the electrode.

27. The method of claim 25, wherein the electrode comprises an anode.

28. The method of claim 25, wherein the electrode comprises a cathode.

29. The method of claim 1, further comprising a step of incorporating the polymeric composition as a component of an energy storage device.

30. The method of claim 29, wherein the formed polymeric composition is incorporated as a polymer electrolyte of the energy storage device.

31. The method of claim 29, wherein the formed polymeric composition is incorporated as a component of an electrode of the energy storage device.

32. The method of claim 31, wherein the formed polymeric composition is incorporated as a surface coating of the electrode.

33. The method of claim 31, wherein the electrode comprises an anode.

34. The method of claim 31, wherein the electrode comprises a lithium anode.

35. The method of claim 31, wherein the electrode comprises a sodium anode.

36. The method of claim 31, wherein the electrode comprises a potassium anode.

37. The method of claim 31, wherein the electrode comprises a cathode.

38. An energy storage device, wherein the energy storage device comprises a polymeric composition, wherein the polymeric composition comprises alternating metal-organic molecule units.

39. The energy storage device of claim 38, wherein the energy storage device is a battery.

40. The energy storage device of claim 39, wherein the battery is selected from the group consisting of all solid-state batteries, alkali metal-based batteries, lithium-ion based batteries, lithium batteries, sodium batteries, potassium batteries, or combinations thereof.

41. The energy storage device of claim 38, wherein the polymeric composition is a component of an electrode.

42. The energy storage device of claim 41, wherein the polymeric composition is a surface coating on the electrode.

43. The energy storage device of claim 41, wherein the electrode is an anode.

44. The energy storage device of claim 41, wherein the anode is a lithium anode.

45. The energy storage device of claim 41, wherein the anode is a sodium anode.

46. The energy storage device of claim 41, wherein the anode is a potassium anode.

47. The energy storage device of claim 41, wherein the electrode is a cathode.

48. The energy storage device of claim 38, wherein the polymeric composition is a component of a polymer electrolyte.

49. The energy storage device of claim 48, wherein the electrolyte is a solid-state polymer electrolyte.

50. The energy storage device of claim 38, wherein the metal comprises an alkali metal.

51. The energy storage device of claim 50, wherein the alkali metal is selected from the group consisting of Li, Na, K, or combinations thereof.

52. The energy storage device of claim 38, wherein the organic molecule is selected from the group consisting of diethanolamine (DEA), triethanolamine (TEA), glycerol (GL), triglycerol (TGL), glycerol propoxylate (GLP), glycerol ethoxylate (GLE), trimethylolpropane ethoxylate (TMPE), polyethylene glycol (PEG), chitosan (CS), hydroquinone (HQ), ethylene glycol (EG), diols, triols, polyols, hydroquinone (HQ), tetrafluorohydroquinone (FHQ), 1,4- benzenedicarboxylic acid (BDC), 2,6-naphthalene dicarboxylic acid (NDC) 1 ,2-ethanediol (EDO), 1,4-butanediol (BDO), 1,6-hexanediole (HDO), fumaric acid (FC), 2,4-hexadiyene-l,6- diol (HDD), 1 ,2,4-trihydroxybenzene (THB), lactic acid (LC), 2,2-bis(hydroxymethyl)-l,3- propanediole (BHMPD), alpha- thioglycerol (TGL), 1,2,4-butanetriol (BT), 1,2,5,6-hexanetriol (HT), 2-hydroxymethyl-l,3-propanediol (HMPD), l-(4-nitrophenyl)glycerol (NPGL), or combinations thereof.

53. The energy storage device of claim 38, wherein the organic molecule is selected from the group consisting of alkyl groups, alkene groups, alkyne groups, carbonyl groups, carboxylic acid groups, alcohol groups, ether groups, phenol groups, amido groups, amide groups, amine groups, methyl groups, ethyl groups, isopropyl groups, isobutyl groups, glycerol groups, aromatic groups, phenyl groups, benzene groups, quinone groups, or combinations thereof.

54. The energy storage device of claim 38, wherein the polymeric composition comprises the following formula:

-//-M-[O-R]_n-O-M-//-, wherein M represents the metal, wherein R represents the organic molecule, wherein n is an integer of 1 or more, and wherein -//- represents the alternating metal-organic molecule units.

55. The energy storage device of claim 54, wherein R is selected from the group consisting of alkyl groups, alkene groups, alkyne groups, carbonyl groups, carboxylic acid groups, alcohol groups, ether groups, phenol groups, amido groups, amide groups, amine groups, methyl groups, ethyl groups, isopropyl groups, isobutyl groups, glycerol groups, aromatic groups, phenyl groups, benzene groups, quinone groups, or combinations thereof.

56. The energy storage device of claim 54, wherein M comprises one or more alkali metals selected from the group consisting of Li, Na, K, or combinations thereof.

57. The energy storage device of claim 38, wherein the formed polymeric composition has a mass of more than about 750 ng/cm².

58. The energy storage device of claim 38, wherein the polymeric composition has a thickness of about 0.5 nm to about 2000 nm.

59. The energy storage device of claim 38, wherein the polymeric composition is in the form of a metal alkoxide-based polymer, a homopolymer of a metal alkoxide-based polymer, a heteropolymer of a metal alkoxide-based polymer, or combinations thereof.